WO2011044989A1 - Verfahren zur herstellung von feinteiligen lithiumtitan-spinellen und deren verwendung - Google Patents
Verfahren zur herstellung von feinteiligen lithiumtitan-spinellen und deren verwendung Download PDFInfo
- Publication number
- WO2011044989A1 WO2011044989A1 PCT/EP2010/005915 EP2010005915W WO2011044989A1 WO 2011044989 A1 WO2011044989 A1 WO 2011044989A1 EP 2010005915 W EP2010005915 W EP 2010005915W WO 2011044989 A1 WO2011044989 A1 WO 2011044989A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- container
- mixing
- mixture
- lithium titanium
- lithium
- Prior art date
Links
Classifications
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/60—Mixing solids with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F29/00—Mixers with rotating receptacles
- B01F29/60—Mixers with rotating receptacles rotating about a horizontal or inclined axis, e.g. drum mixers
- B01F29/63—Mixers with rotating receptacles rotating about a horizontal or inclined axis, e.g. drum mixers with fixed bars, i.e. stationary, or fixed on the receptacle
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
-
- 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
Definitions
- the present invention relates to a method for
- Lithium titanium spinel Li 4 Ti 5 0i 2 enjoys increasing
- the lithium titanium spinel be as finely divided as possible, i. has a small particle size. Such finely divided
- Lithium titanium spinel is preferred in battery manufacturing because the fine granularity has good electrochemical properties such as high capacity and fast charge / discharge capability
- Li 4 Ti 5 0i 2 consists in a solid state reaction between a titanium compound, typically Ti0 2 , and a
- Lithium compound typically L1 2 CO 3 , at high
- step is costly and often leads to contamination due to abrasion.
- Organotitanium compounds such as titanium isopropoxide or titanium tetrabutoxide go out, which contain the titanium already in a more reactive, since finely divided form.
- Such a method is disclosed for example in DE 103 19 464 AI.
- the starting compounds of that process are far more expensive than TiO 2 .
- the use of organic solvents can be a problem as well the organic wastes produced in the process (for example, butanol or isopropanol).
- the titanium content of these starting compounds is lower than that of TiO 2 , so that production of lithium titanium spinel by means of the process described is usually uneconomical.
- a mixture containing a lithium compound and Ti0 2 is obtained by the following method:
- lithium titanate is understood to mean according to the invention all lithium titanium spinels of the type Li 1 + x Ti 2 -x0 4 with 0 ⁇ x ⁇ 1/3 of the space group Fd 3m and generally also all mixed lithium titanium oxides of the generic formula Li x Ti y O ( 0 ⁇ y, y ⁇ 1).
- Lithium compound such as Li 2 0, LiOH, lithium acetate, oxalate, nitrate, sulfate, or carbonate can be used.
- Lithium carbonate is the least expensive lithium compound and therefore most preferred. In contrast, in the context of the present invention, it is precisely desired to avoid aggregation of such microparticles. Rather, a finely divided starting material for the production of lithium titanium spinel should be obtained according to the invention. It is therefore surprising that the method known from WO 01/44113 in modified form
- the starting materials ie the lithium compound and Ti0 2 pressed by the centrifugal forces occurring against the inner wall of the container and thus get into through the elongated member and the
- an “elongated element” is mentioned, this is understood to mean any element whose dimension in one dimension, here called “longitudinal direction”, more than twice its dimension in a further dimension, here “thickness direction” In this case, it may be both a rod-shaped element and a leaf or lamellar element.
- the TiO 2 is preferably used in its anatase modification.
- the rotation of the container takes place at a rotational frequency between about 20 Hz and about 60 Hz.
- the power which is supplied to the container and its contents by the drive for rotation comparatively low.
- the internal energy and accordingly the temperature of the mixture can be kept relatively small so that little or no mechanical fusion or caking of particles takes place. As a result, the fineness of the
- the duration of the mixing step can be selected according to the requirement of the material. It has proved to be advantageous if the mixing step takes place over a period of between 5 minutes and 60 minutes. It is in this
- a period of time has been found between 5 and 15 minutes for the mixing process. It should be noted, however, that the rotation speed of the container used must also be taken into account in the time period selected for the mixing process. Thus, lower rotational frequencies of rotation generally require a longer mixing time.
- the temperature of the container and / or the temperature of the elongate element is kept at 50 ° C or less.
- Heat energy can be limited or completely prevented. This embodiment is particularly advantageous when longer mixing times are selected.
- Cooling jacket is flowed through by a cooling fluid.
- the elongated member may be provided with a jacket within which the cooling fluid, in particular a cooling liquid is circulated.
- the cooling may also be accomplished by passing coolant through an internal cavity of the elongated member.
- the heat generated in the mixing process can be particularly good
- thermosensors can be used to monitor the temperature of the container and / or the elongate member, and the outputs of the thermal sensors can be fed to a controller in a known manner to automatically control the temperature of the container and / or the elongated element to the desired preset value.
- the first end of the elongate element, which is directed against the inner wall of the container, is preferably at a fixed distance d of a few mm from this wall
- this distance d is between 2 and 5 mm, the range between 2 and 3 mm being especially
- Lithium compound such as Li 2 C0 3 and Ti0 2 can also be in the container for the mixing process, a carbonaceous compound such as carbon black, eg Ketjen Black, acetylene black, etc. or a Kohlenstoffprecursors such as lactose, a polymer, starch, etc., which during sintering Carbon decomposes, be added.
- a carbonaceous compound such as carbon black, eg Ketjen Black, acetylene black, etc. or a Kohlenstoffprecursors such as lactose, a polymer, starch, etc., which during sintering Carbon decomposes, be added.
- the carbon black or the carbonaceous compound causes in the subsequent further processing of the mixture according to the invention to lithium titanium spinel a
- the compound is preferably between 15% by weight and 20% by weight, preferably between 5 and 10% by weight, very particularly preferably between 5 and 7% by weight, of the total mixture.
- the invention also relates to a mixture containing a lithium compound, in particular L1 2 CO 3 , and Ti0 2 , which is prepared by the above method, wherein the
- Primary particle size dg 0 of the mixture is less than or equal to 1 ⁇ . If doped lithium titanium spinel using the
- Metal compound preferably an oxide or a carbonate, acetate or oxalate added.
- the metal of the metal compound is selected from Sc, Y, Al, Mg, Ga, B, Fe, Cr, Mn, V, preferably Al, Mg, Ga and Sc, most preferably Al.
- the doping metal cations which can either sit on lattice sites of titanium or lithium, are preferably present in an amount of from 0.05 to 3% by weight, preferably from 1 to 3% by weight, based on total spinel.
- Method produced mixture can be used as, for example
- Impurities for example, by abrasions in a ball mill, prevented or reduced.
- the invention also relates to a process for the preparation of finely divided lithium titanium spinel starting from
- the method comprising sintering the mixture.
- Sintering is one
- Sintering at a temperature between 800 ° C and 850 ° C takes place.
- Particularly preferred is a
- Lithium titanium spinels typically have a diameter of 390-500 nm. That is, according to the method, lithium titanium spinel of extremely small particle size can be produced, resulting in the
- Lithium titanate material contains, is particularly high.
- such an anode has a high cycle stability.
- the time period preferably used for the sintering process in the process according to the invention is between 12 and 18
- phase-pure lithium titanium spinel can be obtained.
- pure phase or "phase-pure lithium titanium spinel” means according to the invention that no rutile phase can be detected in the end product by means of XRD measurements within the usual measurement accuracy.
- the lithium titanium spinel of the present invention is rutile free in this preferred embodiment.
- Final product can be obtained. It may, however, be necessary to comminute the agglomerates of the primary particles which may be present by means of short grinding operations, as described e.g. with a
- Ball mill can be performed. As a result, it is possible to dispense with a process step which is necessary according to the prior art for the production of finely divided lithium titanium spinel, which entails a time and cost saving. Of course, the resulting product may be further finely ground, if necessary for a specific application. The milling process is carried out using methods known per se to those skilled in the art.
- the doped or non-doped lithium titanium spinel produced according to the invention is preferably used as the anode material in rechargeable lithium-ion batteries.
- the present invention relates to a
- a rechargeable lithium-ion battery comprising an anode and a cathode and an electrolyte, wherein the anode
- prepared lithium titanium spinel Li 4 Ti 5 0i 2 contains.
- the anode according to the invention has a specific
- FIG. 1 shows a device which can be used in carrying out a method according to the invention
- Figs. 5a-5c are graphs showing the cycle life of an Li 4 Ti 5 O 2 produced by a process according to the invention as an anode material and one according to a process of the prior art the art produced Li 4 Ti 5 0i 2 as an anode material;
- FIG. 1 shows a schematic cross-sectional view through a device as it can be used when carrying out a method according to the invention.
- the device comprises a container 1 with an inner wall la.
- the container is designed essentially rotationally symmetrical.
- an elongate element 2 here a rod-shaped element, with a first end la, which is directed against the inner wall la of the container 1, and a second end 2b.
- the elongated element 2 can be fixed, for example on a fixed axis 3. In this way, the elongated element 2 remains stationary during rotation of the container about its axis 3.
- the first end 2a of the elongate element 2 directed against the container wall 1a may be provided with a shoe 2c having a convex, for example a hemispherical,
- the shoe 2c or the first end 2a defines, together with the nearest part of the housing inner wall la, a gap of thickness d, within which the starting materials are subjected to different forces during the rotation of the container 1, in particular shearing and frictional forces.
- cooling device (not shown) to the outer wall of the container 1 and / or the elongated
- Container inner wall was 3 mm. About 440 g of the above-described composition of the starting materials were treated for 1 h at a power consumption of 1 kW without cooling.
- Treatment duration at speeds up to 50 Hz below 75 ° C. Now the speed was varied between 10 and 50 Hz and the treatment time between 5 min and 15 min.
- FIGs 3a and 3b are SEM photographs are shown according to the invention produced mixtures of Li 2 C0 3 and Ti0 2, which were treated at a rotational frequency of 30 Hz respectively over 10 min.
- the mixture of Figure 3a was placed in a preheated apparatus which had already been heated and the mixture of Figure 3b in a cold apparatus.
- the product temperature at the end of the treatment was 63 ° C in the case of Figure 3a and 35 ° C in the case of Figure 3b.
- the sample of Figure 3b makes a more homogenous impression, but both samples have a much greater homogeneity than the prior art comparative sample treated in a Lödige mixer.
- Results were obtained with a treatment with a rotation frequency of 30 Hz to 40 Hz and a duration of 10 min.
- FIGS. 4a to 4d show SEM images of samples
- Figures 4a and 4b show a sample at different magnification, which was placed in a cold output container
- Figures 4c and 4d a sample which was placed in a 63 ° C warm container.
- a primary particle size of less than 1 ⁇ m was obtained, which shows an open-pore secondary structure.
- the product of Figures 4c and 4d shows a slightly greater sintering.
- FIG. 4e a comparison product obtained according to WO 02/46109 is shown in an enlargement corresponding to that of FIGS. 4b and 4d. It should be noted that this product was produced with admixture of carbon black (in this process, reaction acceleration takes place during sintering by the combustion of the blended carbon black). It can be a similar open-pored structure as in the cases of Figures 4a to 4d are recognized.
- FIGS. 5a to 5c show the behavior of the comparison product.
- Lithium titanium spinel significantly increases by the treatment according to the invention and in the embodiments of the invention almost reaches the theoretically possible value of 175 mAh / g.
- the current carrying capacity also increases significantly. The effect which was to be expected on the basis of the homogeneity of the starting mixture achieved by the process according to the invention was therefore confirmed.
- composition of the starting materials described above was treated for 1 / 2h at a power consumption of 900W without cooling.
- the temperature rose up to 75 ° C in the stator.
- Figure 6a shows a SEM image of the mixture thus obtained, while Figure 6b shows a mixture of the same
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10760267A EP2488453A1 (de) | 2009-10-15 | 2010-09-28 | Verfahren zur herstellung von feinteiligen lithiumtitan-spinellen und deren verwendung |
JP2012533506A JP2013507316A (ja) | 2009-10-15 | 2010-09-28 | 微細分散したチタン酸リチウムスピネルの生成方法及びその使用方法 |
US13/502,277 US20120328950A1 (en) | 2009-10-15 | 2010-09-28 | Process for the preparation of finely dispersed lithium titanium spinels and their use |
KR1020147023885A KR20140116226A (ko) | 2009-10-15 | 2010-09-28 | 미립자 리튬 티타늄 스피넬의 제조 방법 및 그의 용도 |
KR1020127010968A KR20120062004A (ko) | 2009-10-15 | 2010-09-28 | 미립자 리튬 티타늄 스피넬의 제조 방법 및 그의 용도 |
CN201080046253.2A CN102596812B (zh) | 2009-10-15 | 2010-09-28 | 制备细粒锂钛尖晶石的方法及其应用 |
CA2776818A CA2776818A1 (en) | 2009-10-15 | 2010-09-28 | Process for the preparation of finely dispersed lithium titanium spinels and their use |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102009049470.7 | 2009-10-15 | ||
DE102009049470A DE102009049470A1 (de) | 2009-10-15 | 2009-10-15 | Verfahren zur Herstellung von feinteiligen Lithiumtitan-Spinellen und deren Verwendung |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011044989A1 true WO2011044989A1 (de) | 2011-04-21 |
Family
ID=42985365
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2010/005915 WO2011044989A1 (de) | 2009-10-15 | 2010-09-28 | Verfahren zur herstellung von feinteiligen lithiumtitan-spinellen und deren verwendung |
Country Status (9)
Country | Link |
---|---|
US (1) | US20120328950A1 (de) |
EP (1) | EP2488453A1 (de) |
JP (1) | JP2013507316A (de) |
KR (2) | KR20140116226A (de) |
CN (1) | CN102596812B (de) |
CA (1) | CA2776818A1 (de) |
DE (1) | DE102009049470A1 (de) |
TW (1) | TWI423928B (de) |
WO (1) | WO2011044989A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015180592A (ja) * | 2015-03-23 | 2015-10-15 | 日本ケミコン株式会社 | チタン酸リチウム結晶構造体 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2538254C1 (ru) * | 2013-07-17 | 2015-01-10 | Хожбауди Хамзатович Альвиев | Способ получения наноразмерных порошков композита на основе титаната лития |
CN103474637A (zh) * | 2013-08-30 | 2013-12-25 | 厦门钨业股份有限公司 | 锂离子电池正极材料及其制备方法 |
US20220393163A1 (en) * | 2021-06-04 | 2022-12-08 | Scandium International Mining Corporation | Lithium-ion battery with scandium doping for cathode, anode, and electrolyte materials |
Citations (5)
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US5545468A (en) | 1993-03-17 | 1996-08-13 | Matsushita Electric Industrial Co., Ltd. | Rechargeable lithium cell and process for making an anode for use in the cell |
WO2001044113A1 (en) | 1999-12-15 | 2001-06-21 | Lg Chemical Co., Ltd | A method for preparing lithium manganese spinel oxide having improved electrochemical performance |
WO2002046109A2 (en) | 2000-12-05 | 2002-06-13 | Owens Corning | Methods and apparatus for the cooling of filaments in a filament forming process |
DE10319464A1 (de) | 2003-04-29 | 2004-11-18 | Basf Ag | Verfahren zur Herstellung von nanokristallinen Lithiumtitanat-Spinellen |
EP1722439A1 (de) | 2005-05-13 | 2006-11-15 | Kabushiki Kaisha Toshiba | Batterie mit nichtwässrigem Elektrolyten, Lithium-Titanium-Mischoxid, Batterieblock und Fahrzeug |
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US2979951A (en) * | 1958-12-30 | 1961-04-18 | Central Farmers Fertilizer Com | Temperature sensing apparatus |
JP4639432B2 (ja) * | 2000-06-07 | 2011-02-23 | パナソニック株式会社 | 非水系二次電池 |
EP1337241B1 (de) * | 2000-11-30 | 2008-01-02 | Vectura Limited | Verfahren zur vorbereitung von mikropartikeln zur verwendung in pharmazeutischen zusammensetzungen zur inhalation |
CA2327370A1 (fr) * | 2000-12-05 | 2002-06-05 | Hydro-Quebec | Nouvelle methode de fabrication de li4ti5o12 pur a partir du compose ternaire tix-liy-carbone: effet du carbone sur la synthese et la conductivite de l'electrode |
CA2389555A1 (fr) * | 2002-05-30 | 2003-11-30 | Hydro Quebec | Procede de preparation de poudres ceramiques en presence de carbone, poudres ainsi obtenues et leur utilisation |
CA2394056A1 (fr) * | 2002-07-12 | 2004-01-12 | Hydro-Quebec | Particules comportant un noyau non conducteur ou semi conducteur recouvert d'un couche conductrice, leurs procedes d'obtention et leur utilisation dans des dispositifs electrochimiques |
FR2874603B1 (fr) * | 2004-08-31 | 2006-11-17 | Commissariat Energie Atomique | Compose pulverulent d'oxyde mixte de titane et de lithium dense, procede de fabrication d'un tel compose et electrode comportant un tel compose |
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JP5190916B2 (ja) * | 2007-03-15 | 2013-04-24 | 独立行政法人産業技術総合研究所 | 電極用複合粉末及びその製造方法 |
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-
2009
- 2009-10-15 DE DE102009049470A patent/DE102009049470A1/de not_active Withdrawn
-
2010
- 2010-09-28 KR KR1020147023885A patent/KR20140116226A/ko not_active Application Discontinuation
- 2010-09-28 JP JP2012533506A patent/JP2013507316A/ja active Pending
- 2010-09-28 KR KR1020127010968A patent/KR20120062004A/ko active Application Filing
- 2010-09-28 EP EP10760267A patent/EP2488453A1/de not_active Withdrawn
- 2010-09-28 US US13/502,277 patent/US20120328950A1/en not_active Abandoned
- 2010-09-28 CA CA2776818A patent/CA2776818A1/en not_active Abandoned
- 2010-09-28 CN CN201080046253.2A patent/CN102596812B/zh not_active Expired - Fee Related
- 2010-09-28 WO PCT/EP2010/005915 patent/WO2011044989A1/de active Application Filing
- 2010-10-14 TW TW099135023A patent/TWI423928B/zh not_active IP Right Cessation
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US5545468A (en) | 1993-03-17 | 1996-08-13 | Matsushita Electric Industrial Co., Ltd. | Rechargeable lithium cell and process for making an anode for use in the cell |
WO2001044113A1 (en) | 1999-12-15 | 2001-06-21 | Lg Chemical Co., Ltd | A method for preparing lithium manganese spinel oxide having improved electrochemical performance |
WO2002046109A2 (en) | 2000-12-05 | 2002-06-13 | Owens Corning | Methods and apparatus for the cooling of filaments in a filament forming process |
DE10319464A1 (de) | 2003-04-29 | 2004-11-18 | Basf Ag | Verfahren zur Herstellung von nanokristallinen Lithiumtitanat-Spinellen |
EP1722439A1 (de) | 2005-05-13 | 2006-11-15 | Kabushiki Kaisha Toshiba | Batterie mit nichtwässrigem Elektrolyten, Lithium-Titanium-Mischoxid, Batterieblock und Fahrzeug |
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Title |
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JP2015180592A (ja) * | 2015-03-23 | 2015-10-15 | 日本ケミコン株式会社 | チタン酸リチウム結晶構造体 |
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CN102596812B (zh) | 2014-12-17 |
DE102009049470A1 (de) | 2011-04-28 |
EP2488453A1 (de) | 2012-08-22 |
KR20140116226A (ko) | 2014-10-01 |
TWI423928B (zh) | 2014-01-21 |
CN102596812A (zh) | 2012-07-18 |
US20120328950A1 (en) | 2012-12-27 |
JP2013507316A (ja) | 2013-03-04 |
CA2776818A1 (en) | 2011-04-21 |
KR20120062004A (ko) | 2012-06-13 |
TW201118040A (en) | 2011-06-01 |
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