# US 10,312,508 B2 · Lithium metal composite oxide powder

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- Number: US 10,312,508 B2
- Document ID: US10312508B2
- Status: Granted
- Kind: B2
- Application number: 15/508,184
- Filed: 2015-09-03
- Published: 2017-10-05
- Granted: 2019-06-04
- Earliest claimed: 2014-09-03
- Assignees: Mitsui Mining & Smelting Co., Ltd.
- Applicants: Mitsui Mining & Smelting Co., Ltd.
- Inventors: Tetsuya Mitsumoto; Daisuke Washida; Toshikazu Matsuyama; Daisuke Inoue; Hideaki Matsushima; Yoshimi Hata; Hitohiko Ide; Shinya Kagei
- Web page: https://patentgrep.com/patent/US10312508B2

## CPC

- H01M 4/366: {as layered products}
- C01G 53/44: containing manganese
- C01G 53/502: containing lithium and cobalt
- C01G 53/504: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
- C01G 53/66: containing alkaline earth metals, e.g. SrNiO3 or SrNiO2
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- 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 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- 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 2002/60: Compounds characterised by their crystallite size
- C01P 2002/77: by unit-cell parameters, atom positions or structure diagrams
- C01P 2004/51: Particles with a specific particle size distribution
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2006/11: Powder tap density
- C01P 2006/12: Surface area
- C01P 2006/40: Electric properties
- C01P 2006/80: Compositional purity
- H01M 2004/028: {Positive electrodes}
- H01M 2220/20: Batteries in motive systems, e.g. vehicle, ship, plane
- 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 positive electrode active material comprising a lithium metal composite oxide having a layered crystal structure provides a novel lithium metal composite oxide powder which can suppress the reaction with an electrolytic solution and raise the charge-discharge cycle ability of a battery, and can improve the output characteristics of a battery. A lithium metal composite oxide powder comprises a particle having a surface portion where one or a combination of two or more (“surface element A”) of the group consisting of Al, Ti and Zr is present, on the surface of a particle comprising a lithium metal composite oxide having a layered crystal structure, wherein the amount of surface LiOH is smaller than 0.10% by weight, and the amount of surface Li2CO3 is smaller than 0.25% by weight; in an X-ray diffraction pattern, the ratio of an integral intensity of the (003) plane of the lithium metal composite oxide to that of the (104) plane thereof is higher than 1.15; and the amount of S obtained by a measurement using ICP is smaller than 0.10% by weight of the lithium metal composite oxide powder (100% by weight).

## Claims

### Claim 1

A lithium metal composite oxide powder, comprising a particle having a surface portion where one or a combination of two or more (referred to as “surface element A”) of the group consisting of Al, Ti and Zr is present, on a surface of a particle comprising a lithium metal composite oxide having a layered crystal structure,
wherein an amount of surface LiOH measured by the following measuring method is smaller than 0.10% by weight of the lithium metal composite oxide powder, and an amount of surface Li2CO3 measured by the following measuring method is smaller than 0.25% by weight of the lithium metal composite oxide powder;
in an X-ray diffraction pattern obtained by X-ray diffraction using CuKα radiation, a ratio of an integral intensity of the (003) plane of the lithium metal composite oxide to that of the (104) plane thereof is higher than 1.15; and
an amount of S obtained by a measurement using an inductively coupled plasma (ICP) atomic emission spectrometer is smaller than 0.10% by weight of the lithium metal composite oxide powder (100% by weight),
wherein the amount of surface LiOH and the amount of surface Li2CO3 are measured by a titration that is carried out according to the following procedure by reference to a Winkler method, wherein 10.0 g of a sample is dispersed in 50 ml of ion-exchanged water, immersed therein for 15 min, and thereafter filtered; and the filtrate is titrated with hydrochloric acid; and at this time, by using phenolphthalein and bromophenol blue as indicators, the amount of the surface LiOH and the amount of the surface Li2CO3 are calculated based on the discoloration of the filtrate and an amount of titration at this time,
the lithium metal composite oxide is a lithium metal composite oxide represented by the general formula: Li1+xM1−xO2, wherein x=0 to 0.07 and M is one or a combination of two or more (referred to as “constituent element M”) of the group consisting of Mn, Co, Ni, transition elements in the third group elements through and including the 11th group elements of the periodic table, and elements in the first period through and including the third period of the periodic table, and
a ratio (CA/CM) of a concentration (at %) referred to as “CA”; in the case where the surface element A contains two or more elements, the total concentration of the surface element A to a concentration (at %) referred to as “CM”; in the case where the constituent element M contains two or more elements, the total concentration of the constituent element M is higher than 0 and lower than 0.8, as measured by X-ray photoelectron spectroscopy (XPS).

### Claim 2 (depends on 1)

The lithium metal composite oxide powder according to claim 1, wherein a tap density (TD) thereof is higher than 2.0 g/cm3.

### Claim 3

A lithium metal composite oxide powder comprising a particle having a surface portion where one or a combination of two or more (referred to as “surface element A”) of the group consisting of Al, Ti and Zr is present, on a surface of a particle comprising a lithium metal composite oxide having a layered crystal structure,
wherein an amount of surface LiOH measured by the following measuring method is smaller than 0.10% by weight of the lithium metal composite oxide powder, and an amount of surface Li2CO3 measured by the following measuring method is smaller than 0.25% by weight of the lithium metal composite oxide powder;
in an X-ray diffraction pattern obtained by X-ray diffraction using CuKα radiation, a ratio of an integral intensity of the (003) plane of the lithium metal composite oxide to that of the (104) plane thereof is higher than 1.15; and
an amount of S obtained by a measurement using an inductively coupled plasma (ICP) atomic emission spectrometer is smaller than 0.10% by weight of the lithium metal composite oxide powder (100% by weight),
wherein the amount of surface LiOH and the amount of surface Li2CO3 are measured by a titration that is carried out according to the following procedure by reference to a Winkler method, wherein 10.0 g of a sample is dispersed in 50 ml of ion-exchanged water, immersed therein for 15 min, and thereafter filtered; and the filtrate is titrated with hydrochloric acid; and at this time, by using phenolphthalein and bromophenol blue as indicators, the amount of the surface LiOH and the amount of the surface Li2CO3 are calculated based on the discoloration of the filtrate and an amount of titration at this time,
the lithium metal composite oxide is a lithium metal composite oxide represented by the general formula: Li1+xM1−xO2, wherein x=0 to 0.07 and M is one or a combination of two or more (referred to as “constituent element M”) of the group consisting of Mn, Co, Ni, transition elements in the third group elements through and including the 11th group elements of the periodic table, and elements in the first period through and including the third period of the periodic table, and
a ratio (CA/CNi,) of a concentration (at %) (referred to as “CA”; in the case where the surface element A contains two or more elements, the total concentration) of the surface element A to a concentration (at %) (referred to as “CNi,”) of a constituent element Ni is higher than 0 and lower than 1.0, as measured by X-ray photoelectron spectroscopy (XPS).

### Claim 4

A lithium metal composite oxide powder comprising a particle having a surface portion where one or a combination of two or more (referred to as “surface element A”) of the group consisting of Al, Ti and Zr is present, on a surface of a particle comprising a lithium metal composite oxide having a layered crystal structure,
wherein an amount of surface LiOH measured by the following measuring method is smaller than 0.10% by weight of the lithium metal composite oxide powder, and an amount of surface Li2CO3 measured by the following measuring method is smaller than 0.25% by weight of the lithium metal composite oxide powder;
in an X-ray diffraction pattern obtained by X-ray diffraction using CuKα radiation, a ratio of an integral intensity of the (003) plane of the lithium metal composite oxide to that of the (104) plane thereof is higher than 1.15; and
an amount of S obtained by a measurement using an inductively coupled plasma (ICP) atomic emission spectrometer is smaller than 0.10% by weight of the lithium metal composite oxide powder (100% by weight),
wherein the amount of surface LiOH and the amount of surface Li2CO3 are measured by a titration that is carried out according to the following procedure by reference to a Winkler method, wherein 10.0 g of a sample is dispersed in 50 ml of ion-exchanged water, immersed therein for 15 min, and thereafter filtered; and the filtrate is titrated with hydrochloric acid; and at this time, by using phenolphthalein and bromophenol blue as indicators, the amount of the surface LiOH and the amount of the surface Li2CO3 are calculated based on the discoloration of the filtrate and an amount of titration at this time,
the lithium metal composite oxide is a lithium metal composite oxide represented by the general formula: Li1+xM1−xO2, wherein x=0 to 0.07 and M is one or a combination of two or more (referred to as “constituent element M”) of the group consisting of Mn, Co, Ni, transition elements in the third group elements through and including the 11th group elements of the periodic table, and elements in the first period through and including the third period of the periodic table, and
a concentration (at %) (referred to as “CM”; in the case where the constituent element M contains two or more elements, the total concentration) of the constituent element M is higher than 0 at % and lower than 50 at %; a concentration (at %) (referred to as “CA”; in the case where the surface element A contains two or more elements, the total concentration) of the surface element A is higher than 0 at % and lower than 10 at %; and a concentration (at %) (referred to as “CNi,”) of a constituent element Ni is higher than 0 at % and lower than 25 at %, as measured by X-ray photoelectron spectroscopy (XPS).

### Claim 5 (depends on 1)

The lithium metal composite oxide powder according to claim 1, wherein a ratio of a crystallite size of the (003) plane of the lithium metal composite oxide to that of the (110) plane thereof is higher than 1.0 and lower than 2.5, as calculated by Scherrer's equation using an X-ray diffraction pattern obtained by X-ray diffraction using CuKα1 radiation.

### Claim 6 (depends on 1)

The lithium metal composite oxide powder according to claim 1, wherein a ratio (referred to as “primary particle area/secondary particle area”) of a primary particle area determined by the following measuring method to a secondary particle area determined by the following measuring method from secondary particles having a size corresponding to D50 (referred to as “D50”) according to a volume-based particle size distribution obtained by a measurement by a laser diffraction scattering-type particle size distribution measuring method is 0.004 to 0.035,
wherein the method of measuring the secondary particle area comprises that
the lithium metal composite oxide powder is observed by an electron microscope; 5 secondary particles having a size corresponding to D50 are randomly selected; in the case where the secondary particles are spherical, lengths of the particles are taken as diameters (μm) and areas are calculated; in the case where the secondary particles are in indeterminate shapes, areas are calculated by spherical approximation; and an average value of the 5 areas are determined as a secondary particle area (μm2); and
wherein the method of measuring the primary particle area comprises that
the lithium metal composite oxide powder is observed by an electron microscope; 5 secondary particles having a size corresponding to D50 are randomly selected; 100 primary particles are randomly selected from the selected 5 secondary particles; an average particle diameter of the primary particles is determined using image analysis software, and is taken as a diameter (μm); and an area is calculated by spherical approximation and is determined as a primary particle area (μm2).

### Claim 7 (depends on 1)

The lithium metal composite oxide powder according to claim 1, wherein an amount of surface lithium is smaller than 0.35% by weight.

### Claim 8 (depends on 3)

The lithium metal composite oxide powder according to claim 3, wherein a ratio of a crystallite size of the (003) plane of the lithium metal composite oxide to that of the (110) plane thereof is higher than 1.0 and lower than 2.5, as calculated by Scherrer's equation using an X-ray diffraction pattern obtained by X-ray diffraction using CuKα1 radiation.

### Claim 9 (depends on 4)

The lithium metal composite oxide powder according to claim 4, wherein a ratio of a crystallite size of the (003) plane of the lithium metal composite oxide to that of the (110) plane thereof is higher than 1.0 and lower than 2.5, as calculated by Scherrer's equation using an X-ray diffraction pattern obtained by X-ray diffraction using CuKα1 radiation.

### Claim 10 (depends on 3)

The lithium metal composite oxide powder according to claim 3, wherein a ratio (referred to as “primary particle area/secondary particle area”) of a primary particle area determined by the following measuring method to a secondary particle area determined by the following measuring method from secondary particles having a size corresponding to D50 (referred to as “D50”) according to a volume-based particle size distribution obtained by a measurement by a laser diffraction scattering-type particle size distribution measuring method is0.004 to 0.035,
wherein the method of measuring the secondary particle area comprises that
the lithium metal composite oxide powder is observed by an electron microscope; 5 secondary particles having a size corresponding to D50 are randomly selected; in the case where the secondary particles are spherical, lengths of the particles are taken as diameters (μm) and areas are calculated; in the case where the secondary particles are in indeterminate shapes, areas are calculated by spherical approximation; and an average value of the 5 areas are determined as a secondary particle area (μm2); and
wherein the method of measuring the primary particle area comprises that
the lithium metal composite oxide powder is observed by an electron microscope; 5 secondary particles having a size corresponding to D50 are randomly selected; 100 primary particles are randomly selected from the selected 5 secondary particles; an average particle diameter of the primary particles is determined using image analysis software, and is taken as a diameter (μm); and an area is calculated by spherical approximation and is determined as a primary particle area (μm2).

### Claim 11 (depends on 4)

The lithium metal composite oxide powder according to claim 4, wherein a ratio (referred to as “primary particle area/secondary particle area”) of a primary particle area determined by the following measuring method to a secondary particle area determined by the following measuring method from secondary particles having a size corresponding to D50 (referred to as “D50”) according to a volume-based particle size distribution obtained by a measurement by a laser diffraction scattering-type particle size distribution measuring method is 0.004 to 0.035,
wherein the method of measuring the secondary particle area comprises that
the lithium metal composite oxide powder is observed by an electron microscope; 5 secondary particles having a size corresponding to D50 are randomly selected; in the case where the secondary particles are spherical, lengths of the particles are taken as diameters (μm) and areas are calculated; in the case where the secondary particles are in indeterminate shapes, areas are calculated by spherical approximation; and an average value of the 5 areas are determined as a secondary particle area (μm2); and
wherein the method of measuring the primary particle area comprises that
the lithium metal composite oxide powder is observed by an electron microscope; 5 secondary particles having a size corresponding to D50 are randomly selected; 100 primary particles are randomly selected from the selected 5 secondary particles; an average particle diameter of the primary particles is determined using image analysis software, and is taken as a diameter (μm); and an area is calculated by spherical approximation and is determined as a primary particle area (μm2).

### Claim 12 (depends on 3)

The lithium metal composite oxide powder according to claim 3, wherein an amount of surface lithium is smaller than 0.35% by weight.

### Claim 13 (depends on 4)

The lithium metal composite oxide powder according to claim 4, wherein an amount of surface lithium is smaller than 0.35% by weight.

### Claim 14 (depends on 3)

The lithium metal composite oxide powder according to claim 3, wherein a tap density (TD) thereof is higher than 2.0 g/cm3.

### Claim 15 (depends on 4)

The lithium metal composite oxide powder according to claim 4, wherein a tap density (TD) thereof is higher than 2.0 g/cm3.