JP2012121803A - 炭素被覆スピネル型チタン酸リチウム及びその製造方法 - Google Patents
炭素被覆スピネル型チタン酸リチウム及びその製造方法 Download PDFInfo
- Publication number
- JP2012121803A JP2012121803A JP2012020818A JP2012020818A JP2012121803A JP 2012121803 A JP2012121803 A JP 2012121803A JP 2012020818 A JP2012020818 A JP 2012020818A JP 2012020818 A JP2012020818 A JP 2012020818A JP 2012121803 A JP2012121803 A JP 2012121803A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- lithium
- titanium oxide
- present
- lithium titanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/6268—Thermal treatment of powders or mixtures thereof other than sintering characterised by the applied pressure or type of atmosphere, e.g. in vacuum, hydrogen or a specific oxygen pressure
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62828—Non-oxide ceramics
- C04B35/62839—Carbon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/636—Polysaccharides or derivatives thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/443—Nitrates or nitrites
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5409—Particle size related information expressed by specific surface values
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/549—Particle size related information the particle size being expressed by crystallite size or primary particle size
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
【解決手段】リチウム塩、酸化チタン、及び炭素含有化合物を溶媒中で混合するステップ(a)と、ステップ(a)で得られた混合物を乾燥するステップ(b)と、乾燥した混合物を焼成するステップとを含むことにより、容量特性が改良される。
【選択図】図1
Description
LiOH・H2O及びアナターゼ型TiO2を出発材料とした。市販のLiOH・H2O(メルク社製)の場合、含水量はバッチ毎に異なるため、合成前に測定した。まず、LiOH・H2Oを水に溶解し、次いでアナターゼ型TiO2及びラクトースを攪拌しながら添加して、LiOH/TiO2/ラクトースの縣濁液を30〜35℃で調製した。
本発明のチタン酸リチウム(Li4Ti5O12)の製造
9.2kgのLiOH・H2Oを水45Lに溶解し、次いで20.8kgのTiO2を添加した。ラクトースを様々な量で添加した。ラクトース量を更に変化させた。すなわち、30gラクトース/kg(LiOH+TiO2)のバッチ、60gラクトース/kg(LiOH+TiO2)のバッチ、及び90gラクトース/kg(LiOH+TiO2)のバッチを使用して、本発明のチタン酸リチウム中の炭素量を変化させた。
実施例1の製造方法により、ラクトース未添加で炭素未被覆のチタン酸リチウムを製造した。
Claims (14)
- (a)リチウム塩、酸化チタン、及び炭素含有化合物を溶媒中で混合するステップと、
(b)前記ステップ(a)で得られた混合物を乾燥するステップと、
(c)乾燥した前記混合物を焼成するステップとを含む、
炭素含有リチウムチタン酸化物の製造方法。 - 前記乾燥は噴霧乾燥により行われる、請求項1に記載の方法。
- 前記溶媒は水である、請求項1又は2に記載の方法。
- ステップ(a)において、前記リチウム塩及び前記酸化チタンは、得られるリチウムチタン酸化物における原子比Li/Tiが4:5となるように混合される、請求項1〜3のいずれか一項に記載の方法。
- 前記リチウム塩は、LiOH、Li2O、LiNO3、LiHCO3、及び、LiCH3COOからなる群から選ばれる、請求項1〜4のいずれか一項に記載の方法。
- 前記酸化チタンはアナターゼ型又は非晶質である、請求項1〜5のいずれか一項に記載の方法。
- 前記炭素含有化合物は、炭化水素及びその誘導体、炭水化物及びその誘導体、及び、ポリマーからなる群から選ばれる、請求項1〜6のいずれか一項に記載の方法。
- 前記炭素含有化合物は、ラクトース、スクロース、及び、サッカロースからなる群の糖類から選ばれる、請求項7に記載の方法。
- 前記噴霧乾燥は90〜350℃の温度勾配で行われる、請求項2に記載の方法。
- 前記焼成は保護雰囲気下で700〜1000℃で行われる、請求項1〜9のいずれか一項に記載の方法。
- 請求項1〜10のいずれか一項に記載の方法により得られるリチウムチタン酸化物。
- 請求項11に記載のリチウムチタン酸化物を含む電極。
- 請求項12に記載の電極を含むリチウムイオン二次電池。
- C/10における充電/放電容量は165mAh/g超である、請求項13に記載のリチウムイオン二次電池。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008050692.3 | 2008-10-07 | ||
DE102008050692.3A DE102008050692B4 (de) | 2008-10-07 | 2008-10-07 | Kohlenstoffbeschichteter Lithiumtitan-Spinell |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011530412A Division JP5671467B2 (ja) | 2008-10-07 | 2009-10-07 | 炭素被覆スピネル型チタン酸リチウム |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2012121803A true JP2012121803A (ja) | 2012-06-28 |
JP2012121803A5 JP2012121803A5 (ja) | 2013-02-14 |
JP5657582B2 JP5657582B2 (ja) | 2015-01-21 |
Family
ID=41665177
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011530412A Active JP5671467B2 (ja) | 2008-10-07 | 2009-10-07 | 炭素被覆スピネル型チタン酸リチウム |
JP2012020818A Expired - Fee Related JP5657582B2 (ja) | 2008-10-07 | 2012-02-02 | 炭素被覆スピネル型チタン酸リチウム及びその製造方法 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011530412A Active JP5671467B2 (ja) | 2008-10-07 | 2009-10-07 | 炭素被覆スピネル型チタン酸リチウム |
Country Status (9)
Country | Link |
---|---|
US (2) | US20110217593A1 (ja) |
EP (1) | EP2349931B1 (ja) |
JP (2) | JP5671467B2 (ja) |
KR (1) | KR101358000B1 (ja) |
CN (1) | CN102186775B (ja) |
CA (1) | CA2738853A1 (ja) |
DE (1) | DE102008050692B4 (ja) |
TW (1) | TWI461366B (ja) |
WO (1) | WO2010040516A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016098608A1 (ja) * | 2014-12-16 | 2016-06-23 | 大塚化学株式会社 | チタン酸リチウム粒子と炭素質物質の複合体の製造方法及びチタン酸リチウム粒子と炭素質物質の複合体 |
JP2016526008A (ja) * | 2013-06-05 | 2016-09-01 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | リチウムチタンスピネルの調製方法及びその使用 |
KR20160113811A (ko) * | 2015-03-23 | 2016-10-04 | 한국과학기술연구원 | 탄소, 질소 코팅된 리튬티타늄산화물 입자의 제조방법, 전극 활물질 및 리튬이차전지 |
JPWO2019009432A1 (ja) * | 2017-07-07 | 2020-04-09 | 株式会社村田製作所 | 二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010006082A1 (de) | 2010-01-28 | 2011-08-18 | Süd-Chemie AG, 80333 | Leitmittelzusatzfreie Elektrode für eine Sekundärlithiumionenbatterie |
DE102010018041A1 (de) * | 2010-04-23 | 2011-10-27 | Süd-Chemie AG | Kohlenstoffhaltiges Verbundmaterial enthaltend eine sauerstoffhaltige Lithium-Übergangsmetallverbindung |
EP2586086B1 (en) | 2010-06-25 | 2017-03-08 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | An electrode material for a lithium-ion battery and a method of manufacturing the same |
CN101944590B (zh) * | 2010-08-19 | 2013-03-27 | 东莞新能源科技有限公司 | 碳包覆钛酸锂的制备方法 |
DE102011016836A1 (de) | 2011-04-12 | 2012-10-18 | Süd-Chemie AG | Verfahren zur Herstellung von Lithiumtitan-Spinell |
KR101400557B1 (ko) * | 2011-06-28 | 2014-05-27 | 공주대학교 산학협력단 | 리튬이온이차전지용 비정질 탄소 복합화 음극재의 제조방법 및 이를 통해 제조된 비정질 탄소 복합화 음극재 |
WO2013002483A2 (ko) * | 2011-06-28 | 2013-01-03 | 공주대학교 산학협력단 | 리튬이온이차전지용 비정질 탄소 복합화 음극재의 제조방법 및 이를 통해 제조된 비정질 탄소 복합화 음극재 |
JP5916007B2 (ja) * | 2011-09-28 | 2016-05-11 | 日本ケミコン株式会社 | チタン酸リチウムとカーボンナノファイバーとの複合体の製造方法 |
CN103066265B (zh) * | 2011-10-24 | 2015-03-04 | 中国科学院物理研究所 | 钠离子电池负极活性物质及其制备方法和应用 |
EP2595224A1 (en) | 2011-11-18 | 2013-05-22 | Süd-Chemie IP GmbH & Co. KG | Doped lithium titanium spinel compound and electrode comprising the same |
FR2983190B1 (fr) * | 2011-11-28 | 2014-04-11 | Renault Sa | Obtention d'un materiau a base de li4ti5o12 avec broyage en presence de carbone |
US9048496B2 (en) * | 2012-03-07 | 2015-06-02 | A123 Systems Llc | Surface treatment of electrochemically active materials for rechargeable cells |
KR101282593B1 (ko) * | 2012-05-08 | 2013-07-12 | 한국과학기술연구원 | 리튬 티타늄 산화물계 음극활물질 나노입자의 카본코팅방법 및 이에 의해 제조된 카본코팅된 리튬 티타늄 산화물계 음극활물질 나노입자 |
GB2510413A (en) * | 2013-02-04 | 2014-08-06 | Leclanch Sa | Electrolyte composition for electrochemical cells |
KR101479626B1 (ko) * | 2013-05-03 | 2015-01-06 | 삼화콘덴서공업주식회사 | Lto/탄소 복합체, lto/탄소 복합체 제조방법, lto/탄소 복합체를 이용한 이용한 음극활물질 및 음극활물질을 이용한 하이브리드 슈퍼커패시터 |
KR101486649B1 (ko) * | 2013-05-24 | 2015-01-29 | 세종대학교산학협력단 | 나트륨 이차전지용 음극 재료 및 이를 포함하는 나트륨 이차전지 |
WO2014200076A1 (ja) * | 2013-06-14 | 2014-12-18 | 株式会社クラレ | 不定比チタン化合物・炭素複合体及びその製造方法、並びに負極活物質及びリチウムイオン二次電池 |
WO2016088193A1 (ja) | 2014-12-02 | 2016-06-09 | 株式会社 東芝 | 負極活物質、非水電解質電池及び電池パック |
EP3034565A1 (de) * | 2014-12-16 | 2016-06-22 | Technische Hochschule Nuernberg Georg-Simon-Ohm | Titanhaltige, elektrisch leitfähige nanostrukturen |
CN105845922B (zh) | 2015-01-30 | 2018-11-09 | 株式会社东芝 | 活性物质、非水电解质电池、电池包及电池组 |
WO2016121947A1 (ja) | 2015-01-30 | 2016-08-04 | 株式会社 東芝 | 組電池及び電池パック |
CN104577074B (zh) * | 2015-02-03 | 2017-01-25 | 北京师范大学 | 一种钛酸锂/碳复合材料的制备方法 |
JP6067902B2 (ja) | 2015-03-13 | 2017-01-25 | 株式会社東芝 | 活物質、非水電解質電池、電池パック、組電池、及び自動車 |
KR101906511B1 (ko) * | 2016-12-27 | 2018-12-06 | 한국철도기술연구원 | 탄소 코팅 음극 활물질 제조방법 |
JP6751042B2 (ja) | 2017-03-24 | 2020-09-02 | 株式会社東芝 | 活物質、電極、二次電池、電池パック、及び車両 |
CN109244415A (zh) * | 2018-09-29 | 2019-01-18 | 北京泰丰先行新能源科技有限公司 | 一种球形碳包覆钛酸盐复合负极材料的制备方法 |
CN110627135B (zh) * | 2019-09-27 | 2022-03-18 | 天津巴莫科技有限责任公司 | 一种化学气相沉积包覆碳的方法及制备的包覆高电压三元材料 |
CN112736233B (zh) * | 2021-01-14 | 2023-01-24 | 武汉船用电力推进装置研究所(中国船舶重工集团公司第七一二研究所) | 一种锂离子电池电极活性物质、制备方法及其电极和电池 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005504693A (ja) * | 2000-12-05 | 2005-02-17 | ハイドロ−ケベック | Li4Ti5O12,Li(4−α)ZαTi5O12,又はLi4ZβTi(5−β)O12を主成分とする粒子群,それらの粒子群の獲得方法、及び、電気化学装置に於けるそれらの粒子群の利用方法 |
JP2005276597A (ja) * | 2004-03-24 | 2005-10-06 | Mitsubishi Chemicals Corp | リチウム二次電池正極活物質用リチウム遷移金属複合酸化物粉体、リチウム二次電池正極及びリチウム二次電池 |
JP2010086955A (ja) * | 2008-09-04 | 2010-04-15 | Toyo Ink Mfg Co Ltd | 電池電極用複合材料 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3502118B2 (ja) | 1993-03-17 | 2004-03-02 | 松下電器産業株式会社 | リチウム二次電池およびその負極の製造法 |
CA2270771A1 (fr) | 1999-04-30 | 2000-10-30 | Hydro-Quebec | Nouveaux materiaux d'electrode presentant une conductivite de surface elevee |
JP4768901B2 (ja) | 1999-06-03 | 2011-09-07 | チタン工業株式会社 | リチウムチタン複合酸化物及びその製造方法、並びにその用途 |
US7211350B2 (en) * | 2001-01-29 | 2007-05-01 | Rutgers University Foundation | Nanostructure lithium titanate electrode for high cycle rate rechargeable electrochemical cell |
DE10319464A1 (de) | 2003-04-29 | 2004-11-18 | Basf Ag | Verfahren zur Herstellung von nanokristallinen Lithiumtitanat-Spinellen |
FR2865576B1 (fr) * | 2004-01-28 | 2006-04-28 | Commissariat Energie Atomique | Procede de preparation de materiaux composites comprenant un compose actif d'electrode et un compose conducteur electronique tel que le carbone notamment pour accumulateurs au lithium |
KR100766896B1 (ko) | 2005-11-29 | 2007-10-15 | 삼성에스디아이 주식회사 | 연료 전지용 고분자 전해질 막 및 이를 포함하는 연료 전지시스템 |
US7968231B2 (en) * | 2005-12-23 | 2011-06-28 | U Chicago Argonne, Llc | Electrode materials and lithium battery systems |
CA2569991A1 (en) * | 2006-12-07 | 2008-06-07 | Michel Gauthier | C-treated nanoparticles and agglomerate and composite thereof as transition metal polyanion cathode materials and process for making |
CN100491602C (zh) * | 2006-12-12 | 2009-05-27 | 成都理工大学 | 钛酸锂晶须的制备方法 |
CN100530780C (zh) * | 2006-12-29 | 2009-08-19 | 深圳市贝特瑞电子材料有限公司 | 复合钛酸锂电极材料及其制备方法 |
-
2008
- 2008-10-07 DE DE102008050692.3A patent/DE102008050692B4/de not_active Expired - Fee Related
-
2009
- 2009-09-28 TW TW098132663A patent/TWI461366B/zh not_active IP Right Cessation
- 2009-10-07 US US13/123,089 patent/US20110217593A1/en not_active Abandoned
- 2009-10-07 CN CN200980139531.6A patent/CN102186775B/zh not_active Expired - Fee Related
- 2009-10-07 WO PCT/EP2009/007196 patent/WO2010040516A1/de active Application Filing
- 2009-10-07 CA CA2738853A patent/CA2738853A1/en not_active Abandoned
- 2009-10-07 KR KR1020117009922A patent/KR101358000B1/ko active IP Right Grant
- 2009-10-07 EP EP09737344.3A patent/EP2349931B1/de not_active Not-in-force
- 2009-10-07 JP JP2011530412A patent/JP5671467B2/ja active Active
-
2012
- 2012-02-02 JP JP2012020818A patent/JP5657582B2/ja not_active Expired - Fee Related
-
2014
- 2014-02-28 US US14/193,923 patent/US9085491B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005504693A (ja) * | 2000-12-05 | 2005-02-17 | ハイドロ−ケベック | Li4Ti5O12,Li(4−α)ZαTi5O12,又はLi4ZβTi(5−β)O12を主成分とする粒子群,それらの粒子群の獲得方法、及び、電気化学装置に於けるそれらの粒子群の利用方法 |
JP2005276597A (ja) * | 2004-03-24 | 2005-10-06 | Mitsubishi Chemicals Corp | リチウム二次電池正極活物質用リチウム遷移金属複合酸化物粉体、リチウム二次電池正極及びリチウム二次電池 |
JP2010086955A (ja) * | 2008-09-04 | 2010-04-15 | Toyo Ink Mfg Co Ltd | 電池電極用複合材料 |
Non-Patent Citations (2)
Title |
---|
JPN6014017217; G.J.Wang et al.: 'Preparation and characteristic of carbon-coated Li4Ti5O12 anode material' Journal of Power Sources Vol.174, No.2, 20070626, p.1109-1112, Elsevier B.V. * |
JPN6014017219; 鈴木典雄他: 'Li4Ti5O12の導電性材料による被覆効果とその電気化学的特性' 第10回化学電池材料研究会ミーティング講演要旨集 , 20080609, p.3-4 * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016526008A (ja) * | 2013-06-05 | 2016-09-01 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | リチウムチタンスピネルの調製方法及びその使用 |
US10170758B2 (en) | 2013-06-05 | 2019-01-01 | Johnson Matthey Public Limited Company | Process for the preparation of lithium titanium spinel and its use |
US10749173B2 (en) | 2013-06-05 | 2020-08-18 | Johnson Matthey Public Limited Company | Process for the preparation of lithium titanium spinel and its use |
WO2016098608A1 (ja) * | 2014-12-16 | 2016-06-23 | 大塚化学株式会社 | チタン酸リチウム粒子と炭素質物質の複合体の製造方法及びチタン酸リチウム粒子と炭素質物質の複合体 |
KR20170097648A (ko) * | 2014-12-16 | 2017-08-28 | 오츠카 가가쿠 가부시키가이샤 | 티타늄산리튬 입자와 탄소질 물질의 복합체의 제조 방법 및 티타늄산리튬 입자와 탄소질 물질의 복합체 |
JPWO2016098608A1 (ja) * | 2014-12-16 | 2017-09-28 | 大塚化学株式会社 | チタン酸リチウム粒子と炭素質物質の複合体の製造方法及びチタン酸リチウム粒子と炭素質物質の複合体 |
KR102003140B1 (ko) * | 2014-12-16 | 2019-07-23 | 오츠카 가가쿠 가부시키가이샤 | 티타늄산리튬 입자와 탄소질 물질의 복합체의 제조 방법 및 티타늄산리튬 입자와 탄소질 물질의 복합체 |
US10665360B2 (en) | 2014-12-16 | 2020-05-26 | Otsuka Chemical Co., Ltd. | Method for producing composite body of lithium titanate particles and carbonaceous material, and composite body of lithium titanate particles and carbonaceous material |
KR20160113811A (ko) * | 2015-03-23 | 2016-10-04 | 한국과학기술연구원 | 탄소, 질소 코팅된 리튬티타늄산화물 입자의 제조방법, 전극 활물질 및 리튬이차전지 |
KR101693711B1 (ko) | 2015-03-23 | 2017-01-06 | 한국과학기술연구원 | 탄소, 질소 코팅된 리튬티타늄산화물 입자의 제조방법, 전극 활물질 및 리튬이차전지 |
JPWO2019009432A1 (ja) * | 2017-07-07 | 2020-04-09 | 株式会社村田製作所 | 二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 |
Also Published As
Publication number | Publication date |
---|---|
JP5671467B2 (ja) | 2015-02-18 |
KR101358000B1 (ko) | 2014-02-04 |
DE102008050692B4 (de) | 2014-04-03 |
JP5657582B2 (ja) | 2015-01-21 |
TWI461366B (zh) | 2014-11-21 |
US20110217593A1 (en) | 2011-09-08 |
TW201024222A (en) | 2010-07-01 |
WO2010040516A1 (de) | 2010-04-15 |
US9085491B2 (en) | 2015-07-21 |
US20140175687A1 (en) | 2014-06-26 |
CA2738853A1 (en) | 2010-04-15 |
CN102186775A (zh) | 2011-09-14 |
JP2012505137A (ja) | 2012-03-01 |
CN102186775B (zh) | 2015-11-25 |
EP2349931B1 (de) | 2018-12-05 |
KR20110069128A (ko) | 2011-06-22 |
DE102008050692A1 (de) | 2010-04-08 |
EP2349931A1 (de) | 2011-08-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5657582B2 (ja) | 炭素被覆スピネル型チタン酸リチウム及びその製造方法 | |
EP2911223B1 (en) | Titanium-niobium composite oxide-based electrode active material and lithium secondary battery using the same | |
JP5450159B2 (ja) | 電極用酸化チタン系化合物及びそれを用いたリチウム二次電池 | |
KR101361589B1 (ko) | 리튬 티타늄 스피넬의 제조 방법 및 그의 용도 | |
CA2761239C (en) | Composite material containing a mixed lithium-metal oxide | |
JP6030708B1 (ja) | チタンニオブ酸化物負極活物質の製造方法 | |
JP6517787B2 (ja) | リチウムチタンスピネルの調製方法及びその使用 | |
JP6200529B2 (ja) | 二次電池用負極活物質の製造方法 | |
JP2017152217A (ja) | 二次電池用負極活物質の製造方法 | |
JP6434555B2 (ja) | リチウムイオン二次電池用負極活物質複合体及びその製造方法 | |
EP3799159B1 (en) | Positive electrode material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery | |
JP2006012616A (ja) | リチウム二次電池用正極材およびその製造方法 | |
JP6126191B1 (ja) | 二次電池用酸化物系負極活物資及びその製造方法 | |
KR20220064316A (ko) | 나노구조화된 리튬 티타네이트 또는 리튬 알루미네이트 내에 캡슐화된 전이 금속 산화물 입자, 및 리튬 이온 배터리에서의 그의 용도 | |
EP3279146A1 (en) | Lithium-containing transition metal oxide and lithium ion secondary cell using same | |
JP6270771B2 (ja) | ポリアニオン系化合物の合成方法 | |
JP2021057107A (ja) | リチウムイオン二次電池用正極材料、リチウムイオン二次電池用正極、及びリチウムイオン二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20120830 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121005 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121005 |
|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20121005 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121116 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20130326 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140430 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20140725 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20140730 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20140819 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20140822 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140926 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141104 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141126 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5657582 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |