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WO2012169331A1 - Particules primaires de titanate de lithium, agrégat de titanate de lithium, batterie secondaire au lithium-ion mettant en oeuvre les particules primaires de titanate de lithium ou l'agrégat de titanate de lithium et condensateur au lithium-ion mettant en oeuvre les particules primaires de titanate de lithium ou l'agrégat de titanate de lithium - Google Patents

Particules primaires de titanate de lithium, agrégat de titanate de lithium, batterie secondaire au lithium-ion mettant en oeuvre les particules primaires de titanate de lithium ou l'agrégat de titanate de lithium et condensateur au lithium-ion mettant en oeuvre les particules primaires de titanate de lithium ou l'agrégat de titanate de lithium Download PDF

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Publication number
WO2012169331A1
WO2012169331A1 PCT/JP2012/062724 JP2012062724W WO2012169331A1 WO 2012169331 A1 WO2012169331 A1 WO 2012169331A1 JP 2012062724 W JP2012062724 W JP 2012062724W WO 2012169331 A1 WO2012169331 A1 WO 2012169331A1
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Prior art keywords
lithium titanate
lithium
primary particles
aggregate
negative electrode
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PCT/JP2012/062724
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English (en)
Japanese (ja)
Inventor
新井　良幸
英樹 堺
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Toho Titanium Co Ltd
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Toho Titanium Co Ltd
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Priority to JP2013519428A priority Critical patent/JP5940529B2/ja
Publication of WO2012169331A1 publication Critical patent/WO2012169331A1/fr
Anticipated expiration legal-status Critical
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • 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
    • 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
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to lithium titanate primary particles suitable for lithium ion secondary batteries and electrodes of capacitors, and lithium titanate aggregates.
  • Lithium ion secondary batteries have rapidly spread in recent years because of their excellent cycle characteristics.
  • An electrode active material of a lithium secondary battery in particular, a negative electrode active material, has an alkali metal titanate compound having a high discharge potential and excellent safety, for example, a lithium titanium compound having a spinel structure or a ramsdellite structure Attention has been focused on titanium compounds and the like.
  • the spinel type lithium titanate has a theoretical capacity of 175 mAh / g, and the change in volume during charge and discharge is small, so it is excellent in cycle characteristics.
  • a method for producing spinel-type lithium titanate a mixture of lithium carbonate, lithium hydroxide, lithium nitrate and lithium oxide selected from lithium oxide and lithium oxide and titanium oxide is calcined at 670 ° C. or more and less than 800 ° C. Then, a method is proposed in which a composition composed of TiO 2 and Li 2 TiO 3 or a composition composed of TiO 2 , Li 2 TiO 3 and Li 4 Ti 5 O 12 is prepared and then this firing is carried out. (See, for example, Patent Document 1).
  • the shape of secondary particles in which primary particles are aggregated is spherical, and the specific surface area is 0.5 to 10 m 2 / g
  • Method using lithium titanate having an oil absorption of 30 g / 100 g or more and 60 g / 100 g or less and the main component is Li 4/3 Ti 5/3 O 4 as a negative electrode active material see, for example, Patent Document 2
  • Li A method of using lithium titanate containing 4 Ti 5 O 12 as a main component, a small ratio of impurities such as TiO 2 and Li 2 TiO 3 , and a crystallite diameter of 700 ⁇ to 800 ⁇ as a negative electrode active material see, for example, Patent Document 3) Etc.
  • Patent Literatures 2 to 5 has been essentially improved, and the improvement of the characteristics such as the discharge characteristics and the cycle characteristics of the lithium secondary battery characteristics is insufficient. .
  • This invention is made in view of such a subject, and makes it a main purpose to provide the lithium titanate particle active material which can improve the electric capacity and the cycling characteristics at the time of rapid charge and discharge more.
  • the inventors of the present invention conducted intensive studies, and as a result, when using lithium titanate primary particles having a specific shape as the negative electrode active material, the inventors were able to rapidly charge and discharge lithium ion secondary batteries. Capacitance and cycle characteristics, and rapid charge and discharge characteristics of a lithium ion capacitor can be further improved, and the present invention has been completed.
  • the lithium titanate primary particles according to the present invention are characterized in that they have a step-like structure in which smooth polygonal planes are stacked.
  • the lithium titanate aggregate according to the present invention is a lithium titanate aggregate formed by aggregating the lithium titanate primary particles having the step-like structure and the lithium titanate primary particles having any other shape.
  • the number of primary particles of lithium titanate having the step-like structure is 10% or more with respect to the total number of primary particles.
  • a lithium ion secondary battery comprises a positive electrode having a positive electrode active material capable of inserting and extracting lithium, and a lithium ion using the above lithium titanate primary particles or lithium titanate aggregate as a negative electrode active material A negative electrode for a secondary battery, and an ion conductive medium interposed between the positive electrode and the negative electrode for a lithium ion secondary battery to conduct lithium ions.
  • a negative electrode current collector is provided with a negative electrode active material layer provided with the above-mentioned negative electrode active material layer containing lithium titanate primary particles or lithium titanate aggregates.
  • a non-aqueous electrolytic solution including a lithium ion-containing electrolyte interposed between the positive electrode and the negative electrode.
  • the lithium titanate primary particles or the lithium titanate aggregate of the present invention in the lithium ion secondary battery, the electric capacity and the cycle characteristics at the time of rapid charge and discharge can be further enhanced.
  • the rapid charge / discharge characteristics (5 C or more: the current value for discharging all the battery capacity in 1 hour is “1 C”
  • the charge and discharge of 5 C or more can indicate that charge and discharge are performed at a current five times the current value).
  • the lithium titanate primary particles of the present invention are composed of step-like crystal faces, they are considered to exhibit a specifically low resistance when absorbing and releasing Li ions. Further, since the affinity between the lithium titanate primary particles or the lithium titanate aggregate of the present invention and the conductive assistant (carbon-based material) constituting the negative electrode is high, the possibility of reducing the contact resistance is considered.
  • FIG. It is a SEM photograph (50,000 times) of the lithium titanate aggregate obtained in Example 1.
  • FIG. It is a SEM photograph (5000 times) of the lithium titanate aggregate obtained in Example 1. It is a SEM photograph (50,000 times) of the lithium titanate aggregate obtained in Example 2. It is a SEM photograph (50,000 times) of the lithium titanate aggregate obtained in Example 3. It is a SEM photograph (50,000 times) of the lithium titanate aggregate obtained by the comparative example 1.
  • FIG. It is a SEM photograph (5000 times) of the lithium titanate aggregate obtained by comparative example 1. It is a SEM photograph (50,000 times) of the lithium titanate aggregate obtained in Comparative Example 2. It is sectional drawing which shows the structure of the coin cell used for evaluation of the lithium secondary battery characteristic evaluation method of an Example.
  • the lithium titanate primary particles according to the present invention are lithium titanate primary particles characterized in that they have a structure in which polygonal smooth flat surfaces are stacked in a step-like manner.
  • the shape of the smooth, polygonal surface of the lithium titanate primary particles according to the present invention is mainly square, and the stepped structure has a step (thickness of the plane) of 5 to 100 nm and a length of the stepped portion
  • the depth (step depth) is 5 to 500 nm, and the width of the step portion is 100 to 1000 nm.
  • the stepped structure is preferably a structure in which three or more steps of polygonal smooth flat surfaces are stacked.
  • the step-like structure is a polygon (for example, triangle, square (square, rectangle, etc.) with one side of 100 to 1000 nm on the top surface of the lithium titanate primary particle.
  • a pentagon and a hexagon are formed adjacent to smooth flat crystal planes (hereinafter abbreviated as A plane).
  • the lithium titanate of the lithium titanate primary particles according to the present invention is represented by the general formula Li x Ti Y O 12 , for example, Li 4 + x Ti 5 O 12 (0 ⁇ x ⁇ 3) having a spinel structure or And Li 2 + y Ti 3 O 7 (0 ⁇ y ⁇ 3) having a ramsteride structure.
  • the A plane is a crystal plane of ⁇ 111 ⁇ plane.
  • a lithium titanate aggregate having such a structure as an active material of a negative electrode for a lithium ion secondary battery, a large current (0.875 A / g or more (current value relative to the weight of the negative electrode active material)) can be obtained.
  • the electric capacity and the cycle characteristic at the time of rapid charge and discharge (5 C or more) can be further enhanced.
  • rapid charge and discharge characteristics can be improved.
  • the lithium oxide aggregate may be an aggregate characterized in that the number of lithium titanate primary particles of the present invention is 10% or more with respect to the total number of primary particles.
  • An aggregate refers to an aggregate in which primary particles that form an aggregate can be monodispersed by pulverizing treatment or mixing treatment with a solvent (such as water or an inert organic solvent). , Aggregates formed by bonding of primary particles by sintering or the like.
  • the lithium titanate aggregate of the present invention is preferable if all primary particles are particles of the shape according to the present invention, but if it is contained at least 10% or more, different shapes can be obtained without impairing the effects of the present invention. Particles can be mixed.
  • the ratio of lithium titanate primary particles according to the present invention, which are formed stepwise from a plurality of polygonal smooth flat surfaces, to form lithium titanate aggregates according to the present invention is more preferably the total number of primary particles.
  • lithium titanate particle aggregate having 30% or more is preferable, and 80% or more is more preferable.
  • the lithium titanate aggregate having a shape according to the present invention as an active material of a negative electrode for a lithium ion secondary battery, large current (0.875 A / g or more (current value relative to weight of negative electrode active material))
  • the electric capacity and the cycle characteristic at the time of rapid charge and discharge (5 C or more) can be further enhanced.
  • rapid charge and discharge characteristics can be improved.
  • the proportion of the number of particles is determined by the following method. Using an electron microscope, 100 fields of view are randomly observed at a magnification (10,000 to 100,000 times) at which the crystal surface of primary particles of lithium titanate aggregates can be sufficiently observed. Among the number of primary particles that can be observed in the field of view and the number of primary particles, the number of primary particles having the structure of the present invention is measured. This measurement is performed for 100 fields of view, and all primary particle numbers (M) and a plurality of polygonal smooth planes according to the present invention are stepwisely formed, and a part of the plurality of connecting planes are regularly arranged. The ratio N / M of the primary particle number (N) having a repeated stepwise structure is determined and determined.
  • the lithium titanate particle aggregate according to the present invention is not particularly limited, but the particle diameter is 20 ⁇ m or less, preferably 1 ⁇ m to 5 ⁇ m, and the specific surface area is 4.6 m 2 as measured by laser diffraction method.
  • the tap density is in the range of 0.6 to 1.5 g / cm 3 .
  • the shape is not particularly limited, for example, spherical, polyhedral, or indeterminate, but in view of battery characteristics, a shape having as small anisotropy as possible is advantageous, and spherical is more preferable.
  • the lithium titanate aggregate according to the present invention includes Li 4 + X Ti 5 O 12 (0 ⁇ x 3 3) having a spinel structure, in particular Li 4 Ti 5 O 12 .
  • a single phase is more preferable, but other phases such as titanium oxide and Li 2 TiO 3 may be mixed within a range not impairing the effects of the present invention, and the single phase conversion ratio is 90% or more (partially And Li 2 TiO 3 and TiO 2 may be mixed).
  • a lithium titanate aggregate having such a structure as an active material of a negative electrode for a lithium ion secondary battery, a large current (0.875 A / g or more (current value relative to the weight of the negative electrode active material)) can be obtained.
  • the electric capacity and the cycle characteristic at the time of rapid charge and discharge (5 C or more) can be further enhanced.
  • rapid charge and discharge characteristics can be improved.
  • the semi-quantitative software (“X'Part-HighScore Plus Ver. 2") of the analysis software "X'Part-HighScore Plus Ver. 2” is the diffraction result of measuring the lithium titanate aggregate according to the present invention using Semi-quantitative values analyzed for three components of Li 4 Ti 5 O 12 , TiO 2 (rutile phase) and Li 2 TiO 3 using PANalytical Co., Ltd.
  • Semi-quantitative values of Li 4 Ti 5 O 12 I A
  • semiquantitative values of Li 2 TiO 3 I C Based on, it is a value obtained from the following equation.
  • RIR Reference Intensity Ratio: intensity ratio of the strongest line of the card's diffraction line to the strongest line of Al 2 O 3 (corundum)
  • Single phase conversion rate I A / (I A + I B + I C )
  • the lithium titanate primary particles and lithium titanate aggregates according to the present invention can be prepared, for example, using lithium hydroxide and lithium carbonate as lithium raw materials, titanium oxide as metatitanium materials, metatitanic acid, orthotitanic acid, or mixtures thereof.
  • the mixed powder of can be obtained by firing under specific firing conditions.
  • lithium hydroxides and lithium carbonates used as raw materials are preferably of high purity, and usually 99.0% by weight or more is preferable. Further, it is desirable that the water content of lithium hydroxide and lithium carbonate be sufficiently removed, and the content thereof is desirably 0.1% by weight or less.
  • the average particle size is desirably 0.01 to 100 ⁇ m, and in particular, in the case of lithium carbonate, 50 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 0.01 ⁇ m or more.
  • titanium oxide, metatitanic acid, orthotitanic acid, or a mixture thereof used as a titanium raw material also have high purity, specifically 99.0% by weight or more, preferably 99.5% by weight or more, Desirably, each of Fe, Al, Si and Na contained as impurities is less than 20 ppm and Cl is less than 500 ppm. Desirably, each of Fe, Al, Si and Na is less than 10 ppm, and Cl is less than 100 ppm, more desirably less than 50 ppm.
  • titanium oxide When titanium oxide is used as a titanium raw material, its specific surface area is preferably 10 m 2 / g or more, preferably 20 m 2 / g to 250 m 2 / g, and more preferably 30 m 2 / g to 250 m 2 / g. It is preferable from the viewpoint of the single phase conversion rate of the lithium titanate to be obtained, that is, the battery characteristics and the capacitor characteristics.
  • the specific surface area of titanium oxide is related to the calcination temperature mentioned later.
  • the lithium compound and the titanium raw material are used as target values of Li / Ti ratio (atomic ratio) of lithium titanate, for example, 0.68 to 0.82 According to the value selected from the range, after weighing both raw materials, water or a slurry of 10 to 50% by weight of aqueous medium is mixed well, and then dried by heating or spray drying. A vibration mill, a ball mill, etc. are suitably used for mixing of both raw materials. The dried mixture is bulked or compressed at a pressure of about 0.5 t / cm 2 and subjected to firing as a molded body.
  • Li / Ti ratio atomic ratio
  • the firing is performed while maintaining the temperature at 700 to 950 ° C., preferably 720 to 950 ° C.
  • calcination is performed at a temperature as low as 600 to 700 ° C. for about 30 minutes to 5 hours, and then in the second stage, the temperature is increased to 700 to 950 ° C., preferably 720 to 950 ° C. May be adopted.
  • titanium oxide as a titanium raw material
  • the specific surface area of titanium oxide is 20 to 250 m 2 / g
  • the firing temperature is 700 to 850 ° C.
  • the specific surface area is 10 to 20 m 2 / g
  • firing is performed
  • the temperature is preferably 800 to 950 ° C. in view of the primary particle diameter and purity (referred to as the degree of single phase) of the target product lithium titanate, and further, battery characteristics and capacitor characteristics.
  • the temperature rising rate at the time of firing is preferably 1 ° C./min or less, preferably 0.5 ° C./min or less.
  • the temperature rising rate affects the firing time, it is necessary to set the temperature rising rate in consideration of the balance between the production efficiency and the characteristics. After the heating and firing, if necessary, it may be crushed using a hammer mill, pin mill or the like.
  • the lithium ion secondary battery of the present invention is a lithium ion secondary battery using a positive electrode having a positive electrode active material capable of inserting and extracting lithium, and the above lithium titanate primary particles or lithium titanate aggregate as a negative electrode active material A negative electrode, and an ion conductive medium interposed between the positive electrode and the negative electrode for a lithium ion secondary battery and conducting lithium ions.
  • the positive electrode of the lithium ion secondary battery of the present invention is, for example, a mixture of a positive electrode active material, a conductive material, a binder, and a solvent, and the paste is applied and dried on the surface of the positive electrode current collector. It can be formed compressed to increase density.
  • an oxide containing lithium and a transition metal element, or a polyanion compound can be used as the positive electrode active material.
  • lithium cobalt composite oxide such as Li (1-n) CoO (0 ⁇ n ⁇ 1, the same applies hereinafter
  • lithium nickel composite oxide such as Li (1-n) NiO 2
  • Lithium manganese complex oxide Li (1-n) MnO 2 , Li (1-n) Mn 2 O 4 etc.
  • lithium iron complex phosphorus oxide LiFePO 4 etc.
  • lithium vanadium complex oxide LiV 2 O 3) Etc.
  • the positive electrode current collector is not particularly limited as long as it is formed of a conductive material, but for example, a foil or mesh formed of a metal such as aluminum, copper, stainless steel, or nickel plated steel can be used .
  • the binder plays a role of holding the active material particles and the conductive material particles.
  • fluorine-containing resins such as polytetrafluoroethylene, polyvinylidene fluoride and fluororubber, or thermoplastic resins such as polypropylene and polyethylene can be used.
  • the conductive material is for securing the electrical conductivity of the positive electrode, and is obtained, for example, by mixing one or two or more kinds of powdery carbon materials such as carbon black, acetylene black, natural graphite, artificial graphite, and cokes. The thing can be used.
  • an organic solvent such as N-methyl-2-pyrrolidone can be used.
  • the negative electrode for a lithium ion secondary battery of the present invention includes the negative electrode active material containing the lithium titanate primary particles or the lithium titanate aggregate of the present invention.
  • the negative electrode of the lithium ion secondary battery of the present invention is, for example, a mixture of a negative electrode active material, a conductive material and a binder, and an appropriate solvent added thereto to apply a paste-like negative electrode material to the surface of the current collector. It can be dried and compressed as needed to increase electrode density.
  • the conductive material, the binder, the solvent and the like used for the negative electrode for a lithium ion secondary battery of the present invention those exemplified for the positive electrode can be used.
  • the current collector of the negative electrode in addition to copper, nickel, stainless steel, titanium, aluminum, calcined carbon, conductive polymer, conductive glass, Al-Cd alloy, etc., adhesion, conductivity and reduction resistance are improved.
  • adhesion, conductivity and reduction resistance for the purpose, for example, one obtained by treating the surface of copper or the like with carbon, nickel, titanium, silver or the like can also be used.
  • the shape of the current collector can be the same as that of the positive electrode.
  • a non-aqueous electrolytic solution in which a support salt is dissolved in an organic solvent, an ionic liquid, a gel electrolyte, a solid electrolyte, or the like can be used as the ion conductive medium.
  • the non-aqueous electrolyte is preferred.
  • the supporting salt for example, known materials such as LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 3 ), LiN (C 2 F 5 SO 2 ) 2 and the like Supporting salts can be used.
  • the concentration of the supporting salt is preferably 0.1 to 2.0 M, and more preferably 0.8 to 1.2 M.
  • organic solvent examples include ethylene carbonate (EC), propylene carbonate (PC), ⁇ -butyrolactone ( ⁇ -BL), diethyl carbonate (DEC), dimethyl carbonate (DMC), butylene carbonate (BC), ethyl methyl carbonate
  • organic solvents used for conventional secondary batteries and capacitors such as EMC may be used alone or in combination of two or more.
  • the ionic liquid is not particularly limited, but 1-methyl-3-propylimidazolium bis (trifluorosulfonyl) imide, 1-ethyl-3-butylimidazolium tetrafluoroborate, N -Methyl-N-propyl pyrrolidinium bis (fluorosulfonyl) imide and the like can be used.
  • the gel electrolyte is not particularly limited, but, for example, polymers such as polyvinylidene fluoride, polyethylene glycol, polyacrylonitrile, etc., or saccharides such as amino acid derivatives and sorbitol derivatives may contain an electrolytic solution containing a support salt. Gel electrolyte can be mentioned.
  • an inorganic solid electrolyte As a solid electrolyte, an inorganic solid electrolyte, an organic solid electrolyte, etc. are mentioned.
  • the inorganic solid electrolyte for example, a nitride of Li, a halide, an oxy acid salt and the like are well known. Among them, Li 4 SiO 4, Li 4 SiO 4 -LiI-LiOH, xLi 3 PO 4 - (1-x) Li 4 SiO 4, Li 2 SiS 3, Li 3 PO 4 -Li 2 S-SiS 2, sulfide A phosphorus compound etc. are mentioned. These may be used alone or in combination of two or more.
  • organic solid electrolyte examples include polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyvinylidene fluoride, polyphosphazene, polyethylene sulfide, polyhexafluoropropylene and the like and derivatives thereof. These may be used alone or in combination of two or more.
  • the lithium ion secondary battery of the present invention may include a separator between the negative electrode and the positive electrode.
  • the separator is not particularly limited as long as it has a composition that can withstand the use range of the lithium ion secondary battery, but, for example, a polymeric nonwoven fabric such as a polypropylene non-woven fabric or a polyphenylene sulfide non-woven fabric, or an olefin resin such as polyethylene or polypropylene A microporous membrane is mentioned. These may be used alone or in combination of two or more.
  • the shape of the lithium ion secondary battery of the present invention is not particularly limited, and examples thereof include coin type, button type, sheet type, laminated type, cylindrical type, flat type, and square type.
  • the present invention may be applied to a large one used for an electric car or the like.
  • the lithium ion capacitor of the present invention comprises a negative electrode current collector provided with a negative electrode active material including a layer of the lithium titanate primary particles or lithium titanate aggregate of the present invention as a negative electrode active material, and a positive electrode current collector.
  • a lithium ion capacitor comprising: a positive electrode body; and a non-aqueous electrolytic solution containing an electrolyte containing lithium ions interposed between the positive electrode and the negative electrode.
  • a lithium ion capacitor is a storage element using a non-aqueous electrolytic solution containing an electrolyte containing lithium ions, and a non-Faraday reaction by adsorption / desorption of anions similar to the electric double layer capacitor at the positive electrode, and a negative electrode It is a storage element which performs charge and discharge by the Faraday reaction by occlusion / discharge
  • the lithium ion capacitor can achieve both excellent output characteristics and high energy density by performing charge and discharge by non-Faraday reaction at the positive electrode and Faraday reaction at the negative electrode.
  • the positive electrode of the lithium ion capacitor of the present invention is, for example, a positive electrode active material, optionally mixed with a conductive material and a binder, and an appropriate solvent added to form a paste, which is coated and dried on the surface of a positive electrode current collector. It can be compressed and formed as required.
  • the positive electrode active material is preferably a porous carbon material, specifically, activated carbon.
  • a binder in the positive electrode active material layer polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), fluororubber, a styrene-butadiene copolymer, and the like can be used.
  • the conductive agent can be mixed with a conductive filler made of a conductive carbon material.
  • a conductive filler made of a conductive carbon material.
  • ketjen black, acetylene black, vapor grown carbon fiber, graphite, a mixture thereof, and the like are preferable.
  • a conductive layer containing a conductive filler and a binder can be provided in advance on the positive electrode current collector before the positive electrode active material layer is applied to reduce the resistance of the positive electrode body itself.
  • the conductive filler acetylene black, ketjen black, vapor grown carbon fiber, and a mixture thereof are preferable.
  • the coating method can be exemplified by a bar coating method, a transfer roll method, a T-die method, a screen printing method and the like, and a coating method can be appropriately selected according to the physical properties of the paste and the coating thickness.
  • the negative electrode of the lithium ion capacitor of the present invention may be prepared, for example, by mixing the lithium titanate of the present invention as a negative electrode active material, a conductive material and a binder according to need, adding an appropriate solvent to form a paste, It can be applied to the surface of the body, dried and compressed if necessary.
  • PVdF, PTFE, fluororubber, styrene-butadiene copolymer and the like can be used as the binder.
  • a conductive material made of a carbonaceous material that is more conductive than the negative electrode active material can be mixed. Examples of the conductive material include acetylene black, ketjen black, vapor grown carbon fiber, and a mixture thereof.
  • a conductive layer containing a conductive filler and a binder may be provided on the negative electrode current collector in advance.
  • the conductive filler acetylene black, ketjen black, vapor grown carbon fiber, and a mixture thereof are preferable.
  • the molded positive electrode body and negative electrode body are laminated or wound laminated through a separator as needed, and inserted into a metal can or an outer package formed of a laminate film.
  • a separator it is possible to use a microporous membrane made of polyethylene used in a lithium ion secondary battery, a microporous membrane made of polypropylene, a nonwoven paper made of cellulose used in an electric double layer capacitor, or the like.
  • a metal can and a laminate film can be used for the exterior body.
  • the metal can is made of aluminum
  • the laminate film used for the outer package is a film in which a metal foil and a resin film are laminated (for example, a three-layer structure consisting of an outer layer resin film / metal foil / interior resin film Thing is illustrated.
  • the outer layer resin film is for preventing the metal foil from being damaged by contact or the like, and resins such as nylon and polyester can be suitably used.
  • the metal foil is for preventing permeation of moisture and gas, and foils of copper, aluminum, stainless steel, etc. can be suitably used.
  • the inner resin film protects the metal foil from the electrolytic solution stored inside, and is for melting and sealing at the time of heat sealing, and polyolefin and acid-modified polyolefin can be suitably used.
  • examples of the electrolyte include LiN (SO 2 C 2 F 5 ) 2 , LiBF 4 and LiPF 6 .
  • solvents for non-aqueous electrolytes that dissolve these electrolytic chambers cyclic carbonates represented by ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • MEC chain carbonate
  • ⁇ BL ⁇ -butyrolactone
  • the ratio of the number of primary particles having a structure in which the crystal plane which is the ⁇ 111 ⁇ plane is formed stepwise 100 views are randomly observed at 10,000 to 100,000 times where the primary crystal surface of lithium titanate can be sufficiently observed.
  • the number (M) of primary particles that can be observed in the field of view and, among the primary particles, composed of smooth surfaces of a plurality of polygons and having a step-like structure in which some connecting planes are regularly repeated Measure the number of primary particles (N). This measurement is performed for 100 views, and the ratio N / M of the number of primary particles (N) having a primary particle number (M) and a smooth plane and at least a part of the side surfaces having a step structure is obtained. Decided.
  • the particle size distribution of lithium titanate primary particles was measured from the SEM observation image (magnification: 10,000 to 100,000).
  • the particle size distribution of lithium titanate aggregates (average particle size D50 (50% particle size by cumulative particle size distribution in volume integrated particle size distribution) is measured using a particle size distribution analyzer LA-920 (manufactured by HORIBA, Ltd.) using sodium hexametaphosphate A measurement sample was put into a 0.2% aqueous solution, and after being subjected to dispersion treatment for 3 minutes with an ultrasonic dispersion device (output 30 W-range 5) incorporated in LA-920, measurement was performed.
  • the coin cell 10 shown in FIG. 8 is manufactured.
  • the electrode 1 is a pressed product of the above lithium titanate particles
  • the counter electrode 2 is a metal Li plate
  • the electrolyte 3 is a 1: 1 (volume ratio) mixed solution of ethylene carbonate and dimethyl carbonate with 1 mol / l of LiPF 6.
  • Celgard # 2400 manufactured by Celgard, Inc. was used for the separator 4.
  • the gasket 6 is attached to the outer periphery of the coin can, the can lid 7 is placed thereon, and the outer periphery is crimped and sealed to make a coin cell 10. All the assembly work of coin cell 10 was performed in the glove box of argon atmosphere which managed dew point below -80 ° C.
  • the coin cell 10 was set to the holder installed in a 30 degreeC thermostat, and evaluation of a charge / discharge characteristic was measured using Hokuto Denko charge / discharge apparatus HJ1001SD. First, a current (0.1 C) of 17.5 mA per 1 g of lithium titanate aggregate is applied to discharge until the voltage reaches 1.0 V, and the voltage is further maintained at 1.0 V for 6 hours to be sufficiently discharged ( Initial discharge).
  • Example 1 565.4 g of titanium oxide powder of 99.9% purity (manufactured by Toho Titanium Co., Ltd., specific surface area of 30 m 2 / g) and 20.9 g of lithium carbonate powder of 99.5% purity (manufactured by Kanto Chemical Co., Ltd.) 215.9 g of lithium hydroxide monohydrate (manufactured by Kanto Chemical Co., Ltd.) having a purity of 99.0% was weighed, and was put into a nylon 10 L ball mill. After 10 kg of zirconia balls, 2.5 kg of pure water and 40 g of a dispersing agent (Kao Co., Ltd., Poise 532A) were added, they were mixed and pulverized for 8 hours by a ball mill.
  • a dispersing agent Kao Co., Ltd., Poise 532A
  • the obtained slurry was spray granulated with hot air at 220 ° C. using a spray dryer (manufactured by Yamato Scientific Co., Ltd., GB 210-B) to obtain spherical granulated mixed powder.
  • this mixed powder is put into alumina-made sheaths, heated to 800 ° C. at a heating rate of 0.5 ° C./min, calcined at 800 ° C. for 6 hours, and cooled to room temperature at a temperature lowering rate of 1 ° C./min.
  • An aggregate of lithium titanate was obtained.
  • the obtained lithium titanate aggregate had Li 4 Ti 5 O 12 as a main component.
  • the electron micrograph of the obtained lithium titanate aggregate is shown in FIG. 1, FIG.
  • the obtained lithium titanate aggregate has a step-like structure in which most of primary particles are composed of smooth surfaces of a plurality of polygons, and connecting planes of a part of the plurality of planes are regularly repeated.
  • the shape of each step is rectangular, and the step difference is 5 to 100 nm, the step length (depth) is 5 to 500 nm, and the step width is 100 to 1000 nm. It is an aggregate.
  • Table 1 shows the results of the single phase conversion rate, the electric capacities at current values of 0.1 C and 10 C, and the capacity retention rate.
  • the specific surface area by BET method using nitrogen adsorption was 6.0 m ⁇ 2 > / g.
  • the particle size of the lithium titanate primary particles was 0.1 to 0.5 ⁇ m, and the average particle size of the lithium titanate aggregate was 4.2 ⁇ m.
  • the flat surface of the lithium titanate primary particle was subjected to limited field diffraction with a transmission electron microscope.
  • the flat surface was a ⁇ 111 ⁇ surface (surface spacing: 4.835 ⁇ ) of Li 4 Ti 5 O 12 .
  • the same measurement results obtained for the other 10 primary lithium titanate primary particles all resulted in ⁇ 111 ⁇ planes. Therefore, the ⁇ 111 ⁇ plane is selectively formed on the flat surface of the lithium titanate primary particles.
  • Example 2 565.4 g of titanium oxide powder of Example 1, 20.9 g of lithium carbonate powder, 215.9 g of lithium hydroxide monohydrate, 573.5 g of titanium oxide powder, 106.1 g of lithium carbonate powder, lithium hydroxide.
  • a lithium titanate aggregate was produced in the same manner as in Example 1 except that 121.6 g of monohydrate was used.
  • the obtained lithium titanate aggregate had Li 4 Ti 5 O 12 as a main component.
  • the electron micrograph of the obtained lithium titanate aggregate is shown in FIG.
  • the obtained lithium titanate aggregate has a step-like structure in which many primary particles are composed of smooth surfaces of a plurality of polygons and connecting planes of a part of the plurality of planes are regularly repeated. Although it is an aggregate which is a primary particle which it has, the primary particle number of the said shape was small compared with Example 1.
  • Table 1 shows the results of the single phase conversion rate, the electric capacities at current values of 0.1 C and 10 C, and the capacity retention rate.
  • the specific surface area by BET method using nitrogen adsorption was 5.2 m ⁇ 2 > / g.
  • the particle size of the lithium titanate primary particles was 0.1 to 0.5 ⁇ m, and the average particle size of the lithium titanate aggregate was 4.0 ⁇ m.
  • the flat surface of the lithium titanate primary particles was subjected to limited field diffraction by a transmission electron microscope.
  • the flat surface was a ⁇ 111 ⁇ surface (surface spacing: 4.835 ⁇ ) of Li 4 Ti 5 O 12 .
  • Example 3 565.4 g of titanium oxide powder of Example 1, 20.9 g of lithium carbonate powder, 215.9 g of lithium hydroxide monohydrate, 581.8 g of titanium oxide powder, 193.8 g of lithium carbonate powder, lithium hydroxide. After 24.6 g of monohydrate and drying and granulating the obtained slurry after ball mill mixing with a spray drier in a dryer at 110 ° C. in a dryer, it is crushed in a mortar to make uniform A lithium titanate aggregate was produced in the same manner as in Example 1 except that the mixed powder was obtained.
  • the obtained lithium titanate aggregate had Li 4 Ti 5 O 12 as a main component.
  • the electron micrograph of the obtained lithium titanate aggregate is shown in FIG.
  • the obtained lithium titanate aggregate has a step-like structure in which a part of primary particles is constituted of smooth surfaces of a plurality of polygons, and a connecting plane of a part of the plurality of planes is regularly repeated It is an aggregate which is a primary particle having.
  • Table 1 shows the results of the single phase conversion rate, the electric capacities at current values of 0.1 C and 10 C, and the capacity retention rate.
  • the specific surface area by BET method using nitrogen adsorption was 5.5 m ⁇ 2 > / g.
  • the particle diameter of the lithium titanate primary particles was 0.2 to 0.5 ⁇ m, and the average particle diameter of the lithium titanate aggregate was 3.7 ⁇ m.
  • the flat surface of the lithium titanate primary particles was subjected to limited field diffraction by a transmission electron microscope.
  • the flat surface was a ⁇ 111 ⁇ surface (surface spacing: 4.835 ⁇ ) of Li 4 Ti 5 O 12 .
  • Comparative Example 1 565.4 g of titanium oxide powder of Example 1, 20.9 g of lithium carbonate powder, 215.9 g of lithium hydroxide monohydrate, and 583.6 g of titanium oxide powder (manufactured by Toho Titanium Co., Ltd., specific surface area 8 m 2 G), lithium carbonate powder 216.4 g, lithium titanate aggregates were prepared in the same manner as in Example 1 except that the heating rate was changed to 4 ° C./min and the cooling rate was 4 ° C./min. Made.
  • the obtained lithium titanate aggregate was mainly composed of Li 4 Ti 5 O 12 .
  • the electron micrograph of the obtained lithium titanate particle is shown in FIG. 5, FIG.
  • the obtained lithium titanate particles are aggregates of primary particles, but primary particles have a plurality of polygonal smooth flat surfaces and primary particles having a step-like structure repeated regularly. It was not observed.
  • Table 1 shows the results of the single phase conversion rate, the electric capacities at current values of 0.1 C and 10 C, and the capacity retention rate.
  • the specific surface area by BET method using nitrogen adsorption was 4.5 m ⁇ 2 > / g.
  • the particle diameter of the lithium titanate primary particles was 0.2 to 0.7 ⁇ m, and the average particle diameter of the lithium titanate aggregate was 4.1 ⁇ m.
  • Example 1 99.9% purity titanium oxide powder (manufactured by Toho Titanium Co., Ltd., specific surface area 30 m 2 / g) 565.4 g and purity 99.5% lithium carbonate powder (manufactured by Kanto Chemical Co., Ltd.) 20.9 g of 215.9 g of lithium hydroxide monohydrate (manufactured by Kanto Chemical Co., Ltd.) having a purity of 99.0% and titanium oxide powder having a purity of 98.7% (manufactured by Sakai Chemical Industry Co., Ltd., ratio A lithium titanate coagulated in the same manner as in Example 1 except that 565.4 g of surface area 10 m 2 / g) and 227.3 g of lithium hydroxide monohydrate (manufactured by Kanto Chemical Co., Ltd.) having a purity of 99.0% were used. I got a collective.
  • the obtained lithium titanate aggregate had Li 4 Ti 5 O 12 as a main component.
  • the electron micrograph of the obtained lithium titanate aggregate is shown in FIG.
  • the obtained lithium titanate aggregate has a step-like structure in which a part of primary particles is constituted of smooth surfaces of a plurality of polygons, and a connecting plane of a part of the plurality of planes is regularly repeated Almost no aggregates were observed which were primary particles having.
  • a primary particle having a step-like structure which is composed of a plurality of polygonal smooth flat surfaces of the obtained lithium titanate aggregate, and in which a part of the plurality of flat surfaces is continuously connected.
  • Table 1 shows the results of the ratio, single phase ratio, electric capacity at current values of 0.1 C and 10 C, and capacity maintenance ratio.
  • the specific surface area by BET method using nitrogen adsorption was 3.8 m ⁇ 2 > / g.
  • the particle size of the lithium titanate primary particles was 0.4 to 1.0 ⁇ m, and the average particle size of the lithium titanate aggregate was 4.5 ⁇ m.

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Abstract

L'invention concerne une matière active à base de particules de titanate de lithium, apte à améliorer les caractéristiques de cycle et la capacité électrique pendant une charge et une décharge à grande vitesse. L'invention concerne également ces particules primaires de titanate de lithium qui se caractérisent en ce qu'elles présentent une structure étagée dans laquelle sont stratifiées des plaques polygonales lisses. L'invention concerne également un agrégat de titanate de lithium contenant les particules primaires présentant la structure étagée et d'autres particules primaires de titanate de lithium constituant un agrégat de forme arbitraire, ledit agrégat se caractérisant en ce que le nombre de particules primaires présentant la structure étagée n'est pas inférieur à 10% du nombre total des particules primaires. L'invention concerne encore une batterie secondaire au lithium-ion et un condensateur au lithium-ion, chacun mettant en oeuvre les particules primaires ou l'agrégat.
PCT/JP2012/062724 2011-06-10 2012-05-11 Particules primaires de titanate de lithium, agrégat de titanate de lithium, batterie secondaire au lithium-ion mettant en oeuvre les particules primaires de titanate de lithium ou l'agrégat de titanate de lithium et condensateur au lithium-ion mettant en oeuvre les particules primaires de titanate de lithium ou l'agrégat de titanate de lithium Ceased WO2012169331A1 (fr)

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KR20190020647A (ko) * 2016-06-22 2019-03-04 니폰 케미콘 가부시키가이샤 하이브리드 커패시터 및 그 제조 방법
EP3547421A4 (fr) * 2016-11-22 2020-08-12 POSCO Chemical Co., Ltd Oxyde composite de lithium-titane, son procédé de préparation et batterie secondaire au lithium le comprenant
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KR101795977B1 (ko) * 2013-08-19 2017-11-08 고쿠리츠켄큐카이하츠호진 상교기쥬츠 소고켄큐쇼 용액 함침시킨 다공성 티탄 화합물을 사용한 티탄 산화물의 제조 방법
JP6363550B2 (ja) 2014-12-16 2018-07-25 日本ケミコン株式会社 金属化合物粒子群の製造方法、金属化合物粒子群及び金属化合物粒子群を含む蓄電デバイス用電極
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JP7082082B2 (ja) 2019-04-03 2022-06-07 信越化学工業株式会社 生体電極組成物、生体電極、及び生体電極の製造方法

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EP3547421A4 (fr) * 2016-11-22 2020-08-12 POSCO Chemical Co., Ltd Oxyde composite de lithium-titane, son procédé de préparation et batterie secondaire au lithium le comprenant
CN111789585A (zh) * 2019-04-03 2020-10-20 信越化学工业株式会社 生物体电极组成物、生物体电极、以及生物体电极的制造方法
CN111789585B (zh) * 2019-04-03 2023-04-25 信越化学工业株式会社 生物体电极组成物、生物体电极、以及生物体电极的制造方法

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