# US 8,541,137 B2 · Nonaqueous electrolyte battery containing a negative electrode of lithium-titanium composite oxide, battery pack and vehicle

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- Number: US 8,541,137 B2
- Document ID: US8541137B2
- Status: Granted
- Kind: B2
- Application number: 13/659,382
- Filed: 2012-10-24
- Published: 2013-02-28
- Granted: 2013-09-24
- Earliest claimed: 2005-05-13
- Assignees: Kabushiki Kaisha Toshiba
- Applicants: Hiroki Inagaki; Norio Takami
- Inventors: Hiroki Inagaki; Norio Takami
- Web page: https://patentgrep.com/patent/US8541137B2

## CPC

- 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)
- C01G 23/00: Compounds of titanium {(preparation of Ti-compounds from ores or scraps C22B34/12)}
- C01G 23/005: {Alkali titanates}
- C01G 45/1228: of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
- C01G 51/50: of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
- C01G 53/502: containing lithium and cobalt
- H01M 4/364: {as mixtures}
- 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
- C01P 2002/32: spinel-type (AB2O4)
- C01P 2002/60: Compounds characterised by their crystallite size
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/74: by peak-intensities or a ratio thereof only
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2006/40: Electric properties
- 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 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/027: {Negative electrodes}
- H01M 2300/004: Three solvents
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

A nonaqueous electrolyte battery, containing a case and provided in the case, a positive electrode containing at least one selected from the group consisting of spinel type lithium-manganese-nickel composite oxide and lithium phosphate oxide having an olivine structure, a negative electrode and a nonaqueous electrolyte. The negative electrode comprises a lithium-titanium composite oxide, wherein a crystallite diameter of the lithium-titanium composite oxide is not larger than 6.9×102 {acute over (Å)}. The lithium-titanium composite oxide comprises: rutile TiO2; anatase TiO2; Li2TiO3; and a lithium titanate having a spinel structure. A main peak intensity relative to lithium titanate set at 100, as determined by X-ray diffractometry, of each of lithium titanate having a spinel structure, the rutile TiO2, the anatase TiO2 and Li2TiO3 is not larger than 7.

## Claims

### Claim 1

A nonaqueous electrolyte battery, comprising:
a case;
a positive electrode provided in the case and comprising at least one selected from the group consisting of spinel type lithium-manganese-nickel composite oxide and lithium phosphate oxide having an olivine structure;
a negative electrode provided in the case and containing a lithium-titanium composite oxide comprising a crystallite diameter not larger than 6.9×102 Å; and
a nonaqueous electrolyte provided in the case;
wherein in a X-ray diffractometry curve of the lithium-titanium composite oxide, none of a main peak intensity of a rutile type TiO2, a main peak intensity of an anatase type TiO2 and a main peak intensity of Li2TiO3 is larger than 7 when a main peak intensity of a lithium titanate having a spinel structure is set at 100.

### Claim 2 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein the crystallite diameter of the lithium-titanium composite oxide is not smaller than 1.5×102 Å.

### Claim 3 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein the crystallite diameter of the lithium-titanium composite oxide is not smaller than 2.6×102 Å.

### Claim 4 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein none of the main peak intensity of the rutile type TiO2, the main peak intensity of the anatase type TiO2 and the main peak intensity of Li2TiO3 is larger than 3.

### Claim 5 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein the lithium-titanium composite oxide comprises an element X which consists of at least one of Na and K, and an amount of the element X is not smaller than 0.10% by weight and not larger than 3.04% by weight.

### Claim 6 (depends on 5)

The nonaqueous electrolyte battery according to claim 5, wherein the element X is positioned in a Li site of lithium titanate.

### Claim 7 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein the nonaqueous electrolyte comprises at least two solvents selected from the group consisting of propylene carbonate, ethylene carbonate and γ-butyrolactone.

### Claim 8 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein the nonaqueous electrolyte comprises γ-butyrolactone.

### Claim 9 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein the nonaqueous electrolyte comprises at least three solvents selected from the group consisting of propylene carbonate, ethylene carbonate, γ-butyrolactone, and vinylene carbonate.

### Claim 10 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein the lithium-titanium composite oxide comprises particles having an average particle diameter not larger than 1 μm.

### Claim 11 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein the positive electrode comprises a spinel type lithium-manganese-nickel composite oxide which is LixMn2-yNiyO4, wherein each of molar ratios x and y is a value from 0 (inclusive) to 1 (inclusive).

### Claim 12 (depends on 1)

The nonaqueous electrolyte battery according to claim 1, wherein the positive electrode comprises a lithium phosphate oxide and the lithium phosphate oxide is at least one oxide selected from the group consisting of LixFePO4, LixFe1-yMnyPO4 and LixCoPO4, wherein each of molar ratios x and y is a value from 0 (inclusive) to 1 (inclusive).

### Claim 13

A battery pack comprising nonaqueous electrolyte batteries,
each of the nonaqueous electrolyte batteries comprising:
a case;
a positive electrode provided in the case and comprising at least one selected from the group consisting of spinel type lithium-manganese-nickel composite oxide and lithium phosphate oxide having an olivine structure;
a negative electrode provided in the case and containing a lithium-titanium composite oxide comprising a crystallite diameter not larger than 6.9×102 Å; and
a nonaqueous electrolyte provided in the case;
wherein in a X-ray diffractometry curve of the lithium-titanium composite oxide, none of a main peak intensity of a rutile type TiO2, a main peak intensity of an anatase type TiO2 and a main peak intensity of Li2TiO3 is larger than 7 when a main peak intensity of a lithium titanate having a spinel structure is set at 100.

### Claim 14 (depends on 13)

The battery pack according to claim 13, further comprising a protective circuit which detects a voltage of each of the nonaqueous electrolyte batteries.

### Claim 15 (depends on 13)

The battery pack according to claim 13, wherein the positive electrode comprises a spinel type lithium-manganese-nickel composite oxide which is LixMn2-yNiyO4, wherein each of molar ratios x and y is a value from 0 (inclusive) to 1 (inclusive).

### Claim 16 (depends on 13)

The battery pack according to claim 13, wherein the positive electrode comprises a lithium phosphate oxide and the lithium phosphate oxide is at least one oxide selected from the group consisting of LixFePO4, LixFe1-yMnyPO4 and LixCoPO4, wherein each of molar ratios x and y is a value from 0 (inclusive) to 1 (inclusive);
at least one oxide selected from the group consisting of LixFePO4, LixFe1-yMnyPO4 and LixCoPO4, as the lithium phosphate oxide, where each of molar ratios x and y falls within a range of 0 to 1.

### Claim 17 (depends on 13)

A vehicle comprising a battery pack defined in claim 13.