WO2012147854A1 - チタン酸リチウムの製造方法 - Google Patents
チタン酸リチウムの製造方法 Download PDFInfo
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- WO2012147854A1 WO2012147854A1 PCT/JP2012/061213 JP2012061213W WO2012147854A1 WO 2012147854 A1 WO2012147854 A1 WO 2012147854A1 JP 2012061213 W JP2012061213 W JP 2012061213W WO 2012147854 A1 WO2012147854 A1 WO 2012147854A1
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- lithium titanate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
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- 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
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- 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
- C01P2006/80—Compositional purity
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- 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
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a method for producing lithium titanate.
- it is related with the manufacturing method of lithium titanate which can be manufactured efficiently at low cost.
- this invention relates to the lithium titanate manufactured by the said method, the electrode active material containing the same, and an electrical storage device.
- Lithium titanate is being developed as a material for an electricity storage device, and is used as an electrode active material having excellent safety and life characteristics as an anode active material for an electricity storage device, particularly a lithium secondary battery.
- Lithium secondary batteries are rapidly spreading for small batteries such as portable device power supplies, and are also being developed for large-sized lithium secondary batteries for the electric power industry and automobiles. Electrode active materials for these large lithium secondary batteries are required to have long-term reliability and high input / output characteristics. Lithium titanate, which has excellent safety and life characteristics, is particularly promising for negative electrode active materials. Yes.
- Patent Document 1 describes a compound in which 0.8 ⁇ x ⁇ 1.4 and 1.6 ⁇ y ⁇ 2.2 in lithium titanate represented by the general formula Li x Ti y O 4 , Typical examples include LiTi 2 O 4 , Li 1.33 Ti 1.66 O 4, and Li 0.8 Ti 2.2 O 4 .
- Patent Document 2 a predetermined amount of a lithium compound and a titanium compound are mixed in a liquid medium, dried and then fired (Patent Document 2).
- Patent Document 3 A spray drying method (Patent Document 3) performed by spray drying, a dry method (Patent Documents 1 and 4) in which a predetermined amount of a lithium compound and a titanium compound are mixed in a dry method and fired are known.
- Lithium titanate is produced by firing a lithium compound and a titanium compound in both the dry method and the wet method, but because of the solid phase diffusion reaction, the reactivity between these raw materials is low, In addition to lithium titanate, by-products having different compositions and unreacted raw materials are likely to remain. For this reason, sufficient electric capacity cannot be obtained when used in a battery.
- a higher firing temperature is advantageous in terms of reactivity, but lithium volatilization loss is likely to occur, and since lithium titanate particles shrink and sinter and grain growth proceeds, the specific surface area of lithium titanate particles And the rate characteristics are likely to deteriorate when used in a battery.
- the present inventors From the viewpoint of improving the reactivity between the lithium compound and the titanium compound, the present inventors have conducted extensive research on a method for efficiently producing the target lithium titanate. The inventors have found that the above problems can be solved by heating a lithium compound having a volume average particle size of 5 ⁇ m or less, and completed the present invention.
- the method for producing lithium titanate according to the present invention by using a lithium compound having a volume average particle size of 5 ⁇ m or less, the reactivity between the titanium compound and the lithium compound is improved, and the intended lithium titanate is efficiently produced. Can do. That is, according to the method of the present invention, the generation of subphases having different compositions and the remaining of unreacted raw materials are small, and the progress of sintering and the decrease in specific surface area are small. Moreover, the target lithium titanate can be reliably and stably manufactured even at a heating temperature lower than that of the conventional manufacturing method. In addition, when lithium titanate manufactured by the above method is used as an electrode active material, an electricity storage device having excellent battery characteristics, particularly rate characteristics, can be manufactured.
- FIG. 3 is a powder X-ray diffraction pattern of Samples 1, 4, and 6.
- FIG. It is a graph which shows the rate characteristic of the electrical storage device of samples A and B.
- Specific surface area In the present specification, the specific surface area is measured by the BET one-point method by nitrogen adsorption.
- As the apparatus Monosorb manufactured by Yuasa Ionics or Monosorb model MS-22 manufactured by Quantachrome Instruments was used.
- the average particle diameter of the lithium compound means a volume average particle diameter measured by a laser diffraction method.
- the volume average particle size is determined by using a laser diffraction / scattering type particle size distribution measuring apparatus, using ethanol as the dispersion medium, setting the refractive index to 1.360 for ethanol, and appropriately setting the lithium compound according to the compound type. It is measured. For example, when the lithium compound is lithium carbonate, the refractive index is 1.500.
- LA-950 manufactured by Horiba Ltd. was used as a laser diffraction / scattering particle size distribution analyzer.
- the average particle size of the primary particles of the titanium compound is obtained by measuring the particle size of 100 primary particles in an image using a transmission electron microscope and taking the average value (electron microscopy). ).
- the average secondary particle diameter of the secondary particle of a titanium compound means the volume average particle diameter measured by the laser diffraction method.
- the volume average particle size is determined using a laser diffraction / scattering type particle size distribution measuring device, pure water is used as a dispersion medium, the refractive index is 1.333 for pure water, and the titanium compound is appropriately selected according to the type of compound. Set and measured. For example, when the titanium compound is anatase type titanium oxide, the refractive index is 2.520.
- LA-950 manufactured by Horiba Ltd. was used as a laser diffraction / scattering particle size distribution measuring apparatus.
- the average particle diameter of the lithium titanate precursor mixture refers to a volume average particle diameter measured by a laser diffraction method.
- the volume average particle size is determined by using a laser diffraction / scattering type particle size distribution measuring apparatus, using ethanol as a dispersion medium, a refractive index of 1.360 for ethanol, and the numerical value of the compounded lithium compound for the measurement particles. It was measured using. For example, when the lithium compound is lithium carbonate, the refractive index is 1.567.
- LA-950 manufactured by Horiba Ltd. was used as a laser diffraction / scattering particle size distribution measuring apparatus.
- the average particle size of primary particles of lithium titanate is obtained by measuring the particle size of 100 primary particles in an image using a transmission electron microscope and taking the average value (electron microscope). Law).
- the average secondary particle diameter of the secondary particle of lithium titanate means the volume average particle diameter measured by the laser diffraction method.
- the volume average particle size is determined by using a laser diffraction / scattering type particle size distribution measuring device, using pure water as a dispersion medium, a refractive index of 1.333 for water, and appropriately for lithium titanate depending on the compound type. Set and measure.
- the lithium titanate is Li 4 Ti 5 O 12
- the refractive index is 2.700.
- LA-950 manufactured by Horiba Ltd. was used as the laser diffraction / scattering particle size distribution measuring apparatus.
- the bulk density is determined by a cylinder type (a sample is placed in a measuring cylinder and calculated from volume and mass).
- Impurities such as sodium and potassium are measured by an atomic absorption method, SO 4 and chlorine are measured by an ion chromatography method or a fluorescent X-ray measuring device, and silicon, calcium, iron, chromium, nickel, Other elements such as manganese, copper, zinc, aluminum, magnesium, niobium and zirconium are measured by the ICP method.
- SO 4 a fluorescent X-ray measurement apparatus (RIGAKU RIX-2200) was used.
- This invention is a manufacturing method of lithium titanate, Comprising: It is a manufacturing method of lithium titanate which heats at least the following 2 types of compounds.
- Titanium compound (2) A lithium compound having a volume average particle size of 5 ⁇ m or less.
- Titanium compound As the titanium compound, an inorganic titanium compound or an organic titanium compound such as titanium alkoxide can be used.
- the inorganic titanium compound TiO (OH) 2 or TiO 2 ⁇ H metatitanic acid represented by 2 O, Ti (OH) 4 or titanate compounds such as ortho-titanate represented by TiO 2 ⁇ 2H 2 O, Titanium oxide (crystalline titanium oxide or amorphous titanium oxide such as rutile type, anatase type, brookite type, or bronze type), or a mixture thereof can be used.
- titanium oxide having an X-ray diffraction pattern having only a diffraction peak from a single crystal structure
- titanium oxide has a plurality of crystal structures such as those having an anatase type diffraction peak and a rutile type diffraction peak. It may have a diffraction peak.
- crystalline titanium oxide is preferable.
- the titanium compound is preferably fine in terms of reactivity with the lithium compound, and the average primary particle diameter (electron microscopy) is preferably in the range of 0.001 ⁇ m to 0.3 ⁇ m, more preferably 0.005 to 0.3 ⁇ m. Preferably, the range is 0.01 ⁇ m to 0.3 ⁇ m, and more preferably 0.04 to 0.28 ⁇ m.
- the specific surface area of the titanium compound is preferably larger value in terms of reactivity with the lithium compound is preferably 20 ⁇ 300m 2 / g, more preferably 50 ⁇ 300m 2 / g, 60 ⁇ 300m 2 / g Is more preferable, and 60 to 100 m 2 / g is more preferable.
- the average secondary particle diameter is preferably 0.05 to 5 ⁇ m, more preferably 0.1 to 3.0 ⁇ m, More preferably, it is 0.5 to 2.0 ⁇ m.
- the titanium compound preferably has a high purity, and usually has a purity of 90% by weight or more, more preferably 99% by weight or more.
- Impurity Cl or SO 4 is preferably 0.5% by weight or less. Moreover, the following ranges are more preferable as other elements. Silicon (1000 ppm or less), calcium (1000 ppm or less), iron (1000 ppm or less), niobium (0.3 wt% or less), zirconium (0.2 wt% or less).
- Lithium compound It is important that the lithium compound used in the present invention has a volume average particle size of 5 ⁇ m or less from the viewpoint of reactivity with the titanium compound, and the lower limit can be appropriately set.
- a preferred volume average particle size is in the range of 0.5 to 5 ⁇ m, more preferably in the range of 1 to 5 ⁇ m.
- the volume average particle diameter may be 4 ⁇ m or less, preferably in the range of 0.5 to 4 ⁇ m, more preferably in the range of 1 to 4 ⁇ m.
- the single phase ratio of the lithium titanate is an index indicating the content of the target lithium titanate represented by the following formula 1, and is preferably 95% or more, more preferably 96% or more, and 97% or more. Is more preferable.
- X is the main peak intensity of the target lithium titanate in powder X-ray diffraction measurement using Cuk ⁇ rays
- Y i is the main peak intensity of each subphase.
- Such a lithium compound may be produced by setting production conditions as appropriate and producing a volume average particle size of 5 ⁇ m or less.
- a volume average particle size larger than 5 ⁇ m may be manufactured or purchased, and the lithium compound may be refined to 5 ⁇ m or less.
- a known method can be used for the refining treatment.
- the volume average particle diameter of the lithium compound is preferably 5 ⁇ m or less by pulverization, and more preferably 4 ⁇ m or less.
- Lithium compound particles generally have a polyhedral shape, but when pulverized, the particle diameter is reduced and the corners of the polyhedron are rounded. For this reason, it is estimated that the fluidity
- pulverizers can be used for pulverization of lithium compounds, for example, dry type such as flake crusher, hammer mill, pin mill, bantam mill, jet mill, fret mill, pan mill, edge runner, roller mill, mix muller, vibration mill, etc.
- a pulverizer is preferred.
- D90 cumulative frequency 90% diameter
- D90 is 10 ⁇ m or less, preferably 9 ⁇ m or less, more preferably When the thickness is 7 ⁇ m or less, the effect of the present invention is easily obtained, which is preferable.
- lithium compound hydroxides, salts, oxides and the like can be used without particular limitation, and examples thereof include lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, and lithium oxide. These 1 type can be used and 2 or more types may be used together.
- lithium compounds lithium hydroxide, lithium carbonate, and lithium oxide are preferably used in order to avoid remaining acidic roots in lithium titanate, and lithium hydroxide and lithium carbonate are preferably used because of easy pulverization. More preferred is lithium carbonate.
- the acidic root means a sulfate group (SO 4 ) and a chlorine group (Cl).
- the lithium compound preferably has a high purity, and usually a purity of 98.0% by weight or more is good.
- Li 2 CO 3 is 98.0% by weight or more, preferably 99.0% by weight or more, and an impurity metal element such as Na, Ca, K, or Mg is present. 1000 ppm or less, and Cl and SO 4 are 1000 ppm or less, preferably 500 ppm or less. Further, it is desirable that the moisture is sufficiently removed, and the content is desirably 0.3% by weight or less.
- the lithium compound preferably has a high specific surface area from the viewpoint of reactivity. For example, in the case of lithium carbonate, 0.8 m 2 / g or more is preferable, and a range of 1.0 to 3.0 m 2 / g is more preferable.
- Lithium titanate compound having the same crystal structure as the target lithium titanate This lithium titanate compound is used as necessary, and suppresses sintering of the generated lithium titanate, or The lithium titanate compound is considered to act as a seed crystal, and the heating process described later can be performed at a relatively low temperature, and the particle growth of lithium titanate in the heating process is appropriately controlled. This makes it easier to produce lithium titanate. For this reason, it is necessary to have the same crystal structure as the target lithium titanate.
- the particle diameter (electron microscopy) of the lithium titanate compound is not particularly limited, and the same particle diameter as that of the target lithium titanate (electron microscopy), for example, about 0.5 to 2.0 ⁇ m. Those having an average particle size of may be used.
- the lithium titanate compound can be produced by the method of the present invention.
- the blending amount is preferably 1 to 30 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the raw material titanium compound, in terms of Ti amount.
- a mixing aid or the like may be used.
- the ratio (B / A) of the volume average particle size (A ⁇ m) of the secondary particles of the titanium compound to the volume average particle size (B ⁇ m) of the lithium compound is preferably 0.1 to 80, preferably 0.1 to 20 is more preferable, and 0.1 to 8 is even more preferable.
- B / A in such a range, the lithium titanate precursor mixture having a relatively uniform particle size and a narrow particle size distribution can be easily obtained, so that the reaction between the lithium compound and the titanium compound can be easily achieved. It is easy to obtain a lithium titanate precursor mixture having higher properties.
- the range of B / A is more preferably 1.0 to 5.0, and further preferably 1.0 to 4.0.
- a mixture (hereinafter also referred to as “precursor mixture”) by mixing the raw materials.
- the mixing is preferably performed by dry-mixing at least (1) a titanium compound and (2) a lithium compound having a volume average particle size of 5 ⁇ m or less, and (3) having the same crystal structure as the target lithium titanate.
- a lithium titanate compound for production it is preferable to dry-mix the lithium titanate compound together with the above two types.
- a known mixer can be used.
- dry mixers such as a Henschel mixer, a V-type mixer, a powder mixer, a double cone blender, and a tumbler mixer are preferably used.
- a tumbler mixer There is no restriction
- the precursor mixture may be prepared by simultaneously pulverizing the lithium compound and pulverizing the titanium compound (hereinafter, this method may be referred to as “pulverized mixing”).
- pulverized mixing a known pulverizer may be used.
- dry pulverization such as flake crusher, hammer mill, pin mill, bantam mill, jet mill, cyclone mill, fret mill, pan mill, edge runner, roller mill, mix muller, vibration mill, etc.
- An airflow crusher such as a jet mill or a cyclone mill is more preferable.
- both the titanium compound and the lithium compound may be put into a pulverizer. Either one of the pulverizations may be started first, the other may be added later, both may be added and then pulverization may be started, and both may be mixed in advance using a known mixer such as a Henschel mixer. May be put into a pulverizer and pulverized. By performing pulverization in the state where the titanium compound and the lithium compound coexist in this way, a lithium titanate precursor mixture in which the titanium compound and the lithium compound are sufficiently mixed can be obtained. The titanium compound and the lithium compound may have a desired size after pulverization.
- the mixing degree of the titanium compound and the lithium compound is likely to be higher than when only the fine particles are mixed, and in addition, the particle diameters are uniform.
- a lithium titanate precursor mixture containing a lithium compound and a titanium compound having a narrow particle size distribution is easily obtained. Thereby, it is easy to obtain a lithium titanate precursor mixture having higher reactivity between the lithium compound and the titanium compound, which is preferable.
- the titanium compound has a low bulk density, specifically, a bulk density in the range of 0.2 to 0.7 g / cm 3 , highly reactive titanic acid Since a lithium precursor mixture is obtained, it is preferable. It is considered that such a titanium compound having a low bulk density is easily dispersed on the air flow in the pulverizer and easily mixed with the lithium compound.
- the range of the bulk density is more preferably 0.2 to 0.6 g / cm 3 , and further preferably 0.2 to 0.5 g / cm 3 .
- a pulverized mixture has a high volume (low bulk density) and a large occupied volume per mass, so that productivity, for example, throughput per unit time / equipment (material input amount) decreases. Therefore, it is preferable to apply pressure to the pulverized mixture to suppress bulkiness and to obtain an appropriate bulk density. Furthermore, it is preferable to apply pressure because the titanium compound and the lithium compound are easily brought into contact with each other, and a lithium titanate precursor mixture having a high reactivity between the lithium compound and the titanium compound is easily obtained.
- a means for applying pressure a means for forming by pressurization (compression), a means for pressurization (compression) and pulverization, or the like can be used.
- a known pressure molding machine or compression molding machine can be used, and examples thereof include a roller compactor, a roller crusher, and a pellet molding machine.
- a pressure pulverizer or a compression pulverizer can be used as a means for applying pressure simultaneously with pulverization. Any material can be used as long as it is pulverized by pressure or compression force. For example, at least one pulverizer selected from a fret mill, a pan mill, an edge runner, a roller mill, and a mix muller can be used.
- the pulverization principle of these pulverizers is to apply pressure to the sample and pulverize the sample with the high pressure.
- the operation state will be described using a fret mill as an example.
- the sample under the roller is ground by rotating the heavy weight roller.
- a plurality of compounds are simultaneously mixed by being ground under a roller for a certain period of time.
- pressure can be applied to the mixed powder simultaneously with pulverization, and it is not necessary to provide a separate compression step, and the process can be simplified.
- the bulk density of the lithium titanate precursor mixture is preferably 0.2 to 0.7 g / cm 3 and more preferably 0.4 to 0.6 g / cm 3 .
- the bulk density is lower than the above range, the contact between the titanium compound and the lithium compound is low, and the reactivity is lowered.
- the bulk density is higher than the above range, the gas generated during the reaction in the heating process becomes difficult to escape or the heat conduction is inhibited. In this case, the reactivity also decreases. As a result, the single phase ratio of the lithium titanate obtained in any case is lowered.
- a lithium titanate precursor having a bulk density in the above range is easily obtained, and is preferably less than 0.5 t / cm 2 , more preferably 0.15 to 0. More preferably, it is 45 t / cm 2 .
- the lithium titanate precursor mixture preferably has one peak in the frequency curve when the particle size distribution is measured in a state dispersed in ethanol.
- the volume average particle diameter is preferably 0.5 ⁇ m or less
- D90 (cumulative frequency 90% diameter) is preferably 10 ⁇ m or less
- the volume average particle diameter is 0.45 ⁇ m or less
- D90 (cumulative frequency 90% diameter). ) Is more preferably 6 ⁇ m or less.
- a raw material is put into a heating furnace, heated to a predetermined temperature, and allowed to react for a certain period of time.
- a heating furnace it can carry out using a fluidized furnace, a stationary furnace, a rotary kiln, a tunnel kiln etc., for example.
- the heating temperature is preferably 700 ° C. or higher, and preferably 950 ° C. or lower.
- a preferable heating temperature is 700 ° C. to 800 ° C. Within this range, a lithium titanate having a single phase ratio of 95% or more, particularly 97% or more, which will be described later, and stable sintering and grain growth is stable. Can be manufactured.
- the heating time can be appropriately set, and about 3 to 6 hours is appropriate.
- the heating atmosphere is not limited, but is preferably an oxidizing atmosphere such as air or oxygen gas, a non-oxidizing atmosphere such as nitrogen gas or argon gas, or a reducing atmosphere such as hydrogen gas or carbon monoxide gas. Is preferred.
- the lithium titanate thus obtained may be crushed or crushed as necessary after cooling.
- the above-mentioned known pulverizer can be used.
- the lithium titanate of the present invention is preferable because it has less sintering and grain growth, so that when pulverized and pulverized, the lithium titanate particles are easily broken and easily dispersed in a paste when an electrode of an electricity storage device is produced.
- the lithium titanate thus obtained has a large specific surface area, specifically 1.0 m 2 / g or more is preferable, 2.0 to 50.0 m 2 / g is more preferable, and 2.0 More preferred is 40.0 m 2 / g.
- the bulk density and volume average particle diameter of lithium titanate can be appropriately set, and the bulk density is preferably 0.1 to 0.8 g / cm 3 , more preferably 0.2 to 0.7 g / cm 3. preferable.
- the volume average particle diameter is preferably 1 to 10 ⁇ m. Moreover, it is preferable that there are few impurities and specifically, the following range is more preferable.
- this invention is an electrode active material, Comprising: It contains the lithium titanate of this invention mentioned above, It is characterized by the above-mentioned.
- the present invention is an electricity storage device, characterized by using lithium titanate obtained by the above-described production method of the present invention.
- This electricity storage device is composed of an electrode, a counter electrode, a separator, and an electrolytic solution, and the electrode is obtained by appropriately forming or applying a conductive material and a binder to the electrode active material.
- the conductive material include conductive assistants such as carbon black, acetylene black, and ketjen black.
- the binder examples include fluorine resins such as polytetrafluoroethylene, polyvinylidene fluoride, and fluorine rubber, and styrene butadiene rubber. Water-soluble resins such as carboxymethyl cellulose and polyacrylic acid.
- the electrode active material can be used as a positive electrode, and a lithium-containing metal, lithium alloy, or a carbon-containing material such as graphite can be used as a counter electrode.
- the electrode active material is used as a negative electrode, and a lithium / manganese composite oxide, a lithium / cobalt composite oxide, a lithium / nickel composite oxide, a lithium / cobalt / manganese / nickel composite oxide, or a lithium / vanadine composite oxide is used as the positive electrode.
- Lithium / transition metal composite oxides such as olivine, and olivine type compounds such as lithium / iron / composite phosphate compounds can be used.
- a porous polypropylene film or the like is used, and for the electrolyte, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ⁇ -butyl lactone, 1,2-dimethoxyethane, etc.
- Conventional materials such as those obtained by dissolving lithium salts such as LiPF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiBF 4 in the above solvent can be used.
- the lithium titanate of the present invention is used not only as an active material of a lithium secondary battery, but also attached to the surface of another type of active material, blended with an electrode, contained in a separator, or as a lithium ion conductor. You may use it. Moreover, you may use as an active material of a sodium ion battery.
- Lithium carbonate pulverization Lithium carbonate powder (purity: 99.2%) is used as a sample a, and this sample a is used with a jet mill (STJ-200 manufactured by Seishin Enterprise Co., Ltd.) until the volume average particle size is 4 ⁇ m or less
- the sample b was obtained by grinding. Further, the crushing was strengthened by lowering the feed amount as compared with the production of sample b, and sample c was obtained. Further, the pulverization was reduced by increasing the feed amount as compared with the production of sample b, and samples d and e having different particle sizes were obtained.
- Example 2 In Example 1, Sample 2 was obtained in the same manner as in Example 1 except that Sample c was used as the lithium compound.
- Example 3 In Example 1, Sample 3 was obtained in the same manner as in Example 1 except that Sample d was used as the lithium compound.
- Example 1 Sample 4 was obtained in the same manner as in Example 1 except that Sample a was used as the lithium compound.
- Example 1 Sample 5 was obtained in the same manner as in Example 1 except that Sample e was used as the lithium compound.
- Comparative Example 3 In Comparative Example 1, Sample 6 was obtained in the same manner as Comparative Example 1, except that heating was performed in the atmosphere at 800 ° C. for 3 hours.
- lithium titanate Li 4 Ti 5 O 12 having a single phase ratio of 95% or more was obtained even when heated at 750 ° C.
- heating at 750 ° C. does not yield lithium titanate Li 4 Ti 5 O 12 having a single phase ratio of 95% or more.
- heating at 800 ° C. shows that lithium titanate Li 4 Ti 5 O 12 having a single phase ratio of 95% or more was finally obtained. From this, it can be seen that the production method of the present invention makes it possible to synthesize lithium titanate having a single phase ratio of 95% or more even when the heating temperature during lithium titanate synthesis is low, specifically, less than 800 ° C.
- SUS316 stainless steel
- non-aqueous electrolyte a mixed solution of ethylene carbonate and dimethyl carbonate (mixed in a volume ratio of 1: 2) in which LiPF 6 was dissolved at a concentration of 1 mol / liter was used.
- the working electrode was placed in a lower can of a coin-type cell, a porous polypropylene film was placed thereon as a separator, and a non-aqueous electrolyte was dropped from above. Furthermore, a negative electrode, a 0.5 mm thick spacer for adjusting the thickness, and a spring (both made of SUS316) are placed thereon, and an upper can with a polypropylene gasket is covered and the outer peripheral edge is caulked and sealed. An electricity storage device (sample A) was obtained.
- a power storage device (sample B) of a comparative example was obtained in the same manner as the power storage device of sample A, except that sample 6 was used as lithium titanate.
- the target lithium titanate of the present invention can be reliably and stably produced at a low cost and at a heating temperature lower than that of the conventional production method.
- an electricity storage device having excellent battery characteristics, particularly rate characteristics, can be manufactured.
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Abstract
Description
また、上記の方法で製造したチタン酸リチウムを電極活物質として用いると、電池特性、特にレート特性に優れた蓄電デバイスを製造することができる。
比表面積
本願明細書において、比表面積は、窒素吸着によるBET一点法にて測定したものである。装置はユアサアイオニクス社製モノソーブ又はQuantachrome Instruments社製Monosorb型番MS-22を用いた。
本願明細書において、リチウム化合物の平均粒径とは、レーザー回折法で測定した体積平均粒径をいう。体積平均粒径は、レーザー回折/散乱式粒度分布測定装置を用い、分散媒にエタノールを使用し、屈折率をエタノールについては1.360とし、リチウム化合物については化合物種に応じて適宜設定して測定したものである。例えば、リチウム化合物が炭酸リチウムである場合、屈折率は1.500を使用する。レーザー回折/散乱式粒度分布測定装置としては、堀場製作所社製 LA-950を用いた。
本願明細書において、チタン化合物の一次粒子の平均粒径は、透過型電子顕微鏡を用い、画像中の一次粒子100個の粒子径を測定し、その平均値を取ったものである(電子顕微鏡法)。
また、本願明細書において、チタン化合物の二次粒子の平均二次粒子径とは、レーザー回折法で測定した体積平均粒径をいう。体積平均粒径は、レーザー回折/散乱式粒度分布測定装置を用い、分散媒に純水を使用し、屈折率を、純水については1.333とし、チタン化合物については化合物種に応じて適宜設定して測定したものである。例えば、チタン化合物がアナターゼ型酸化チタンの場合、屈折率は2.520を使用する。レーザー回折/散乱式粒度分布測定装置は、堀場製作所社製 LA-950を用いた。
本願明細書において、チタン酸リチウム前駆体混合物の平均粒径とは、レーザー回折法で測定した体積平均粒径をいう。体積平均粒径は、レーザー回折/散乱式粒度分布測定装置を用い、分散媒にエタノールを使用し、屈折率を、エタノールについては1.360とし、測定粒子については配合したリチウム化合物種の数値を用いて測定したものである。例えば、リチウム化合物が炭酸リチウムである場合は、屈折率は1.567を使用する。レーザー回折/散乱式粒度分布測定装置は、堀場製作所社製 LA-950を用いた。
本願明細書において、チタン酸リチウムの一次粒子の平均粒径は、透過型電子顕微鏡を用い、画像中の一次粒子100個の粒子径を測定し、その平均値を取ったものである(電子顕微鏡法)。
また、本願明細書において、チタン酸リチウムの二次粒子の平均二次粒子径とは、レーザー回折法で測定した体積平均粒径をいう。体積平均粒径は、レーザー回折/散乱式粒度分布測定装置を用い、分散媒に純水を使用し、屈折率を、水については1.333とし、チタン酸リチウムについては化合物種に応じて適宜設定して測定する。チタン酸リチウムがLi4Ti5O12である場合、屈折率は2.700を使用する。また、本発明においてはレーザー回折/散乱式粒度分布測定装置は、堀場製作所社製 LA-950を用いた。
本願明細書において、嵩密度は、シリンダー式(メスシリンダに試料を入れ、体積と質量から算出)により求める。
本願明細書において、不純物である、ナトリウム、カリウムは原子吸光法により測定し、SO4、塩素はイオンクロマトグラフィー法又は蛍光X線測定装置により測定し、ケイ素、カルシウム、鉄、クロム、ニッケル、マンガン、銅、亜鉛、アルミニウム、マグネシウム、ニオブ、ジルコニウムなどのその他の元素はICP法により測定する。SO4については、蛍光X線測定装置(RIGAKU RIX-2200)を用いた。
本発明は、チタン酸リチウムの製造方法であって、少なくとも以下の2種の化合物を加熱するチタン酸リチウムの製造方法である。
(1)チタン化合物
(2)体積平均粒径が5μm以下のリチウム化合物。
チタン化合物としては、無機チタン化合物又はチタンアルコキシドのような有機チタン化合物を用いることができる。無機チタン化合物としては、TiO(OH)2又はTiO2・H2Oで表されるメタチタン酸、Ti(OH)4またはTiO2・2H2Oで表されるオルトチタン酸などのチタン酸化合物、酸化チタン(ルチル型、アナターゼ型、ブルッカイト型、ブロンズ型などの結晶性酸化チタンやアモルファス酸化チタン)、あるいはそれらの混合物などを用いることができる。酸化チタンは、X線回折パターンが、単一の結晶構造からの回折ピークのみを有する酸化チタンのほか、例えば、アナターゼ型の回折ピークとルチル型の回折ピークを有するもの等、複数の結晶構造からの回折ピークを有するものであってもよい。中でも、結晶性の酸化チタンが好ましい。
チタン化合物は高純度のものが好ましく、通常純度90重量%以上が良く、99重量%以上がより好ましい。不純物のCl又はSO4が0.5重量%以下が好ましい。また、その他の元素として具体的には次の範囲がより好ましい。ケイ素(1000ppm以下)、カルシウム(1000ppm以下)、鉄(1000ppm以下)、ニオブ(0.3重量%以下)、ジルコニウム(0.2重量%以下)。
本発明で用いるリチウム化合物は、チタン化合物との反応性の点から、体積平均粒径が5μm以下であることが重要であり、下限は適宜設定することができる。好ましい体積平均粒径としては、0.5~5μmの範囲であり、より好ましくは1~5μmの範囲である。また、体積平均粒径を4μm以下、好ましくは0.5~4μmの範囲、より好ましくは1~4μmの範囲としてもよい。体積平均粒径が5μm以下のリチウム化合物を用いてチタン酸リチウムを製造すると、チタン化合物との反応性がよく、目的とするチタン酸リチウムの単相率が高くなる。しかしながら、体積平均粒径が5μmより大きいリチウム化合物を用いると、チタン化合物との反応性が悪くなり、目的とするチタン酸リチウムの単相率が低くなる。
(式1)単相率(%)=100×(1-Σ(Yi/X))
ここで、Xは、Cukα線を用いた粉末X線回折測定における、目的とするチタン酸リチウムのメインピーク強度、Yiは各副相のメインピーク強度である。Li4Ti5O12の場合、Xは2θ=18°付近のピーク強度であり、アナターゼ型又はルチル型TiO2やLi2TiO3が副相として存在しやすいのでYiには2θ=25°付近のピーク強度(アナターゼ型TiO2)、2θ=27°付近のピーク強度(ルチル型TiO2)と2θ=44°付近のピーク強度(Li2TiO3)を用いる。
本発明において酸性根とは、硫酸根(SO4)及び塩素根(Cl)を意味する。
このチタン酸リチウム化合物は、必要に応じて使用するものであり、生成するチタン酸リチウムの焼結を抑制したり、あるいは、種結晶として作用すると考えられ、このチタン酸リチウム化合物を使用すると、後述の加熱工程を比較的低温で行うことができるとともに、加熱工程におけるチタン酸リチウムの粒子成長が適切に制御され、目的とするチタン酸リチウムを製造しやすくなる。このため、目的とするチタン酸リチウムと同じ結晶構造を有する必要がある。チタン酸リチウム化合物の粒子径(電子顕微鏡法)には特に制限は無く、目的とするチタン酸リチウムの粒子径(電子顕微鏡法)と同程度の粒径、例えば、0.5~2.0μm程度の平均粒径のものを用いればよい。チタン酸リチウム化合物は本発明の方法で作製することができる。その配合量は、Ti量換算で、原料のチタン化合物100重量部に対し、1~30重量部が好ましく、5~20重量部がより好ましい。なお、前記の(1)、(2)、(3)のほかに、混合助剤などを用いてもよい。
前駆体混合物を調製するには公知の混合機を用いることができ、例えば、ヘンシェルミキサー、V型混合機、パウダーミキサー、ダブルコーンブレンダー、タンブラーミキサーなどの乾式混合機が好ましく用いられる。混合を行う雰囲気には特に制限は無い。
粒度分布を前記の範囲とすることで、組成の異なる副相の生成や未反応の原料の残存を更に少なくすることができ、焼結の進行や比表面積の低下の少ない、目的とするチタン酸リチウムを、従来の製造方法よりも低い加熱温度でも確実に安定して製造することができる。
リチウム化合物として炭酸リチウム粉末(純度99.2%)を試料aとし、この試料aをジェットミル(セイシン企業社製 STJ-200)を用いて体積平均粒径が4μm以下になるまで粉砕し、試料bを得た。また、試料b製造時よりも、フィード量を下げることで粉砕を強化し、試料cを得た。また、試料b製造時よりも、フィード量を上げることで粉砕を軽減し、それぞれ粒径が異なる試料d、試料eを得た。
原料である試料a~eの粒度分布を、レーザー回折/散乱式粒子径分布測定装置(堀場製作所社製 LA-950)にて測定した。測定は、分散媒にエタノールを使用し、炭酸リチウム及びエタノールの屈折率を、それぞれ1.500、1.360に設定して行った。結果を表1に示す。試料a~eの体積平均粒径は、それぞれ8.1μm、3.7μm、2.1μm、5.0μm、7.7μmであった。また、D90(累積頻度90%径)はそれぞれ13.0μm、6.2μm、3.1μm、8.1μm、12.0μmであった。
実施例1
チタン化合物として酸化チタン粉末(石原産業株式会社製、純度97.3%、体積平均粒径1.3μm、比表面積93m2/g)と、リチウム化合物として試料bとを、Li/Tiモル比で0.81となるように原料を採取し、ヘンシェル混合器で10分間、1800rpmで混合し、前駆体混合物を調製した。次いで、前駆体混合物を、電気炉を用い大気中750℃で3時間加熱を行い、チタン酸リチウムを合成した。得られたチタン酸リチウムをジェットミルで解砕し、試料1を得た。
実施例1において、リチウム化合物として、試料cを用いた以外は、実施例1と同様にして、試料2を得た。
実施例1において、リチウム化合物として、試料dを用いた以外は、実施例1と同様にして、試料3を得た。
実施例1において、リチウム化合物として、試料aを用いた以外は、実施例1と同様にして、試料4を得た。
実施例1において、リチウム化合物として、試料eを用いた以外は、実施例1と同様にして、試料5を得た。
比較例1において、大気中800℃で3時間の加熱を行った以外は比較例1と同様にして、試料6を得た。
得られた試料1~6について、粉末X線回折装置(リガク社製 UltimaIV Cukα線使用)を用いて粉末X線回折パターンを測定した。試料1,4,6の粉末X線回折測定結果を図1に示す。測定されたピーク強度のうち、Xとして、2θ=18°付近のLi4Ti5O12のピーク強度を、Yとして2θ=27°付近のルチル型TiO2のピーク強度、2θ=25°付近のアナターゼ型TiO2のピーク強度及び2θ=44°付近のLi2TiO3のピーク強度を用いて前述の単相率を算出した。結果を表2に示す。粉砕を行い体積平均粒径が5μm以下の炭酸リチウムを用いた試料1~3では、750℃の加熱でも単相率95%以上のチタン酸リチウムLi4Ti5O12が得られたのに対し、体積平均粒径が5μmを越える炭酸リチウムを用いた場合、750℃での加熱(試料4,5)では単相率が95%以上のチタン酸リチウムLi4Ti5O12は得られず、800℃で加熱(試料6)することでようやく単相率が95%以上のチタン酸リチウムLi4Ti5O12が得られた。このことから、本発明の製造方法により、チタン酸リチウム合成時の加熱温度が低くても、具体的には800℃未満でも、単相率が95%以上のチタン酸リチウムを合成できることがわかる。
単相率が95%以上であった試料1及び試料6について、BET一点法(窒素吸着、ユアサアイオニクス社製モノソーブ)にて比表面積を測定した。その結果、比表面積はそれぞれ4.9m2/g、3.0m2/gであった。このことから、本発明の製造方法により、単相率が95%以上のチタン酸リチウムを合成しても、チタン酸リチウム粒子同士の焼結を抑制し、粉砕が容易で比表面積の低下が抑制されたチタン酸リチウムを合成できることがわかる。
電池特性の評価
(1)蓄電デバイスの作成
試料1のチタン酸リチウムと、導電剤としてのアセチレンブラック粉末、及び結着剤としてのポリフッ化ビニリデン樹脂を重量比で100:5:7で混合し、乳鉢で練り合わせ、ペーストを調製した。このペーストをアルミ箔上に塗布し、120℃の温度で10分乾燥した後、直径12mmの円形に打ち抜き、17MPaでプレスして作用極とした。電極中に含まれる活物質量は、3mgであった。
この作用極を120℃の温度で4時間真空乾燥した後、露点-70℃以下のグローブボックス中で、密閉可能なコイン型セルに正極として組み込んだ。コイン型セルには材質がステンレス製(SUS316)で外径20mm、高さ3.2mmのものを用いた。負極には厚み0.5mmの金属リチウムを直径12mmの円形に成形したものを用いた。非水電解液として1モル/リットルとなる濃度でLiPF6を溶解したエチレンカーボネートとジメチルカーボネートの混合溶液(体積比で1:2に混合)を用いた。
作用極はコイン型セルの下部缶に置き、その上にセパレータとして多孔性ポリプロピレンフィルムを置き、その上から非水電解液を滴下した。さらにその上に負極と、厚み調整用の0.5mm厚スペーサー及びスプリング(いずれもSUS316製)をのせ、ポリプロピレン製ガスケットのついた上部缶を被せて外周縁部をかしめて密封し、本発明の蓄電デバイス(試料A)を得た。
上記で作製した蓄電デバイス(試料A,B)について、種々の電流量で放電容量を測定して容量維持率(%)を算出した。測定は、電圧範囲を1~3Vに、充電電流は0.25Cに、放電電流は0.25C~30Cの範囲に設定して行った。環境温度は25℃とした。容量維持率は、0.25Cでの放電容量の測定値をX0.25、0.5C~30Cの範囲での測定値をXnとすると、(Xn/X0.25)×100の式で算出した。尚、ここで1Cとは、1時間で満充電できる電流値を言い、本評価では、0.48mAが1Cに相当する。容量維持率が高いほうが、レート特性が優れている。結果を、図2に示す。本発明の蓄電デバイス(試料A)は、比較例の蓄電デバイス(試料B)より、レート特性に優れていることが判る。
また、上記の方法で製造したチタン酸リチウムを電極活物質として用いると、電池特性、特にレート特性に優れた蓄電デバイスを製造することができる。
Claims (15)
- 少なくとも以下の2種の化合物を加熱するチタン酸リチウムの製造方法
(1)チタン化合物
(2)レーザー回折法で測定した体積平均粒径が5μm以下のリチウム化合物。 - 前記リチウム化合物は、粉砕により体積平均粒径5μm以下にされたものである請求項1に記載のチタン酸リチウムの製造方法。
- チタン化合物が、レーザー回折法で測定した体積平均粒径が0.5~5μmのチタン化合物である、請求項1又は2に記載のチタン酸リチウムの製造方法。
- チタン化合物の体積平均粒径(Aμm)と、リチウム化合物の体積平均粒径(Bμm)の比(B/A)が、0.1~8である、請求項1~3に記載のチタン酸リチウムの製造方法。
- 下記式1で表される単相率が95%以上である請求項1~4のいずれかに記載のチタン酸リチウムの製造方法
(式1)単相率(%)=100×(1-Σ(Yi/X))
ここで、X,Yiはそれぞれ、Cukα線を用いた粉末X線回折測定における、目的とするチタン酸リチウムのメインピーク強度、各副相のメインピーク強度である。 - 前記加熱温度が700℃~800℃である請求項1~5のいずれかに記載のチタン酸リチウムの製造方法。
- 少なくとも以下の3種の化合物を加熱する請求項1~6のいずれかに記載のチタン酸リチウムの製造方法。
(1)チタン化合物
(2)体積平均粒径が5μm以下のリチウム化合物
(3)目的とするチタン酸リチウムと同じ結晶構造を有するチタン酸リチウム化合物 - 前記加熱の前に、少なくとも(1)チタン化合物と、(2)体積平均粒径が5μm以下のリチウム化合物とを乾式混合する、請求項1~6のいずれかに記載のチタン酸リチウムの製造方法。
- 前記加熱の前に、少なくとも、(1)チタン化合物と、(2)体積平均粒径が5μm以下のリチウム化合物と、(3)目的とするチタン酸リチウムと同じ結晶構造を有するチタン酸リチウム化合物とを乾式混合する、請求項7に記載のチタン酸リチウムの製造方法。
- 前記乾式混合を乾式粉砕機で行う、請求項8又は9に記載のチタン酸リチウムの製造方法。
- 前記乾式粉砕機が気流式粉砕機である、請求項10に記載のチタン酸リチウムの製造方法。
- 前記リチウム化合物が炭酸リチウムである、請求項1~11のいずれかに記載のチタン酸リチウムの製造方法。
- 請求項1~12のいずれかの製造方法で得られたチタン酸リチウム。
- 請求項13に記載のチタン酸リチウムを含む電極活物質。
- 請求項13に記載のチタン酸リチウムを用いた蓄電デバイス。
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JP2013512430A JP5896994B2 (ja) | 2011-04-28 | 2012-04-26 | チタン酸リチウムの製造方法 |
CA2834140A CA2834140A1 (en) | 2011-04-28 | 2012-04-26 | Process for manufacturing lithium titanium oxides |
US14/113,855 US9446964B2 (en) | 2011-04-28 | 2012-04-26 | Process for manufacturing lithium titanium oxides |
CN201280020615.XA CN103502151B (zh) | 2011-04-28 | 2012-04-26 | 生产钛酸锂的方法 |
EP12777196.2A EP2703355A4 (en) | 2011-04-28 | 2012-04-26 | METHOD FOR MANUFACTURING LITHIUM TITANIUM OXIDES |
KR1020137030364A KR101881185B1 (ko) | 2011-04-28 | 2012-04-26 | 티탄산리튬의 제조 방법 |
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US20150050557A1 (en) * | 2013-08-13 | 2015-02-19 | Toyota Jidosha Kabushiki Kaisha | Negative electrode active material for sodium-ion battery and sodium-ion battery |
EP2765634B1 (en) * | 2013-02-07 | 2016-01-20 | Kabushiki Kaisha Toshiba | Electrode, nonaqueous electrolyte battery and battery pack |
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EP2703354A4 (en) * | 2011-04-28 | 2015-03-25 | Ishihara Sangyo Kaisha | METHOD FOR MANUFACTURING LITHIUM TITANATE PRECURSOR, METHOD FOR MANUFACTURING LITHIUM TITANATE, LITHIUM TITANATE, ELECTRODE ACTIVE SUBSTANCE, AND STORAGE DEVICE |
KR102059396B1 (ko) | 2012-01-13 | 2019-12-26 | 알베마를 저머니 게엠베하 | 합금-형성 원소로 코팅된 안정화된 리튬 금속 형성물 및 이의 생산 방법 |
WO2015111694A1 (ja) * | 2014-01-24 | 2015-07-30 | 独立行政法人産業技術総合研究所 | チタン酸化合物、チタン酸アルカリ金属化合物及びそれらの製造方法並びにそれらを活物質として用いた蓄電デバイス |
US11165059B2 (en) * | 2017-03-13 | 2021-11-02 | Lg Chem, Ltd. | Negative electrode active material having high output characteristics and lithium secondary battery including the same |
CN110725006B (zh) * | 2018-07-16 | 2020-10-16 | 中国工程物理研究院材料研究所 | 一种毫米级针状固态氚增殖剂钛酸锂单晶的制备方法 |
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US20140050657A1 (en) | 2014-02-20 |
JPWO2012147854A1 (ja) | 2014-07-28 |
TWI561472B (en) | 2016-12-11 |
KR20140028002A (ko) | 2014-03-07 |
CN103502151B (zh) | 2016-01-13 |
CA2834140A1 (en) | 2012-11-01 |
US9446964B2 (en) | 2016-09-20 |
CN103502151A (zh) | 2014-01-08 |
KR101881185B1 (ko) | 2018-07-23 |
EP2703355A1 (en) | 2014-03-05 |
TW201305055A (zh) | 2013-02-01 |
EP2703355A4 (en) | 2015-01-14 |
JP5896994B2 (ja) | 2016-03-30 |
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