# US 10,374,222 B2 · Electrode material for lithium ion secondary batteries, method for producing electrode material for lithium ion secondary batteries, and lithium ion secondary battery

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- Number: US 10,374,222 B2
- Document ID: US10374222B2
- Status: Granted
- Kind: B2
- Application number: 14/425,296
- Filed: 2013-09-02
- Published: 2015-09-17
- Granted: 2019-08-06
- Earliest claimed: 2012-09-03
- Assignees: Nippon Chemi-Con Corporation
- Applicants: Nippon Chemi-Con Corporation
- Inventors: Katsuhiko Naoi; Wako Naoi; Satoshi Kubota; Yoshihiro Minato; Shuichi Ishimoto; Kenji Tamamitsu
- Web page: https://patentgrep.com/patent/US10374222B2

## CPC

- H01M 4/364: {as mixtures}
- C01G 23/005: {Alkali titanates}
- C01G 45/1242: of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
- C01G 51/42: containing alkali metals, e.g. LiCoO2
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/625: {Carbon or graphite}
- C01P 2004/03: obtained by SEM
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2006/10: Solid density
- C01P 2006/40: Electric properties
- H01M 4/043: {involving compressing or compaction}
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/1397: of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/362: {Composites}
- H01M 4/366: {as layered products}
- 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 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/027: {Negative electrodes}
- H01M 2004/028: {Positive electrodes}
- H01M 2220/20: Batteries in motive systems, e.g. vehicle, ship, plane
- H01M 2220/30: Batteries in portable systems, e.g. mobile phone, laptop
- Y02E 60/10: Energy storage using 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

## Abstract

Provided is an electrode material which leads to a lithium ion secondary battery that has high energy density. An electrode material for a lithium ion secondary battery of the present invention is characterized by containing: a coarse particle of a first active material that is able to act as a positive electrode active material or a negative electrode active material of a lithium ion secondary battery; and a particle of a composite composed of conductive carbon and a second active material attached to the conductive carbon that is able to act as an active material of the same electrode as the first active material. This electrode material for a lithium ion secondary battery is also characterized in that: a diameter of the coarse particle of the first active material is larger than a diameter of the particle of the composite; and the particle of the composite is filled in a gap formed between the particles of the first active material. A conductive agent can be additionally contained in the gap.

## Claims

### Claim 1

An electrode material for a lithium ion secondary battery comprising:
particles of a first active material that can function as a positive electrode active material or a negative electrode active material of a lithium ion secondary battery; and
particles of a composite formed of particles of conductive carbon and particles of a second active material attached to the particles of the conductive carbon that can function as an active material of the same electrode as the first active material, wherein:
the particles of the first active material having a diameter which is larger than the particles of the composite and is in the range of 100 nm to 100 μm,
the particles of the conductive carbon in the composite having a diameter in a range of 10 nm to 300 nm, and the particles of the second active material in the composite having a diameter in a range of 1 nm to 200 nm,
at least a part of a structure in the particles of the conductive carbon in the composite being destroyed,
the particles of the composite filled in a gap formed between the particles of the first active material by kneading the particles of the composite and the particles of the first active material to obtain a kneaded material and adding pressure to the kneaded material, and
the mixture ratio of the particles of the composite and the particles of the first active material being within the range of the mass ratio of 5 to 30:95 to 70.

### Claim 2 (depends on 1)

The electrode material for a lithium ion secondary battery according to claim 1, wherein the second active material is a metal oxide.

### Claim 3 (depends on 1)

The electrode material for a lithium ion secondary battery according to claim 1, wherein the electrode material further comprises particles of a conductive agent composed of conductive carbon which is different from the conductive carbon in the particles of the composite, the particles of the conductive agent have a diameter which is smaller than the particles of the first active material and is in the range of 10 nm to 300 nm, and the particles of the conductive agent are filled in the gap formed between the particles of the first active material.

### Claim 4 (depends on 3)

The electrode material for a lithium ion secondary battery according to claim 3, wherein the electrical conductivity of a mixture of the composite and the conductive agent is 10−3 s/cm or more.

### Claim 5 (depends on 2)

The electrode material for a lithium ion secondary battery according to claim 2, wherein the electrode material further comprises particles of a conductive agent composed of conductive carbon which is different from the conductive carbon in the particles of the composite, the particles of the conductive agent have a diameter which is smaller than the particles of the first active material and is in the range of 10 nm to 300 nm, and the particles of the conductive agent are filled in the gap formed between the particles of the first active material.

### Claim 6 (depends on 5)

The electrode material for a lithium ion secondary battery according to claim 5, wherein the electrical conductivity of a mixture of the composite and the conductive agent is 10−3 s/cm or more.

### Claim 7 (depends on 2)

A method for producing an electrode material for a lithium ion secondary battery according to claim 2, wherein the method comprises:
1) a composite manufacturing process to prepare the particles of the composite formed of the particles of the conductive carbon and the particles of the second active material of the metal oxide attached to the particles of the conductive carbon, which comprises:
a) a preparation step to introduce into a rotatable reactor a reaction solution prepared by adding conductive carbon powder to a solution in which at least one compound of a metal that constitutes the metal oxide is dissolved;
b) a supporting step to support the compound of a metal and/or its reaction product by the conductive carbon powder by turning the reactor to add shear stress and centrifugal force of 1500 kgms−2 or more to the reaction solution; and
c) a heat treatment step to transform the compound of a metal and/or its reaction product supported by the conductive carbon powder into the particles of the second active material having a diameter in a range of 1 nm to 200 nm by heat-treating the conductive carbon powder supporting the compound of a metal and/or its reaction product, and during which, the particles of the conductive carbon having a diameter in a range of 10 nm to 300 nm in which at least a part of a structure in the particles is destroyed is formed from the conductive carbon powder,
and
2) a kneading and pressurizing process to knead the particles of the composite obtained by the composite manufacturing process and the particles of the first active material with a diameter which is larger than the particles of the composite and is in the range of 100 nm to 100 μm within the range of the mass ratio of 5 to 30:95 to 70 to obtain a kneaded material and to add pressure to the kneaded material so that the particles of the first active material draw near to each other and the particles of the composite are pushed out to fill the gap formed between the particles of the first active material.

### Claim 8 (depends on 7)

The method for producing an electrode material for a lithium ion secondary battery according to claim 7, wherein particles of a conductive agent composed of conductive carbon which is different from the conductive carbon in the particles of the composite is further comprised in the electrode material, the particles of the conductive agent have a diameter which is smaller than the particles of the first active material and is in a range of 10 nm to 300 nm, and the particles of the composite, the particles of the first active material, and the particles of the conductive agent are kneaded in the kneading and pressurizing process.

### Claim 9 (depends on 1)

A lithium ion secondary battery with a positive electrode and/or a negative electrode having an active material layer that comprises the electrode material according to claim 1.

### Claim 10 (depends on 2)

A lithium ion secondary battery with a positive electrode and/or a negative electrode having an active material layer that comprises the electrode material according to claim 2.

### Claim 11 (depends on 5)

A lithium ion secondary battery with a positive electrode and/or a negative electrode having an active material layer that comprises the electrode material according to claim 5.