WO2012086557A1 - リチウム二次電池 - Google Patents
リチウム二次電池 Download PDFInfo
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- WO2012086557A1 WO2012086557A1 PCT/JP2011/079259 JP2011079259W WO2012086557A1 WO 2012086557 A1 WO2012086557 A1 WO 2012086557A1 JP 2011079259 W JP2011079259 W JP 2011079259W WO 2012086557 A1 WO2012086557 A1 WO 2012086557A1
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- WIPO (PCT)
- Prior art keywords
- sintered body
- lithium titanate
- lithium
- negative electrode
- positive electrode
- Prior art date
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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
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
- C01P2006/10—Solid density
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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
- C01P2006/16—Pore diameter
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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
- C01P2006/40—Electric properties
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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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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 high capacity, high output lithium secondary battery.
- the active material utilization is 80% or less when the active material filling rate is 80% or more, and the effect is small in terms of improving the energy density and battery capacity of the battery. It is insufficient.
- the present invention has been proposed in view of such circumstances, and an object thereof is to provide a lithium secondary battery having higher energy density and battery capacity.
- the lithium secondary battery of the present invention includes a positive electrode, a negative electrode, and a nonaqueous electrolyte sandwiched between the positive electrode and the negative electrode, and the positive electrode or the negative electrode is made of a lithium titanate sintered body,
- the lithium titanate sintered body has an average pore diameter of 0.10 to 0.20 ⁇ m, a specific surface area of 1.0 to 3.0 m 2 / g, and a relative density of 80 to 90%.
- the lithium secondary battery according to the present invention is a lithium titanate sintered body having an average pore diameter of 0.10 to 0.20 ⁇ m, a specific surface area of 1.0 to 3.0 m 2 / g, and a relative density of 80 to 90%.
- a lithium secondary battery having high energy density and excellent charge / discharge characteristics can be obtained.
- FIG. 1 is a cross-sectional view showing a lithium secondary battery according to an embodiment of the present invention, in which a separator 4 containing a nonaqueous electrolyte is sandwiched between a pair of electrodes composed of a positive electrode 3 and a negative electrode 7. .
- the positive electrode can 1 is bonded to the positive electrode 3 by the positive electrode current collector 2 and is caulked through the insulating packing 8 with the negative electrode can 5 bonded to the negative electrode 7 by the negative electrode current collector 6.
- the positive electrode current collector 2 or the negative electrode current collector 6 is arranged for collecting the current of the positive electrode 3 or the negative electrode 7, and for example, carbon black, graphite, gold, silver, nickel, zinc oxide, tin oxide, indium oxide, oxidation
- a conductive filler composed of at least one of titanium and titanium potassium oxide, and at least one type of acrylic resin, epoxy resin, silicon resin, polyamide resin, phenol resin, polyester resin, and polyimide resin.
- the positive electrode 3 or the negative electrode 7 is made of a lithium titanate sintered body, and has an average pore diameter of 0.10 to 0.20 ⁇ m, a specific surface area of 1.0 to 3.0 m 2 / g, and a relative density of 80 to 90%. is there.
- the positive electrode 3 or the negative electrode 7 is made of a lithium titanate sintered body having a relative density of 80 to 90%, so that the active material is densely packed, and has high energy density and excellent charge / discharge characteristics. It will be.
- the lithium titanate sintered body constituting the positive electrode 3 or the negative electrode 7 has an average pore diameter of 0.10 to 0.20 ⁇ m and a specific surface area of 1.0 to 3.0 m 2 / g.
- the electrolyte solution is sufficiently immersed in the sintered body to ensure a contact area between the electrolyte solution and the electrode active material, and at the same time, the relative density of the lithium titanate sintered body can be increased to 80% or more.
- the packing density can be increased.
- the average pore diameter is less than 0.10 ⁇ m or the specific surface area is larger than 3.0 m 2 / g, it is difficult to increase the relative density of the lithium titanate sintered body to 80% or more, and the energy density cannot be increased. .
- the average pore diameter is larger than 0.20 ⁇ m or the specific surface area is smaller than 1.0 m 2 / g, the relative density is larger than 90% and the energy density is increased, but the electrolyte is made of lithium titanate.
- the contact area between the electrolytic solution and the electrode active material is reduced, and a large voltage drop occurs during charging and discharging.
- the average particle diameter of the particles constituting the lithium titanate sintered body is preferably 0.5 ⁇ m or less.
- the average particle diameter 0.5 ⁇ m or less By making the average particle diameter 0.5 ⁇ m or less, the diffusion distance of Li ions in the particles can be shortened, the ion conduction resistance can be reduced, and the average pore diameter, specific surface area and relative density are in the above ranges. It becomes easy. Further, when the average particle diameter is larger than 0.5 ⁇ m, the discharge potential may be lowered.
- the average pore diameter of a lithium titanate sintered compact using a mercury intrusion method can be computed from the amount of adsorption gas of the sintered compact measured by the gas adsorption method.
- the relative density may be calculated from the sintered body density measured by the Archimedes method and the theoretical density of Li 4 Ti 5 O 12 of 3.48 g / cm 3 .
- the average particle diameter of the particles constituting the lithium titanate sintered body may be obtained, for example, by heat-treating the fracture surface of the sintered body and analyzing the cross-sectional photograph taken with a scanning electron microscope (SEM).
- the thickness of the positive electrode 3 or the negative electrode 7 composed of the lithium titanate sintered body is preferably 20 ⁇ m to 200 ⁇ m. As a result, the absolute amount of the active material necessary for improving the energy density and battery capacity of the battery can be ensured, the electrode has good charge / discharge characteristics, good handling properties and easy handling.
- the bending strength is preferably 50 MPa or more from the viewpoint of handling properties.
- the bending strength can be measured by a four-point bending method or a three-point bending method based on JIS R 1601, and a converted strength based on the sample dimensions can also be used.
- the lithium titanate sintered body contains at least one of rutile type titanium oxide crystal particles and anatase type titanium oxide crystal particles, and Li 4 Ti 5 O 12 by X-ray diffraction (XRD).
- XRD X-ray diffraction
- the X-ray diffraction peak intensity ratio is determined by measuring the peak intensity of the sintered body by an X-ray diffraction method using Cu—K ⁇ rays, and Li 4 Ti 5 O 12 (111) having a diffraction angle 2 ⁇ of around 18.3 °.
- the diffraction angle 2 ⁇ of around 18.3 ° means that it is within an error range of ⁇ 0.3 °.
- an error range of ⁇ 0.3 ° is indicated.
- Lithium titanate (Li 4 Ti 5 O 12 ) is synthesized, for example, by mixing and calcining lithium hydroxide and titanium dioxide.
- rutile titanium oxide and anatase oxidation are used as the impurity phase. Titanium, Li 2 TiO 3 and the like are likely to be contained, and these crystalline phases are inactive or have a small battery capacity, so that the effective capacity of a lithium secondary battery using a lithium titanate sintered body as a negative electrode is reduced. .
- the Li 4 Ti 5 O 12 sintered body used as the positive electrode 3 or the negative electrode 7 is composed of Li 4 Ti 5 O 12 crystal, rutile titanium oxide, and anatase titanium oxide. It is desirable that the XRD peak intensity ratio is in the above range.
- examples of the active material used for the positive electrode 3 include lithium cobalt composite oxide, lithium manganese composite oxide, manganese dioxide, lithium nickel composite oxide, and lithium nickel cobalt composite. Examples thereof include oxides, lithium vanadium composite oxides, and vanadium oxide.
- the positive electrode 3 is also a sintered body having an average pore diameter of 0.10 to 0.20 ⁇ m, a specific surface area of 1.0 to 3.0 m 2 / g, and a relative density of 80 to 90%. Preferably there is.
- examples of the active material used for the negative electrode 7 include carbon materials such as graphite, hard carbon, and soft carbon, alloys that can insert and desorb Li and Li, and the like. Is mentioned.
- any of the following (1) to (3) may be used for the production of an electrode comprising such a lithium titanate sintered body.
- a raw material powder of lithium titanate was mixed with a molding aid, water or a solvent with a dispersant and a plasticizer added as necessary to prepare a slurry, and this slurry was applied to a substrate film and dried. Then, it peels from a base film and it sinters.
- the raw material powder of lithium titanate is directly or granulated, put into a mold, pressed with a press machine, and then sintered.
- the granulated raw material powder of lithium titanate is pressure-formed with a roll press machine, processed on a sheet, and sintered.
- the granulation of (2) and (3) may be either wet granulation or dry granulation from the slurry described in the method (1).
- molding aid examples include one or a mixture of two or more of polyacrylic acid, carboxymethyl cellulose, polyvinylidene fluoride, polyvinyl alcohol, diacetyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, polyvinyl pyrrolidone, butyral, and the like. .
- the base film for example, a resin film of polyethylene terephthalate, polypropylene, polyethylene, tetrafluoroethylene, or the like can be used.
- the firing temperature may be appropriately selected in the range of 700 to 900 ° C. according to the sinterability of the raw material powder.
- the fine lithium titanate raw material contains about 1% by mass of titanium oxide as an unavoidable impurity.
- a low temperature 900 ° C. or lower, preferably 800 ° C. or lower
- lithium titanate at the time of firing is used. Can be prevented, and the amount of impurities can be prevented from increasing.
- the temperature is higher than 900 ° C., titanium oxide is generated as a different phase due to decomposition of lithium titanate, and the electrode characteristics are deteriorated.
- a fine powder (Li 4 Ti 5 O 12 ) having a specific surface area of 20 m 2 / g or more and a primary particle size of 0.1 ⁇ m or less is used. It is preferable to use one of 50 m 2 / g, 0.05 to 0.1 ⁇ m. By using such fine powder, the pore diameter after sintering can be reduced, the specific surface area can be increased, and densification at low temperature can be achieved, so that a dense sintered body having no heterogeneous phase can be obtained.
- the binder is preferably a butyral binder. Since the butyral binder has high strength, the amount added can be reduced, and a high-density sintered body can be obtained.
- the amount of the binder is preferably 10% by volume or less with respect to the active material.
- organic solvent used in the organic electrolyte examples include ethylene carbonate, propylene carbonate, butylene carbonate, ⁇ -butyrolactone, sulfolane, 1,2-dimethoxyethane, 1,3-dimethoxypropane, dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and carbonic acid.
- the solvent which mixed 1 type, or 2 or more types chosen from dimethyl, diethyl carbonate, and methyl ethyl carbonate is mentioned.
- electrolyte salt examples include lithium salts such as LiClO 4 , LiBF 4 , LiPF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , and LiN (C 2 F 5 SO 2 ) 2 .
- separator 4 for example, a nonwoven fabric made of polyolefin fibers or a microporous membrane made of polyolefin fibers can be used.
- the polyolefin fiber include polyethylene fiber and polypropylene fiber.
- the positive electrode can 1 to which the positive electrode 3 is bonded by the positive electrode current collector 2 and the negative electrode can 5 to which the negative electrode 7 is bonded by the negative electrode current collector 6 are caulked through an insulating packing 8 and sealed.
- the shape of the lithium secondary battery of the present invention is not limited to a square shape, a cylindrical shape, a button shape, a coin shape, a flat shape, or the like.
- the positive electrode 3 or the negative electrode 7 is made into a sintered body having a relative density of 80 to 90%, so that the active material is densely packed, and has high energy density and excellent charge / discharge characteristics. .
- an electron conduction aid In the case of an oxide-based active material, an electron conduction aid must be added in order to provide conductivity in a normal usage method.
- the positive electrode 3 or the negative electrode 7 of the lithium secondary battery of the present invention Then, by making the active material a dense sintered body, the contact area between the active material particles increases, and sufficient electron conductivity can be obtained without using an electron conduction aid.
- the electrode which is the positive electrode 3 or the negative electrode 7 is made dense, the penetration of the electrolytic solution into the electrode and the interface between the electrolytic solution and the active material decrease, and the charge / discharge characteristics deteriorate, but the average pore diameter of the electrode Of 0.10 to 0.20 ⁇ m and a specific surface area of 1.0 to 3.0 m 2 / g, the penetration of the electrolyte into the electrode and the contact area between the electrolyte and the active material are secured,
- the electrode can achieve both high energy density and excellent charge / discharge characteristics.
- a slurry is prepared by adding a molding aid, a plasticizer, a dispersant and a solvent to a Li 4 Ti 5 O 12 raw material having a specific surface area of 35 m 2 / g, an average particle size of 0.1 ⁇ m and an impurity content of 0.8%. did.
- the impurity content mentioned here means I T / I LT in the X-ray diffraction of the raw material powder.
- This slurry was applied on a polyethylene terephthalate (PET) film by a doctor blade method and then dried to prepare a green sheet having a thickness of 55 to 65 ⁇ m. This green sheet was punched out so as to have a circular shape with a diameter of 15 mm after firing, and fired at a temperature shown in Table 1 in the air.
- PET polyethylene terephthalate
- the thicknesses of the obtained lithium titanate sintered bodies were all 50 ⁇ m, and the average pore diameter, BET specific surface area, relative density, bending strength, and average particle diameter were measured for each, and the results are shown in Table 1. Further, the XRD peak intensity ratio I T / I LT between the Li 4 Ti 5 O 12 crystal and the titanium oxide crystal is determined from the peak intensity of the lithium titanate sintered body measured by the X-ray diffraction method using Cu—K ⁇ ray. rutile titanium oxide crystal (110) plane and anatase type titanium oxide crystal (101) of the surface, a higher strength to calculate the I T / I LT as I T, as described in Table 1.
- the average pore diameter was measured using a mercury intrusion method.
- the amount of adsorbed gas of the sintered body was measured by a gas adsorption method, and the BET surface area was calculated.
- the relative density was calculated from the sintered body density measured by Archimedes method and the theoretical density of Li 4 Ti 5 O 12 of 3.48 g / cm 3 .
- the bending strength was measured by a four-point bending method based on JIS R 1601.
- the average particle size of the particles constituting the sintered body is obtained by heat-treating the fracture surface of the sintered body, then taking a cross-sectional photograph with a scanning electron microscope (SEM), and with an area of 20,000 times and 10 ⁇ 10 ⁇ m. Calculation was performed by image analysis.
- SEM scanning electron microscope
- a battery cell was assembled with a working electrode obtained by attaching these sintered bodies to a current collecting metal plate with a conductive adhesive and a counter electrode obtained by pressure bonding a Li metal foil to the current collecting metal plate with a separator interposed therebetween.
- a separator a polyethylene non-woven fabric impregnated with an organic electrolyte solution is used, and hexafluorophosphorus is added to a solvent in which ethylene carbonate (EC) and dimethyl carbonate (DMC) are mixed at a volume ratio of 3: 7 as the organic electrolyte solution.
- lithium acid (LiPF 6) was used by dissolving in 1 mol / L.
- the battery cell produced as described above was subjected to a charge / discharge test at a current value corresponding to a 10 hour rate.
- the charge end voltage was 2.5V
- the discharge end voltage was 0.4V.
- the active material utilization rate was 100% for all battery cells.
- the battery capacity per unit volume of the sintered body used for the working electrode was calculated using the measured capacity and listed in Table 1.
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Abstract
Description
(1)チタン酸リチウムの原料粉末を、成形助剤、必要に応じて分散剤、可塑剤を加えた水もしくは溶剤と混合してスラリーを調整し、このスラリーを基材フィルムに塗布、乾燥した後、基材フィルムから剥離させ、焼結させる。
(2)チタン酸リチウムの原料粉末を直接もしくは造粒したものを金型に投入し、プレス機で加圧成形した後、焼結させる。
(3)造粒したチタン酸リチウムの原料粉末をロールプレス機で加圧成形してシート上に加工し、焼結させる。
(2)及び(3)の造粒については、(1)の方法で述べたスラリーから造粒する湿式造粒であっても乾式造粒であってもよい。
Claims (4)
- 正極と、負極と、前記正極と前記負極の間に挟持された非水電解質とを有し、前記正極または前記負極がチタン酸リチウム焼結体からなり、該チタン酸リチウム焼結体が、0.10~0.20μmの平均細孔径、1.0~3.0m2/gの比表面積、80~90%の相対密度を有することを特徴とするリチウム二次電池。
- 前記チタン酸リチウム焼結体を構成する粒子の平均粒子径が0.5μm以下であることを特徴とする請求項1に記載のリチウム二次電池。
- 前記チタン酸リチウム焼結体の抗折強度が50MPa以上であることを特徴とする請求項1または2記載のリチウム二次電池。
- 前記チタン酸リチウム焼結体が、ルチル型の結晶構造を有する酸化チタン結晶粒子およびアナターゼ型の結晶構造を有する酸化チタン結晶粒子のうち少なくとも1種を含有し、前記チタン酸リチウム焼結体のX線回折パターンにおいて、酸化チタン結晶の前記ルチル型の結晶構造の(110)面を示すX線回折ピークおよびアナターゼ型の結晶構造の(101)面を示すX線回折ピークのうち、強度の高い方のX線回折ピークの強度がLi4Ti5O12結晶の(111)面を示すX線回折ピークの強度に対して、1.5%以下であることを特徴とする請求項1乃至3のいずれかに記載のリチウム二次電池。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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KR1020137003826A KR101497990B1 (ko) | 2010-12-24 | 2011-12-17 | 리튬 2차 전지 |
EP11851658.2A EP2658012B1 (en) | 2010-12-24 | 2011-12-17 | Lithium rechargeable battery |
CN201180039702.5A CN103069621B (zh) | 2010-12-24 | 2011-12-17 | 锂二次电池 |
JP2012521410A JP5174283B2 (ja) | 2010-12-24 | 2011-12-17 | リチウム二次電池 |
US13/819,302 US9209451B2 (en) | 2010-12-24 | 2011-12-17 | Lithium rechargeable battery comprising a lithium titanate sintered body |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2010-288124 | 2010-12-24 | ||
JP2010288124 | 2010-12-24 |
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WO2012086557A1 true WO2012086557A1 (ja) | 2012-06-28 |
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PCT/JP2011/079259 WO2012086557A1 (ja) | 2010-12-24 | 2011-12-17 | リチウム二次電池 |
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US (1) | US9209451B2 (ja) |
EP (1) | EP2658012B1 (ja) |
JP (1) | JP5174283B2 (ja) |
KR (1) | KR101497990B1 (ja) |
CN (1) | CN103069621B (ja) |
WO (1) | WO2012086557A1 (ja) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US20140265915A1 (en) * | 2013-03-15 | 2014-09-18 | Apple Inc. | Thin Film Encapsulation Battery Systems |
JP2014231639A (ja) * | 2013-04-30 | 2014-12-11 | 株式会社コベルコ科研 | Li含有酸化物ターゲット接合体 |
JP2014238925A (ja) * | 2013-06-06 | 2014-12-18 | 日本碍子株式会社 | 全固体電池 |
US20150159996A1 (en) * | 2013-12-09 | 2015-06-11 | Seiko Epson Corporation | Measuring method of utilization depth of active material, manufacturing method of lithium secondary battery, and the lithium secondary battery |
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US10141600B2 (en) | 2013-03-15 | 2018-11-27 | Apple Inc. | Thin film pattern layer battery systems |
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WO2020217579A1 (ja) * | 2019-04-26 | 2020-10-29 | 日本碍子株式会社 | リチウム二次電池 |
US10930915B2 (en) | 2014-09-02 | 2021-02-23 | Apple Inc. | Coupling tolerance accommodating contacts or leads for batteries |
JPWO2021100282A1 (ja) * | 2019-11-20 | 2021-05-27 | ||
US11824220B2 (en) | 2020-09-03 | 2023-11-21 | Apple Inc. | Electronic device having a vented battery barrier |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2975668B1 (en) * | 2013-03-14 | 2017-12-20 | Kabushiki Kaisha Toshiba | Battery system |
JP6220365B2 (ja) * | 2015-06-30 | 2017-10-25 | 宇部興産株式会社 | 蓄電デバイスの電極用チタン酸リチウム粉末および活物質材料、並びにそれを用いた電極シートおよび蓄電デバイス |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001192208A (ja) * | 1999-06-03 | 2001-07-17 | Titan Kogyo Kk | 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 |
JP2002042785A (ja) | 2000-07-21 | 2002-02-08 | Kyocera Corp | リチウム電池 |
JP2002289194A (ja) * | 2001-03-27 | 2002-10-04 | Toho Titanium Co Ltd | リチウムイオン二次電池電極活物質製造原料としての二酸化チタン粉、リチウムイオン二次電池電極活物質としてのチタン酸リチウムおよびその製造方法 |
WO2012002122A1 (ja) * | 2010-07-02 | 2012-01-05 | 大塚化学株式会社 | 多孔質チタン酸リチウムの製造方法、多孔質チタン酸リチウム及びそれを用いたリチウム電池 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4413888B2 (ja) * | 2006-06-13 | 2010-02-10 | 株式会社東芝 | 蓄電池システム、車載電源システム、車両、および蓄電池システムの充電方法 |
KR20090101967A (ko) * | 2007-01-19 | 2009-09-29 | 스텔라 케미파 가부시키가이샤 | 축전소자 |
JP5430849B2 (ja) * | 2007-12-27 | 2014-03-05 | 株式会社東芝 | 非水電解質電池 |
DE102008026580A1 (de) | 2008-06-03 | 2009-12-10 | Süd-Chemie AG | Verfahren zur Herstellung von Lithiumtitan-Spinell und dessen Verwendung |
CN101409341B (zh) * | 2008-11-20 | 2010-11-03 | 上海交通大学 | 一种应用于锂离子电池的钛酸锂负极材料的制备方法 |
-
2011
- 2011-12-17 JP JP2012521410A patent/JP5174283B2/ja active Active
- 2011-12-17 CN CN201180039702.5A patent/CN103069621B/zh active Active
- 2011-12-17 US US13/819,302 patent/US9209451B2/en active Active
- 2011-12-17 KR KR1020137003826A patent/KR101497990B1/ko active IP Right Grant
- 2011-12-17 WO PCT/JP2011/079259 patent/WO2012086557A1/ja active Application Filing
- 2011-12-17 EP EP11851658.2A patent/EP2658012B1/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001192208A (ja) * | 1999-06-03 | 2001-07-17 | Titan Kogyo Kk | 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 |
JP2002042785A (ja) | 2000-07-21 | 2002-02-08 | Kyocera Corp | リチウム電池 |
JP2002289194A (ja) * | 2001-03-27 | 2002-10-04 | Toho Titanium Co Ltd | リチウムイオン二次電池電極活物質製造原料としての二酸化チタン粉、リチウムイオン二次電池電極活物質としてのチタン酸リチウムおよびその製造方法 |
WO2012002122A1 (ja) * | 2010-07-02 | 2012-01-05 | 大塚化学株式会社 | 多孔質チタン酸リチウムの製造方法、多孔質チタン酸リチウム及びそれを用いたリチウム電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2658012A4 |
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---|---|---|---|---|
US10439187B2 (en) | 2012-11-27 | 2019-10-08 | Apple Inc. | Laminar battery system |
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US9870902B2 (en) | 2013-04-30 | 2018-01-16 | Kobelco Research Institute, Inc. | Li-containing oxide target assembly |
JP2014231639A (ja) * | 2013-04-30 | 2014-12-11 | 株式会社コベルコ科研 | Li含有酸化物ターゲット接合体 |
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US11211600B2 (en) | 2017-05-15 | 2021-12-28 | Ngk Insulators, Ltd. | Lithium titanate sintered plate |
JP6392493B1 (ja) * | 2017-05-15 | 2018-09-19 | 日本碍子株式会社 | チタン酸リチウム焼結体板 |
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WO2018212038A1 (ja) * | 2017-05-15 | 2018-11-22 | 日本碍子株式会社 | チタン酸リチウム焼結体板 |
JPWO2019221141A1 (ja) * | 2018-05-17 | 2020-12-10 | 日本碍子株式会社 | コイン形リチウム二次電池及びIoTデバイス |
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Also Published As
Publication number | Publication date |
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EP2658012B1 (en) | 2017-07-26 |
KR20130055644A (ko) | 2013-05-28 |
JP5174283B2 (ja) | 2013-04-03 |
EP2658012A4 (en) | 2016-11-23 |
CN103069621A (zh) | 2013-04-24 |
US20130157137A1 (en) | 2013-06-20 |
JPWO2012086557A1 (ja) | 2014-05-22 |
KR101497990B1 (ko) | 2015-03-03 |
US9209451B2 (en) | 2015-12-08 |
EP2658012A1 (en) | 2013-10-30 |
CN103069621B (zh) | 2015-07-22 |
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