WO2017073765A1 - Poudre d'oxyde complexe à base de lithium, de sodium et de titane pour une électrode d'un dispositif de stockage, matériau actif et feuille d'électrode et dispositif de stockage utilisant cette dernière - Google Patents

Poudre d'oxyde complexe à base de lithium, de sodium et de titane pour une électrode d'un dispositif de stockage, matériau actif et feuille d'électrode et dispositif de stockage utilisant cette dernière Download PDF

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WO2017073765A1
WO2017073765A1 PCT/JP2016/082161 JP2016082161W WO2017073765A1 WO 2017073765 A1 WO2017073765 A1 WO 2017073765A1 JP 2016082161 W JP2016082161 W JP 2016082161W WO 2017073765 A1 WO2017073765 A1 WO 2017073765A1
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lithium
storage device
composite oxide
titanium composite
oxide powder
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PCT/JP2016/082161
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English (en)
Japanese (ja)
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敦允 中川
大谷　慎一郎
三好　和弘
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宇部興産株式会社
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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
    • 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
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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 lithium sodium titanium composite oxide powder suitable as an electrode material for an electricity storage device, an active material containing the lithium sodium titanium composite oxide powder, an electrode sheet using the active material, and an electricity storage device It is about.
  • lithium-titanium composite oxides can provide an electricity storage device with excellent input / output characteristics when used as an active material for a negative electrode, and thus are attracting attention as an active material material for electricity storage devices for electric vehicles such as HEV, PHEV, and BEV. ing.
  • lithium titanate having a spinel structure has almost no volume change associated with charge / discharge and can move three-dimensional Li ions, and is particularly excellent in charge / discharge cycle characteristics and input / output characteristics. It is promising as an active material for electricity storage devices.
  • lithium titanate having a spinel structure Li 4 Ti 5 O 12
  • the operating voltage of the electricity storage device to which it is applied Becomes lower and the energy density becomes smaller.
  • an electrode material in which the occlusion and release reaction of lithium proceeds at a relatively low potential it has a crystal structure belonging to space group Cmca or space group Fmmm, which contains alkali metal and alkaline earth metal elements as main constituent elements.
  • Lithium titanium composite oxides have attracted attention, and several compositions have been studied as electrode materials.
  • Patent Document 1 discloses that Li 2 + x ATi 6 O 14 (where A is at least one selected from the group consisting of Na, K, Mg, Ca, Ba, and Sr) having a crystal structure in which the space group is Cmca.
  • T is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Hf, Ta, W, B, Al, Ga, and In.
  • x is 0 ⁇ x ⁇ 5
  • Li 2 + x AT i6- y My O 14 (where A is selected from the group consisting of Na, K, Mg, Ca, Ba, and Sr) M is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Hf, Ta, W, B, Al, Ga, and In. At least one element, x is ⁇ x ⁇ 5 and y is 0 ⁇ y ⁇ 6).
  • A is one or two of Mg, Ca, Ba and Sr, T is Ti, And in the composition formula containing M, M is a part of a kind of composition of Al, V, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, B, Ga, Zr and In. Is specifically disclosed, and it has been shown that a non-aqueous electrolyte battery with improved energy density can be provided.
  • Patent Document 2 discloses Li 2 + n1 Na 2 ⁇ x1 K x1 Ti 6 O 14 (n1 satisfies 0 ⁇ n1 ⁇ 2, x1 satisfies 0 ⁇ x1 ⁇ 1.2), Li 2 + n2 Na 2 ⁇ x2 ⁇ y2 K x2 Rb y2 Ti 6 O 14 (n2 is 0 ⁇ n2 ⁇ 2, x2 and y2 satisfy the 0 ⁇ x2 ⁇ 1.2,0 ⁇ y2 ⁇ 0.5 and 0 ⁇ 5x2 + 12y2 ⁇ 6.
  • Li 2 + n3 Na 2-x3-y3-z3 K x3 Rb y3 Cs z3 Ti 6 O 14 (n3 is 0 ⁇ n3 ⁇ 2, x3, y3 and z3 are 0 ⁇ x3 ⁇ 0.25, 0 ⁇ y3 ⁇ 0.05, 0 ⁇ z3 ⁇ 0.05 and 0 ⁇ y3 + z3 ⁇ 0.05) are described, and a part of the composition containing Na and K as essential elements contained in these compositional formulas is concrete. disclosed, Li 4 Ti 5 O 1 Substantially the same capacity retention ratio is indicated to be obtained when.
  • the conventional lithium titanium composite oxide having a crystal structure belonging to the space group Cmca or the space group Fmmm as described above has poor charge / discharge cycle characteristics at high temperatures, and is excellent in charge / discharge cycle characteristics even in a high temperature environment. This is an important issue for the application to the required electric storage devices for electric vehicles. It is also an important issue to suppress gas generation in a high temperature environment.
  • the present invention provides a lithium sodium titanium composite oxide powder that is excellent in charge / discharge cycle characteristics in a high temperature environment and that suppresses gas generation after the charge / discharge cycle in a high temperature environment, and an active material, and uses the same. It is an object of the present invention to provide an electrode sheet and an electricity storage device.
  • a lithium-titanium composite oxide having a crystal structure belonging to the space group Cmca or the space group Fmmm contains Na and further contains a periodic table as an element for substituting the Ti site.
  • Lithium sodium titanium composite oxide powder containing at least one element selected from Al, Ga, In belonging to Group 13 and V, Nb, Ta belonging to Group 5 of the periodic table has a charge / discharge cycle life at high temperature.
  • the present invention was completed by finding that the amount of gas generated after a long charge / discharge cycle under a high temperature environment was small. That is, the present invention relates to the following matters.
  • (1) has a crystal structure belonging to the space group Cmca or space group Fmmm, the general formula: Li 2 + x Na 2 + y Ti 6-z M z O 14 ( provided that selection, M is Al, Ga, In, V, from Nb and Ta X is ⁇ 0.1 ⁇ x ⁇ 0.1, y is ⁇ 0.1 ⁇ y ⁇ 0.1, and z is 0 ⁇ z ⁇ 1.)
  • a lithium sodium titanium composite oxide powder for an electrode active material of an electricity storage device comprising a lithium sodium titanium composite oxide represented by
  • D BET A lithium sodium titanium composite oxide powder for an electrode active material for an electricity storage device according to 1) or (2).
  • Lithium sodium titanium composite oxidation for electrode active material of an electricity storage device according to any one of (1) to (3), wherein the total pore volume is 0.001 ml / g to 0.5 ml / g Powder.
  • An electrode for an electricity storage device comprising the active material according to (8), at least one conductive agent selected from graphites, carbon blacks, and carbon nanotubes, and a binder. Sheet.
  • the conductive agent contains at least one conductive agent selected from graphites and carbon blacks in addition to carbon nanotubes, and the proportion of carbon nanotubes in the total conductive agent is 1% by mass or more and 49% by mass.
  • the above-mentioned carbon nanotubes are formed by stacking 2 to 30 bell-shaped structural units having a top portion with a closed graphite mesh surface and a trunk portion with an open lower portion sharing a central axis.
  • a plurality of bell-shaped structural unit aggregates, and the carbon nanotubes are formed by connecting a plurality of bell-shaped structural unit aggregates at intervals in a head-to-tail manner to form fibers.
  • the electrode sheet for an electricity storage device according to any one of (9) to (11), wherein
  • An electricity storage device including a positive electrode including a material capable of inserting and extracting lithium as an active material, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.
  • the nonaqueous electrolytic solution is obtained by dissolving an electrolyte salt in a nonaqueous solvent, and ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, and 2,3-butylene are dissolved in the nonaqueous solvent.
  • a ratio of cyclic carbonate having at least one alkylene chain selected from propylene carbonate, 1,2-butylene carbonate and 2,3-butylene carbonate in all cyclic carbonates, comprising at least one cyclic carbonate selected from carbonates Is 55 volume% or more and 100 volume% or less,
  • the electrical storage device as described in (14) characterized by the above-mentioned.
  • the non-aqueous electrolyte is obtained by dissolving an electrolyte salt in a non-aqueous solvent, and dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, It contains a chain ester having at least one methyl group selected from methyl propionate, methyl acetate and ethyl acetate, and the content of all chain esters in the non-aqueous solvent is 60% by volume or more and 90% by volume or less.
  • the non-aqueous electrolyte is obtained by dissolving an electrolyte salt in a non-aqueous solvent, and includes at least LiPF 6 as the electrolyte salt in the non-aqueous electrolyte, and further includes LiBF 4 , LiPO 2 F 2 and The electrical storage according to any one of (14) to (16), wherein at least one lithium salt selected from LiN (SO 2 F) 2 is contained in the nonaqueous electrolytic solution at a concentration of 0.001M to 1M. device.
  • the electricity storage device is a lithium ion secondary battery, and a charging potential in a fully charged state of the negative electrode of the lithium ion secondary battery is 1 with respect to a lithium reference electrode.
  • the charge / discharge cycle life at high temperatures is long, that is, the discharge capacity retention rate after charge / discharge cycles at high temperatures is large, and the gas after charge / discharge cycles It is possible to provide a lithium sodium titanium composite oxide powder with a small amount of generation, an active material containing the same, and an electricity storage device using the active material.
  • FIG. 1 is a diagram showing an X-ray diffraction pattern of Li 2 Na 2 Ti 6 O 14 in the space group Cmca.
  • FIG. 2 is a diagram showing an X-ray diffraction pattern of Li 2 Na 2 Ti 6 O 14 in the space group Fmmm.
  • the lithium sodium titanium composite oxide of the present invention has a general structure: Li 2 + x Na 2 + y Ti 6-z M z O 14 (where M is Al, Ga, In, or C) having a crystal structure belonging to the space group Cmca or the space group Fmmm.
  • a lithium sodium titanium composite oxide powder for an electrode active material for an electricity storage device the main phase being a lithium sodium titanium composite oxide represented by: That is, the lithium sodium titanium composite oxide of the present invention is a lithium titanium composite oxide having a crystal structure belonging to space group Cmca or space group Fmmm, and contains substantially only Na as an alkali metal other than Li. In addition, a part of the Ti site is substituted with at least one element selected from Al, Ga, In, V, Nb, and Ta.
  • M Al, Ga, an In, V, from Nb and Ta X is ⁇ 0.1 ⁇ x ⁇ 0.1
  • y is ⁇ 0.1 ⁇ y ⁇ 0.1
  • z is 0 ⁇ z ⁇ 1.
  • X is ⁇ 0.1 ⁇ x ⁇ 0.1
  • y is ⁇ 0.1 ⁇ y ⁇ 0.1
  • z is 0 ⁇ z ⁇ 1.
  • the other phases are preferably small, and the total of the main peak intensities of the detected other phases is particularly preferably 3 or less.
  • Li 2 + x Na 2 + y Ti 6-z M z O 14 (where M is at least one element selected from Al, Ga, In, V, Nb and Ta, and x is ⁇ 0.1 ⁇ x ⁇ 0.1, y is ⁇ 0.1 ⁇ y ⁇ 0.1, and z is 0 ⁇ z ⁇ 1, and the lithium sodium titanium composite oxide represented by orthorhombic crystal
  • M is at least one element selected from Al, Ga, In, V, Nb and Ta
  • x is ⁇ 0.1 ⁇ x ⁇ 0.1
  • y is ⁇ 0.1 ⁇ y ⁇ 0.1
  • z is 0 ⁇ z ⁇ 1
  • the lithium sodium titanium composite oxide represented by orthorhombic crystal As the X-ray diffraction pattern, there are two types of card data, an X-ray diffraction pattern that is very similar to the case where the space group is Cmca and the case where the space group is Fmmm.
  • Li 2 + x according to the present invention is given.
  • Na 2 + y Ti 6-z M z O 14 (wherein M is at least one element selected from Al, Ga, In, V, Nb and Ta, and x is ⁇ 0.1 ⁇ x ⁇ 0.1) And y is ⁇ 0.1 ⁇ y ⁇ 0.1 and z is 0 ⁇ z ⁇ 1.)
  • the lithium sodium titanium composite oxide represented by It may not always be possible to clearly define whether it belongs to Cmca or the space group Fmmm.
  • the operational effects of the present invention are sufficiently exerted both in the case where it can be determined that it belongs to the space group Cmca and in the case where it can be determined that it belongs to the space group Fmmm. .
  • M in the general formula is at least one element selected from Al, Ga, In, V, Nb, and Ta. From the viewpoint of improving the discharge capacity retention rate after a charge / discharge cycle at high temperature, Al or Nb is Nb is preferable and Nb is particularly preferable.
  • x in the general formula is ⁇ 0.1 ⁇ x ⁇ 0.1.
  • the upper limit of x in the general formula is preferably 0.08 from the viewpoint of maximizing the utilization efficiency of lithium ions of the lithium sodium titanium composite oxide and improving the discharge capacity retention rate after the charge / discharge cycle at a high temperature, More preferably, it is 0.06, Most preferably, it is 0.04.
  • the lower limit of x in the general formula is preferably ⁇ 0.08, more preferably ⁇ 0.06, and particularly preferably ⁇ 0.04.
  • y is ⁇ 0.1 ⁇ y ⁇ 0.1. If y is this range, the discharge capacity maintenance factor after the charge / discharge cycle at high temperature is large, and the amount of gas generated is small.
  • the upper limit of y is preferably 0.08, more preferably 0.06, from the viewpoint of stabilizing the crystal structure of the lithium sodium titanium composite oxide and improving the discharge capacity retention rate after the charge / discharge cycle at high temperature. Yes, most preferably 0.04.
  • the lower limit of y is preferably ⁇ 0.08, more preferably ⁇ 0.06, and most preferably ⁇ 0.04.
  • z is 0 ⁇ z ⁇ 1. If z is in this range, the discharge capacity retention rate after the charge / discharge cycle at a high temperature is large, and the amount of gas generated is small.
  • the upper limit of z is preferably 0.7, more preferably 0.4, from the viewpoint of enhancing the electronic conductivity of the lithium sodium titanium composite oxide and improving the discharge capacity retention rate after the charge / discharge cycle at a high temperature. Particularly preferably 0.2. From the same viewpoint, the lower limit of z is preferably 0.001, more preferably 0.01, and particularly preferably 0.05.
  • the specific surface area of the lithium sodium titanium composite oxide powder of the present invention determined by the BET method is 1 m 2 / g to 50 m 2 / g.
  • the specific surface area is in this range, high input / output characteristics can be realized without impairing the handlinability of the powder. From these viewpoints, 2 m 2 / g to 45 m 2 / g is preferable, and 3 m 2 / g to 40 m 2 / g is particularly preferable.
  • the specific surface area equivalent diameter D BET of the lithium sodium titanium composite oxide powder of the present invention is a specific surface area equivalent diameter calculated from the specific surface area determined by the BET method.
  • the specific surface area equivalent diameter D BET of the lithium sodium titanium composite oxide powder of the present invention is preferably 0.03 ⁇ m to 0.6 ⁇ m.
  • D BET is 0.03 ⁇ m to 0.6 ⁇ m, the charge / discharge capacity of the electricity storage device can be increased.
  • D BET is particularly preferably 0.03 to 0.4 ⁇ m, and if it is within this range, the input characteristics of the electricity storage device are also improved.
  • the peak (Li) of diffraction angle 2 ⁇ 17.6 to 18.6 ° of Li 2 Na 2 Ti 6 O 14 having a crystal structure belonging to space group Cmca or space group Fmmm by X-ray diffraction.
  • the crystal structure of 2 Na 2 Ti 6 O 14 is to belong to the space group Cmca, and the crystallite diameter D X of from the half value width is calculated from the Scherrer formula of (111) peak corresponding to surface).
  • D X of lithium sodium titanium composite oxide powder of the present invention is preferably 80nm or more.
  • D X When D X is at 80nm or more, it is possible to minimize the effects of resistance when the lithium ions move grain boundary, deterioration in battery performance due to polarization increases caused by the grain boundaries lithium ion moves Can be suppressed.
  • the D X is preferably at 500nm or less. D X it is possible to minimize the influence of diffusion resistance inside the particles as long as 500nm or less, it is possible to suppress the deterioration of the cell performance due to polarization increases caused by the internal particles of lithium ions to move. A method for measuring the D X, described in detail in Example.
  • the ratio D BET / D X ( ⁇ m / ⁇ m) of D BET and D X of the lithium sodium titanium composite oxide powder of the present invention is preferably 4 or less, more preferably 3 or less, and 2.5 or less. It is more preferable that it is 2 or less.
  • the total pore volume of the lithium sodium titanium composite oxide powder of the present invention is preferably 0.001 ml / g to 0.5 ml / g.
  • the total pore volume is preferably 0.005 ml / g or more, more preferably 0.01 ml / g or more, from the viewpoint of further improving the discharge capacity maintenance rate after the charge / discharge cycle at a high temperature, Particularly preferred is 0.015 ml / g or more.
  • the total pore volume of the lithium sodium titanium composite oxide powder of the present invention is the total pore volume measured by a gas adsorption method.
  • the volume-median particle size (average particle size, hereinafter referred to as D50) of the lithium sodium titanium composite oxide powder of the present invention is preferably 0.01 ⁇ m or more and 35 ⁇ m or less, and more preferably 10 ⁇ m or more and 35 ⁇ m or less. It is particularly preferably 20 ⁇ m or more and 30 ⁇ m or less.
  • D50 means a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% when integrated from the smaller particle size. The measurement method is described in [5. Particle size distribution].
  • the ratio D50 / D BET ( ⁇ m / ⁇ m) of D50 and D BET of the lithium sodium titanium composite oxide powder of the present invention is preferably 25 or more and 100 or less. If D50 / D BET is within this range, the discharge capacity retention rate after the high-temperature cycle of the electricity storage device to which the lithium sodium titanium composite oxide powder of the present invention is applied as an electrode material is further large, and the amount of gas generated at high temperature is further increased. Few.
  • the lithium sodium titanium composite oxide powder of the present invention includes secondary particles formed by aggregating primary particles made of lithium sodium titanium composite oxide, and D50 / D BET ( ⁇ m / ⁇ m) is This is an index related to the degree of aggregation of primary particles with respect to secondary particles.
  • D50 / D BET ( ⁇ m / ⁇ m) is more preferably 25 or more and 28 or more from the viewpoint of increasing the discharge capacity maintenance rate after the high temperature cycle of the electricity storage device and reducing the amount of gas generated at high temperature. More preferably, it is more preferably 30 or more.
  • D50 / D BET ( ⁇ m / ⁇ m) is more preferably 100 or less, 80 Or less, more preferably 60 or less.
  • the average compressive strength of the secondary particles is preferably 0.3 MPa or more and 7 MPa or less. If the average compressive strength of the secondary particles of the lithium sodium titanium composite oxide powder of the present invention is in this range, the discharge after the high-temperature cycle of the electricity storage device to which the lithium sodium titanium composite oxide powder of the present invention is applied as an electrode material The capacity maintenance rate is further increased. From the viewpoint of increasing the discharge capacity retention rate after the high temperature cycle of the electricity storage device, the average compressive strength of the secondary particles is more preferably 0.4 MPa or more, further preferably 1 MPa or more, and 1.2 MPa. The above is particularly preferable.
  • the average compressive strength of the secondary particles is more preferably 6.2 MPa or less. More preferably, it is more preferably 4.2 MPa or less.
  • the method for measuring the average compressive strength of the secondary particles is described in [7. The average compressive strength of the secondary particles] will be described.
  • the average circularity of the secondary particles is preferably 80% or more. If the average circularity of the secondary particles of the lithium sodium titanium composite oxide powder of the present invention is within this range, the discharge after the high-temperature cycle of the electricity storage device to which the lithium sodium titanium composite oxide powder of the present invention is applied as an electrode material The capacity maintenance rate is further increased. From the viewpoint of further increasing the discharge capacity retention rate after the high-temperature cycle of the electricity storage device, the average circularity of the secondary particles is more preferably 90% or more, further preferably 94% or more, and 95% or more. It is particularly preferred that The method for measuring the average circularity is described in [8. The average circularity of the secondary particles] will be described.
  • Method for producing lithium sodium titanium composite oxide powder In the following, an example of a method for producing the lithium sodium titanium composite oxide powder of the present invention will be described by dividing it into a raw material preparation step and a firing step. It is not limited.
  • a titanium raw material As raw materials for the lithium sodium titanium composite oxide powder of the present invention, a titanium raw material, a lithium raw material, a sodium raw material, and a raw material of M in the above general formula, that is, a raw material of an element that substitutes a part of the titanium site are used.
  • the titanium raw material titanium compounds such as anatase type titanium dioxide and rutile type titanium dioxide are used.
  • As a titanium raw material it is preferable that it reacts easily with a lithium raw material in a short time, and the anatase type titanium dioxide is preferable from the viewpoint. In particular, complete anatase-type titanium dioxide having a rutile ratio of 0% is preferable.
  • lithium compounds such as lithium hydroxide monohydrate, lithium oxide, lithium hydrogen carbonate, and lithium carbonate are used, and lithium hydroxide monohydrate and lithium carbonate are preferable.
  • sodium compounds such as sodium hydroxide monohydrate, sodium oxide, sodium hydrogen carbonate and sodium carbonate are used, but sodium hydroxide monohydrate and sodium carbonate are preferred.
  • the raw material of M in the above general formula that is, the raw material of the element substituting a part of the titanium site, the oxide of M, hydroxide, nitride, phosphide, sulfide, fluoride, chloride, bromide, iodine Or inorganic salts such as carbonates, sulfates, nitrates, borates and phosphates, and organic salts such as acetates. From the viewpoint of ease of synthesis, oxides, fluorides, sulfates, and acetates are preferable.
  • the particle size distribution curve measured by a laser diffraction / scattering type particle size distribution measuring machine of the mixed powder constituting the mixture is such that D95 is 4 ⁇ m or less. It is preferable to prepare.
  • the D95 is to increase the D X, reducing the D BET / D X ( ⁇ m / ⁇ m), from the viewpoint of increasing the total pore volume, more preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, Particularly preferably, it is 1.5 ⁇ m or less.
  • D95 is a particle size in which the cumulative volume frequency calculated by the volume fraction is 95% when integrated from the smaller particle size.
  • the mixture may be a mixed powder prepared as described above, or a granulated powder obtained by granulating the mixed powder prepared as described above. Moreover, it is good also considering the state of the mixture used for baking as the slurry form containing the above mixed powder or granulated powder.
  • the D95 of the granulated powder is not necessarily 4 ⁇ m or less, and is preferably a granulated powder obtained by granulating a mixed powder having a D95 of 4 ⁇ m or less.
  • the above titanium raw material, lithium raw material, sodium raw material, and the raw material of M in the above general formula, that is, the raw material of an element that substitutes a part of the titanium site are mixed.
  • the first method is a method in which the raw materials are mixed and then pulverized simultaneously with mixing.
  • the second method is a method in which each raw material is pulverized and then mixed or mixed while lightly pulverizing.
  • the third method is a method in which powders made of fine particles are produced from each raw material by a method such as crystallization, classified as necessary, and mixed while mixing or lightly pulverizing.
  • the method of pulverizing simultaneously with the mixing of the raw materials is an industrially advantageous method because it involves fewer steps.
  • the obtained mixture is a mixed powder, it can be used as it is for the next firing step.
  • the mixed slurry can be granulated and dried with a spray dryer or the like and then subjected to the next firing step.
  • the resulting mixture is then fired.
  • the mixture is fired at a maximum temperature (holding temperature) of 800 to 1100 ° C. and a holding time of 0.5 to 25 hours at the maximum temperature.
  • the maximum temperature during baking is 850 to 1100 ° C.
  • the holding time at the maximum temperature during firing is preferably 12 hours or less.
  • the maximum temperature during firing is more preferably 880 ° C., and the holding time at the maximum temperature is more preferably 10 hours or less, and particularly preferably 8 hours or less.
  • a shorter holding time is selected.
  • a residence time of 700 ° C. to the maximum temperature (holding temperature) is set in the temperature rising process during firing.
  • it is preferable to shorten the temperature for example, it is preferable to set the temperature rising rate to 200 ° C./h or more.
  • the firing method is not particularly limited as long as it can be fired under such conditions.
  • the firing furnace that can be used include a fixed bed type firing furnace such as a box furnace (muffle furnace) and a tubular furnace, a roller hearth type firing furnace, a mesh belt type firing furnace, a fluidized bed type, and a rotary kiln type firing furnace.
  • a roller hearth-type firing furnace or a mesh belt-type firing furnace that contains the powder in a sagger and fires, in order to make the quality of the obtained lithium sodium titanium composite oxide powder constant, It is preferable to make the temperature distribution uniform, and it is preferable to reduce the amount of powder contained in the mortar.
  • the atmosphere at the time of baking is not specifically limited, It is preferable that it is an atmosphere containing oxygen.
  • the lithium sodium titanium composite oxide powder obtained in the firing step can be used as an active material as it is, but the powder obtained by granulating or further granulating the powder is used. It can also be used as an active material after post-treatment such as heat treatment.
  • the lithium sodium titanium composite oxide powder obtained in the firing step may be slurried using a dispersion medium such as water, and the resulting slurry may be granulated and dried by a spray dryer or the like. -You may heat-process the powder after drying.
  • D50 / D BET ⁇ m / ⁇ m
  • average compressive strength of secondary particles average circularity of secondary particles, and the like.
  • the lithium sodium titanium composite oxide powder obtained in the firing step is slurried, After granulation and drying, heat treatment is preferably performed in a temperature range of 400 ° C. to 650 ° C.
  • the active material of the present invention contains the lithium sodium titanium composite oxide powder of the present invention.
  • One or more substances other than the lithium sodium titanium composite oxide powder of the present invention may be contained. Examples of other substances include carbon materials (pyrolytic carbons, cokes, graphites (artificial graphite, natural graphite, etc.), organic polymer compound combustion bodies, carbon fibers), tin and tin compounds, silicon and silicon compounds. Is used.
  • the electrode sheet of the present invention comprises, as an electrode mixture layer on one or both sides of a current collector, an active material of the present invention, and at least one conductive agent selected from graphites, carbon blacks, and carbon nanotubes.
  • the electrode sheet for an electricity storage device including a binder and is cut according to the design shape of the electricity storage device and used as a negative electrode.
  • graphites include natural graphite (such as flake graphite), artificial graphite, and the like.
  • Examples of carbon blacks include acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, and the like.
  • Carbon nanotubes include single-phase carbon nanotubes, multi-wall carbon nanotubes (graphite layers are multi-layer concentric cylinders) (non-fishbones), cup-stacked carbon nanotubes (fishbones), and nodal carbon nanofibers (Non-fishbone structure), platelet-type carbon nanofibers (like a playing card), and the like. These graphites, carbon blacks, and carbon nanotubes may be appropriately mixed and used.
  • the specific surface area of the carbon blacks is preferably 30 to 3000 m 2 / g, and more preferably 50 to 2000 m 2 / g.
  • the specific surface area of the graphites is preferably 30 to 600 m 2 / g, more preferably 50 to 500 m 2 / g.
  • the aspect ratio of the carbon nanotubes is preferably 10 to 1000.
  • the electrode density is particularly likely to increase, and the capacity can be easily increased.
  • the addition amount of the conductive agent is optimized depending on the specific surface area of the active material and the type and combination of the conductive agent, but is preferably 10% by mass or less, more preferably 8% by mass with respect to the entire electrode mixture layer. Or less, more preferably 6% by mass or less.
  • the electrode sheet of the present invention preferably contains carbon nanotubes as the conductive agent. If carbon nanotubes are included as a conductive agent, the discharge capacity retention rate after a charge / discharge cycle at a high temperature is further increased.
  • carbon nanotubes multi-walled carbon nanotubes (graphite layers are multi-layer concentric cylinders) (non-fish-bone-like) are preferable.
  • a head with a closed graphite network surface described in JP 2012-46864 A or the like is used.
  • a bell-shaped structural unit having a top portion and a body portion having an open bottom includes a plurality of bell-shaped structural unit assemblies formed by stacking 2 to 30 layers sharing a central axis, and a plurality of the bell-shaped structural units.
  • fibrous carbon in which bell-like structural unit aggregates are connected in the Head-to-Tail manner at intervals to form fibers. If this fibrous carbon is contained as a conductive agent, the discharge capacity maintenance rate after a charge / discharge cycle at a high temperature is particularly increased.
  • the electrode sheet of the present invention preferably contains at least one conductive agent selected from graphites and carbon blacks in addition to containing carbon nanotubes as the conductive agent.
  • the proportion of the carbon nanotubes in it is preferably 1% by mass or more and 49% by mass or less, and more preferably 5% by mass or more and 40% by mass or less.
  • the binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), a copolymer of styrene and butadiene (SBR), and a copolymer of acrylonitrile and butadiene (NBR). ), Carboxymethylcellulose (CMC) and the like.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PVP polyvinylpyrrolidone
  • SBR styrene and butadiene
  • NBR copolymer of acrylonitrile and butadiene
  • CMC Carboxymethylcellulose
  • the molecular weight of polyvinylidene fluoride is preferably 20,000 to 200,000. From the viewpoint of securing the binding property of the electrode mixture layer, it is preferably 25,000 or more, more preferably 30,000 or more, and further preferably 50,000 or more. From
  • the amount of the binder added is optimized depending on the specific surface area of the active material and the type and combination of the conductive agents, but is usually 0.2 to 15% by mass with respect to the entire electrode mixture layer. .
  • the content is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 2% by mass or more.
  • the addition amount of the binder is preferably 10% by mass or less, More preferably, it is 5 mass% or less.
  • Examples of the current collector include aluminum, stainless steel, nickel, copper, titanium, baked carbon, and those whose surfaces are coated with carbon, nickel, titanium, and silver. Moreover, the surface of these materials may be oxidized, and unevenness
  • corrugation may be given to the collector surface by surface treatment.
  • Examples of the shape of the current collector include a sheet, a net, a foil, a film, a punched one, a lath body, a porous body, a foamed body, a fiber group, and a nonwoven fabric molded body.
  • the electrode sheet is prepared by adding a solvent to the active material, conductive agent and binder of the present invention, mixing and kneading them, adjusting the viscosity while adding the solvent, and forming a paint. It can be obtained by coating on top, drying and compressing.
  • a method for mixing the active material of the present invention, the conductive agent, and the binder in the solvent is not particularly limited, but the active material of the present invention, the conductive agent, and the binder are simultaneously mixed in the solvent.
  • the method of mixing in the method, the method of mixing the conductive material and the binder in a solvent in advance, and then the additional mixing of the active material of the present invention, the slurry of the active material of the present invention, the conductive agent slurry and the binder solution in advance The method of producing and mixing each is mentioned.
  • the solvent water or an organic solvent can be used.
  • organic solvent include aprotic organic solvents such as N-methylpyrrolidone, dimethylacetamide, and dimethylformamide, or a mixture of two or more kinds, with N-methylpyrrolidone being preferred.
  • the binder When water is used as the solvent, the binder is preferably added at the stage of finally adjusting to a desired viscosity in order not to cause the binder to aggregate.
  • an acidic compound in order to suppress corrosion of aluminum.
  • the acidic compound either an inorganic acid or an organic acid can be used.
  • the inorganic acid phosphoric acid, boric acid and oxalic acid are preferable, and oxalic acid is more preferable.
  • the organic acid is preferably an organic carboxylic acid.
  • an aluminum current collector in which the surface of the aluminum current collector is coated with an alkali-resistant material such as carbon.
  • an organic solvent it is preferable to use the binder by dissolving it in an organic solvent in advance.
  • the conductive agent and the binder of the present invention for example, a kneader of a type in which a stirring bar rotates while rotating in a kneading container such as a planetary mixer
  • a twin-screw extrusion kneader, a planetary stirring and defoaming device, a bead mill, a high-speed swirling mixer, a powder suction continuous dissolution and dispersion device, and the like can be used.
  • the solid content concentration at the stage of starting mixing and kneading is preferably 60 to 90% by mass, more preferably 70 to 90% by mass. If the solid content concentration is 60% by mass or more, sufficient shearing force can be obtained to uniformly disperse the active material of the present invention, the binder, and the conductive agent, and if it is 90% by mass or less, It is possible to avoid applying an extremely large load to the device.
  • the power storage device of the present invention is a power storage device using the electrode sheet of the present invention, and stores and releases energy using intercalation and deintercalation of lithium ions to the electrode containing the active material.
  • it is a hybrid capacitor or a lithium battery.
  • a positive electrode containing a material capable of occluding and releasing lithium as an active material a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte solution
  • hybrid capacitor As the hybrid capacitor, active adsorption and intercalation such as active material whose capacity is formed by the physical adsorption similar to the electrode material of the electric double layer capacitor, such as activated carbon, or graphite, on the positive electrode, This is a device that uses an active material in which capacitance is formed by deintercalation, or an active material in which capacitance is formed by redox, such as a conductive polymer, and uses the active material of the present invention for the negative electrode.
  • active material whose capacity is formed by the physical adsorption similar to the electrode material of the electric double layer capacitor, such as activated carbon, or graphite
  • redox such as a conductive polymer
  • the lithium battery of the present invention is a generic term for a lithium primary battery and a lithium secondary battery.
  • the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
  • the lithium battery is composed of a positive electrode, a negative electrode, a non-aqueous electrolyte solution in which an electrolyte salt is dissolved in a non-aqueous solvent, and the like.
  • a positive electrode which comprises the lithium battery of this invention, a non-aqueous electrolyte, and a lithium battery is demonstrated.
  • the positive electrode has a mixture layer containing a positive electrode active material, a conductive agent, and a binder on one or both surfaces of the positive electrode current collector.
  • the positive electrode active material a material capable of inserting and extracting lithium is used.
  • a composite metal oxide with lithium containing cobalt, manganese, nickel, lithium-containing olivine-type phosphate, or the like These positive electrode active materials can be used singly or in combination of two or more.
  • Such composite metal oxides include LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiCo 1-x Ni x O 2 (0.01 ⁇ x ⁇ 1), LiCo 1/3 Ni 1/3 Mn. 1/3 O 2 , LiNi 1/2 Mn 3/2 O 4 and the like.
  • lithium composite oxides may be substituted with other elements, and a part of cobalt, manganese, nickel may be replaced with Sn. , Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, Bi, Mo, La, etc., or a part of O is replaced with S or F Or it can coat
  • the lithium-containing olivine-type phosphate include LiFePO 4 , LiCoPO 4 , LiNiPO 4 , LiMnPO 4 , LiFe 1-x M x PO 4 (M is selected from Co, Ni, Mn, Cu, Zn, and Cd). At least one, and x is 0 ⁇ x ⁇ 0.5.
  • Examples of the conductive agent and the binder for the positive electrode include the same as those for the negative electrode.
  • Examples of the positive electrode current collector include aluminum, stainless steel, nickel, titanium, calcined carbon, and aluminum or stainless steel having a surface treated with carbon, nickel, titanium, or silver. The surface of these materials may be oxidized, and the surface of the positive electrode current collector may be uneven by surface treatment.
  • Examples of the shape of the current collector include a sheet, a net, a foil, a film, a punched one, a lath body, a porous body, a foamed body, a fiber group, and a nonwoven fabric molded body.
  • Non-aqueous electrolytic solution is obtained by dissolving an electrolyte salt in a nonaqueous solvent.
  • an electrolyte salt in a nonaqueous solvent.
  • an inorganic lithium salt such as LiPF 6 , LiBF 4 , LiPO 2 F 2 , LiN (SO 2 F) 2 , LiClO 4, or LiN (SO 2).
  • LiPF 3 Lithium salts containing a chain-like fluorinated alkyl group such as (CF 3 ) 3 , LiPF 3 (iso-C 3 F 7 ) 3 , LiPF 5 (iso-C 3 F 7 ), (CF 2 ) 2 ( SO 2 ) 2 NLi, (CF 2 ) 3 (SO 2 ) 2 NLi and other lithium salts containing cyclic fluorinated alkylene chains, bis [oxalate-O, O ′] lithium borate and diflu Examples thereof include lithium salts using an oxalate complex such as oro [oxalate-O, O ′] lithium borate as an anion.
  • electrolyte salts are LiPF 6 , LiBF 4 , LiPO 2 F 2 , and LiN (SO 2 F) 2
  • the most preferable electrolyte salt is LiPF 6 .
  • These electrolyte salts can be used singly or in combination of two or more.
  • the preferred combination of these electrolyte salts include LiPF 6, further LiBF 4, LiPO 2 F 2, and LiN (SO 2 F) at least one lithium salt selected from 2 nonaqueous solution Is preferable.
  • the concentration used by dissolving all the electrolyte salts is usually preferably 0.3 M or more, more preferably 0.5 M or more, and further preferably 0.7 M or more with respect to the non-aqueous solvent.
  • the upper limit is preferably 2.5 M or less, more preferably 2.0 M or less, and even more preferably 1.5 M or less.
  • non-aqueous solvent examples include cyclic carbonates, chain carbonates, chain esters, ethers, amides, phosphate esters, sulfones, lactones, nitriles, S ⁇ O bond-containing compounds, and the like, including cyclic carbonates.
  • chain ester is used as a concept including a chain carbonate and a chain carboxylic acid ester.
  • Examples of the cyclic carbonate include one or more selected from ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, and 2,3-butylene carbonate.
  • Ethylene carbonate, propylene carbonate, 1, One or more selected from 2-butylene carbonate and 2,3-butylene carbonate are more preferred from the viewpoint of improving the 50C charge rate characteristics and reducing the amount of gas generated during high-temperature storage.
  • Propylene carbonate, 1,2- One or more cyclic carbonates having an alkylene chain selected from butylene carbonate and 2,3-butylene carbonate are more preferred.
  • the ratio of the cyclic carbonate having an alkylene chain in the total cyclic carbonate is preferably 55% by volume to 100% by volume, and more preferably 60% by volume to 90% by volume.
  • non-aqueous electrolyte a non-aqueous solvent containing one or more cyclic carbonates selected from ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, and 2,3-butylene carbonate, LiPF 6 , LiBF 4 . It is preferable to use a nonaqueous electrolytic solution in which an electrolyte salt containing at least one lithium salt selected from LiPO 2 F 2 and LiN (SO 2 F) 2 is used.
  • cyclic carbonate propylene carbonate, 1, One or more cyclic carbonates having an alkylene chain selected from 2-butylene carbonate and 2,3-butylene carbonate are more preferable.
  • the concentration of the total electrolyte salt is 0.5 M or more and 2.0 M or less, and the electrolyte salt includes at least LiPF 6 and further 0.001 M or more and 1 M or less of LiBF 4 , LiPO 2 F 2 , and LiN. It is preferable to use a nonaqueous electrolytic solution containing at least one lithium salt selected from (SO 2 F) 2 .
  • the proportion of the lithium salt other than LiPF 6 in the non-aqueous solvent is 0.001 M or more, the effect of improving the charge / discharge cycle characteristics of the electricity storage device in a high-temperature environment and the reduction of gas generation after the charge / discharge cycle It is preferable that the effect is easily exhibited, and that it is 1.0 M or less because there is little concern that the effect of improving the charge / discharge cycle characteristics under a high temperature environment and the effect of reducing the amount of gas generated after the charge / discharge cycle are reduced.
  • the proportion of the lithium salt other than LiPF 6 in the non-aqueous solvent is preferably 0.01 M or more, particularly preferably 0.03 M or more, and most preferably 0.04 M or more.
  • the upper limit is preferably 0.8M or less, more preferably 0.6M or less, and particularly preferably 0.4M or less.
  • the non-aqueous solvent is preferably used as a mixture in order to achieve appropriate physical properties.
  • the combination includes, for example, a combination of a cyclic carbonate and a chain carbonate, a combination of a cyclic carbonate, a chain carbonate and a lactone, a combination of a cyclic carbonate, a chain carbonate and an ether, a cyclic carbonate, a chain carbonate and a chain ester.
  • Combinations, combinations of cyclic carbonates, chain carbonates, and nitriles, combinations of cyclic carbonates, chain carbonates, and S ⁇ O bond-containing compounds are included.
  • one or more asymmetric chain carbonates selected from methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, and ethyl propyl carbonate
  • MEC methyl ethyl carbonate
  • MPC methyl propyl carbonate
  • MIPC methyl isopropyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • dipropyl carbonate and dibutyl carbonate
  • pivalate esters such as methyl pivalate, ethyl pivalate, and propyl pivalate
  • Preferred examples include one or more chain carboxylic acid esters selected from methyl propionate, ethyl propionate, propyl propionate, methyl acetate, and ethyl acetate (EA).
  • chain esters having a methyl group selected from dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, methyl propionate, methyl acetate and ethyl acetate (EA) are preferable.
  • a chain carbonate having a methyl group is preferred.
  • chain carbonate it is preferable to use 2 or more types. Further, it is more preferable that both a symmetric chain carbonate and an asymmetric chain carbonate are contained, and it is further more preferable that the content of the symmetric chain carbonate is more than that of the asymmetric chain carbonate.
  • the content of the chain ester is not particularly limited, but it is preferably used in the range of 60 to 90% by volume with respect to the total volume of the nonaqueous solvent.
  • the content is 60% by volume or more, the viscosity of the non-aqueous electrolyte does not become too high, and when the content is 90% by volume or less, the electrical conductivity of the non-aqueous electrolyte is decreased.
  • the above range is preferable because there is little possibility that the effect of improving the discharge cycle characteristics and the effect of reducing the amount of gas generated after the charge / discharge cycle will be reduced.
  • the proportion of the volume occupied by the symmetrical linear carbonate in the linear carbonate is preferably 51% by volume or more, and more preferably 55% by volume or more.
  • the upper limit is more preferably 95% by volume or less, and still more preferably 85% by volume or less.
  • the symmetric chain carbonate contains dimethyl carbonate.
  • the asymmetric chain carbonate preferably has a methyl group, and methyl ethyl carbonate is particularly preferable. In the above case, it is preferable because the effect of improving the charge / discharge cycle characteristics under a higher temperature environment and the effect of reducing the amount of gas generated after the charge / discharge cycle are improved.
  • the ratio of cyclic carbonate and chain ester is cyclic carbonate: chain ester (volume ratio) from the viewpoint of improving the effect of improving charge / discharge cycle characteristics in a high temperature environment and the effect of reducing the amount of gas generated after the charge / discharge cycle.
  • the structure of the lithium battery of the present invention is not particularly limited, and a coin-type battery having a positive electrode, a negative electrode, and a single-layer or multi-layer separator, and a cylindrical battery and a corner having a positive electrode, a negative electrode, and a roll separator.
  • An example is a type battery.
  • an insulating thin film having a large ion permeability and a predetermined mechanical strength is used.
  • polyethylene, polypropylene, cellulose paper, glass fiber paper, polyethylene terephthalate, polyimide microporous film and the like can be mentioned, and a multilayer film constituted by combining two or more kinds can also be used.
  • the surfaces of these separators can be coated with resin such as PVDF, silicon resin, rubber-based resin, particles of metal oxide such as aluminum oxide, silicon dioxide, and magnesium oxide.
  • the pore diameter of the separator may be in a range generally useful for batteries, for example, 0.01 to 10 ⁇ m.
  • the thickness of the separator may be in a range for a general battery, and is, for example, 5 to 300 ⁇ m.
  • a lithium ion secondary battery of the present invention includes a positive electrode containing a material capable of inserting and extracting lithium as an active material, a negative electrode, a separator disposed between the positive electrode and the negative electrode, a non-aqueous electrolyte, It is preferable that the negative electrode includes the electrode sheet of the present invention, and a charging potential in a fully charged state of the negative electrode is 1.05 V or more with respect to a lithium reference electrode. . This is because, in the lithium ion secondary battery of the present invention, when the charge potential in the fully charged state of the negative electrode is in this range, the discharge capacity maintenance rate after the charge / discharge cycle in a high temperature environment is further increased.
  • the charging potential of the negative electrode in a fully charged state is more preferably 1.1 V or more, and particularly preferably 1.15 V or more with respect to the lithium reference electrode.
  • the discharge capacity maintenance rate after the charge / discharge cycle especially in a high temperature environment becomes large.
  • the discharge potential in the fully discharged state of the negative electrode is 1.8 V or less with respect to the lithium reference electrode. More preferably.
  • the discharge capacity retention rate after the charge / discharge cycle in a high temperature environment is further increased.
  • the discharge potential in the complete discharge state of the negative electrode is more preferably 1.7 V or less, and particularly preferably 1.6 V or less with respect to the lithium reference electrode.
  • the active material contained in the positive electrode of the lithium ion secondary battery of the present invention is preferably a composite metal oxide having a spinel structure. This is because the discharge capacity retention rate after the charge / discharge cycle in a high temperature environment is increased.
  • the composite metal oxide having a spinel structure specifically, LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , LiMg 0.5 Mn 1.5 O 4 , LiNi 0.5 Ge Examples thereof include 1.5 O 4 , LiNiVO 4 , LiMnVO 4 , and LiMnVO 4 .
  • a composite metal oxide containing manganese is preferable, LiMn 2 O 4 or LiNi 0.5 Mn 1.5 O 4 is more preferable, and LiMn 2 O 4 is Particularly preferred.
  • the discharge capacity maintenance rate after the charge / discharge cycle in a high temperature environment is particularly large.
  • the composite metal oxide having the spinel structure may be a composition in which a part of the constituent elements is replaced with another element.
  • the present invention is not limited to the following examples, and can be easily inferred from the gist of the invention. Including any combination. In particular, it is not limited to the combination of the solvent which comprises the non-aqueous electrolyte of an Example. Details of the physical property values given in the following examples and comparative examples are described.
  • XRD X-ray diffractometer using CuK ⁇ rays (RINT-TTR-III type, manufactured by Rigaku Corporation) was used as a measuring device.
  • the measurement conditions of the X-ray diffraction measurement are: measurement angle range (2 ⁇ ): 10 ° to 90 °, step interval: 0.02 °, measurement time: 0.25 seconds / step, radiation source: CuK ⁇ ray, tube voltage : 50 kV, current: 300 mA.
  • a peak (Li 2 Na 2 Ti 6 O corresponding to a peak in the range of diffraction angle 2 ⁇ 17.6 to 18.6 ° of Li 2 Na 2 Ti 6 O 14 having a crystal structure belonging to space group Cmca or space group Fmmm.
  • Crystallite diameter (D X ) The crystallite size (D X ) of the lithium sodium titanium composite oxide powder of the present invention was measured using an X-ray diffractometer (RINT-TTR-III, manufactured by Rigaku Corporation) using CuK ⁇ rays.
  • BET diameter (D BET ) The BET diameter (D BET ) of the lithium sodium titanium composite oxide powder of the present invention was obtained from the following formula (2) assuming that all particles constituting the powder were spheres having the same diameter.
  • D BET is the BET diameter ( ⁇ m)
  • ⁇ S is the true density (g / cc) of lithium sodium sodium titanium composite oxide
  • S is [3. Specific surface area (m 2 / g) measured by the method described in “Specific surface area (m 2 / g)”.
  • D BET 6 / ( ⁇ S ⁇ S) (2)
  • the particle size distribution of the lithium sodium titanium composite oxide powder of the present invention was measured using a laser diffraction / scattering type particle size distribution analyzer (Nikkiso Co., Ltd., Microtrack MT3300EXII).
  • a laser diffraction / scattering type particle size distribution analyzer (Nikkiso Co., Ltd., Microtrack MT3300EXII).
  • ion exchange water was used as a measurement solvent.
  • About 50 mg of a sample was put into 50 ml of a measurement solvent, and 1 cc of 0.2% sodium hexametaphosphate aqueous solution as a surfactant was added, and the obtained measurement slurry was processed with an ultrasonic disperser.
  • the measurement slurry subjected to the dispersion treatment was accommodated in a measurement cell, and a measurement solvent was added to adjust the slurry concentration.
  • the particle size distribution was measured when the transmittance of the slurry was within an appropriate range.
  • the volume median particle size D50 of the lithium sodium titanium composite oxide powder of the present invention is calculated from the results obtained by the above particle size distribution measurement, and the cumulative volume frequency calculated by the volume fraction is integrated from the smaller particle size.
  • the particle size was 50%.
  • the total pore volume of the lithium sodium titanium composite oxide powder of the present invention was measured by a gas adsorption method using a fully automatic gas adsorption amount measuring apparatus AC1-iQ (manufactured by QUANTACHROME) as follows. 1 g of lithium sodium titanium composite oxide powder was accommodated in a measuring cell (large cell) having a stem diameter of 6 mm, stored in the measuring device, and deaerated under vacuum at 200 ° C. for 15 hours. With the measurement apparatus, nitrogen gas was used as the adsorption gas, and a fully automatic gas adsorption amount measurement was performed by a constant volume method to measure the total pore volume.
  • Particles were randomly selected and measured one by one to obtain an average value of 50 points, and the average value was defined as “average compressive strength of secondary particles”.
  • the surface detection point of the compression test data was the point where the device automatically detected the surface.
  • the type of indenter was “FLAT50” and the length measurement mode was “single”. For particles with a compressive strength of 3 MPa or less, the “soft sample measurement” mode was used, the test force was 4.90 mN, the load speed was 0.0100 mN / sec, and the load holding time was 5 seconds. For particles with a compressive strength exceeding 3 MPa, the “soft sample measurement” mode was not used, the test force was 4.90 mN, the load speed was 0.0446 mN / sec, and the load holding time was 5 seconds.
  • the circularity is an index of sphericity when a particle is projected on a two-dimensional plane, and is an index instead of sphericity.
  • the perimeter of the perfect circle having the same area as the measurement target particle is expressed as a percentage with respect to the perimeter of the measurement target particle.
  • the value was determined as the circularity of each particle, and the average value was defined as the average circularity.
  • the perimeter of the particles to be measured was determined by image processing of the SEM image, and the circularity was determined by the following equation (3).
  • Circularity (perimeter of a perfect circle having the same area as the particle to be measured) / (perimeter of the particle to be measured) ⁇ 100 (%) (3)
  • Example 1-1 ⁇ Preparation of raw materials> Li 2 CO 3 (Alfa Aesar (ALF) product number: 034418) as a lithium raw material, Na 2 CO 3 (Alfa Aesar (ALF) product number: L13098) as a sodium raw material, anatase TiO 2 (average grain as a titanium raw material) As shown in Table 1, Al 2 (SO 4 ) 3 ⁇ 14 to 18 hydrate (manufactured by Wako Pure Chemical Industries, product number: 010-02125) is used as a raw material for the titanium site substitution element. The composition (Li 2 Na 2 Ti 5.99 Al 0.01 O 14 ).
  • the obtained mixed powder was filled in a high-purity alumina mortar and fired at 900 ° C. for 12 hours in air using a fixed-bed tubular furnace.
  • the rate of temperature increase from room temperature to the maximum temperature (holding temperature) was 200 ° C./h.
  • the fired product obtained was collected, sieved (mesh roughness: 45 ⁇ m), and the powder that passed through the sieve was collected to obtain a lithium sodium titanium composite oxide powder.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring physical properties].
  • the physical properties of the lithium sodium titanium composite oxide powder of Example 1-1 are shown in Table 1 together with other examples and comparative examples.
  • the non-aqueous electrolyte used for the battery for evaluating the characteristics was prepared as follows.
  • a nonaqueous solvent of ethylene carbonate (EC): propylene carbonate (PC): methyl ethyl carbonate (MEC): dimethyl carbonate (DMC) (volume ratio) 10: 20: 20: 50 was prepared, and LiPF was used as an electrolyte salt thereof. 6 was dissolved to a concentration of 1M and LiPO 2 F 2 to a concentration of 0.05M to prepare a non-aqueous electrolyte.
  • Polyvinylidene fluoride and acetylene black which have been previously dissolved in a 1-methyl-2-pyrrolidone solvent, the multi-walled carbon nanotube slurry, and a 1-methyl-2-pyrrolidone solvent are mixed in a planetary stirring deaerator, and then lithium Sodium titanium composite oxide powder was added, and the total solid content concentration was adjusted to 64% by mass and mixed in a planetary stirring deaerator. Further, a 1-methyl-2-pyrrolidone solvent was added to prepare a total solid content concentration of 56% by mass, and the mixture was mixed with a planetary stirring and deaerator to prepare a coating material. The obtained paint was applied to both sides of an aluminum foil and dried to prepare a negative electrode sheet.
  • ⁇ Preparation of positive electrode sheet> In the same production method as in ⁇ Preparation of negative electrode sheet>, as an active material, 90% by mass of lithium manganate (LiMn 2 O 4 ) powder, 5% by mass of acetylene black (conductive auxiliary agent), polyvinylidene fluoride (condensation) A paint containing 5% by mass of the adhesive was prepared, applied onto an aluminum foil and dried, and then applied to the opposite surface and dried to prepare a positive electrode sheet.
  • LiMn 2 O 4 lithium manganate
  • acetylene black conductive auxiliary agent
  • polyvinylidene fluoride condensation
  • the negative electrode sheet was pressed to obtain a predetermined electrode density, and then punched to prepare a negative electrode having a mixture layer having a lead wire connecting portion of 4.2 cm in length and 5.2 cm in width. At this time, the thickness of the mixture layer on one side was 35 ⁇ m, and the amount of the mixture was 70 g / m 2 .
  • a positive electrode having a mixture layer of 4 cm in length and 5 cm in width and having lead wire connecting portions was produced. At this time, the thickness of the mixture layer on one side was 20 ⁇ m, and the amount of the mixture was 70 g / m 2 .
  • the prepared negative electrode and positive electrode, and a 1 mm thick Li metal foil punched out to 14 mm ⁇ as a lithium reference electrode are opposed to each other through a separator made of a microporous polyethylene film, and the aluminum foil lead wire is used as a positive and negative electrode.
  • the nickel foil lead wire to the Li foil add the non-aqueous electrolyte for characteristic evaluation to each other, and vacuum seal with an aluminum laminate, so that the gas after 45 ° C. charge-discharge cycle and charge-discharge cycle
  • a laminate type battery for generation evaluation was produced.
  • the capacity of this laminated battery was 200 mAh.
  • ⁇ Charge / discharge cycle test and measurement of gas generation amount> Charge the laminated battery produced by the method described in ⁇ Preparation of Laminated Battery> in a constant temperature bath at 25 ° C. with a current of 40 mA until the negative electrode potential becomes 1.1 V with respect to the lithium reference electrode.
  • the charging current is 10 mA in a state where the potential of the negative electrode is 1.1 V with respect to the lithium reference electrode
  • 3 cycles of constant current discharge for discharging until the potential became 1.8 V with respect to the lithium reference electrode (however, charging is performed when current flows so that Li is occluded in the negative electrode.
  • the laminate battery was taken out from the thermostat and the volume of the laminate battery (volume of the laminate battery before the cycle test) was measured by Archimedes method. Thereafter, the temperature of the thermostatic bath is set to 45 ° C., and charging is performed at a current of 200 mA until the potential of the negative electrode becomes 1.1 V with respect to the lithium reference electrode. After performing constant current and constant voltage charging in which the charging current reaches 10 mA in a state of 1 V, discharging is performed until the negative electrode potential becomes 1.8 V with respect to the lithium reference electrode at a current of 200 mA. 500 cycles of constant current discharge were performed.
  • the discharge capacity at the first cycle was divided by the discharge capacity at the 500th cycle, and a discharge capacity retention rate after a 500 cycle charge / discharge test at 45 ° C., that is, a 500 cyc discharge capacity retention rate (45 ° C.) was calculated. Then, the temperature of the thermostat was set to 25 ° C. and stored for 1 hour. Next, the laminate battery was taken out from the thermostat, and the volume of the laminate battery (the volume of the laminate battery after storage) was measured by the Archimedes method. The volume of the laminate battery before the cycle test was subtracted from the volume of the laminate battery after the cycle test, and the amount of gas generated after the 500-cycle charge / discharge test at 45 ° C. was calculated.
  • the gas generation amount shown in Table 1 is a relative amount with the gas generation amount in Comparative Example 1 described later as 100%.
  • the characteristics evaluation results of the laminate type battery using the lithium sodium titanium composite oxide powder of Example 1-1 as the electrode sheet are described above, and the lithium sodium titanium titanium composite oxide powder of other examples and comparative examples are used as the electrode sheet. It shows in Table 1 together with the characteristic evaluation result of the used lithium ion secondary battery (laminate type battery).
  • Laminate type battery acetylene black and multi-walled carbon nanotubes used as conductive agents in this example are abbreviated as AB and CNT.
  • Example 1-2 Composition of each example shown in Table 1 for each raw material (Example 1-2: Li 2 Na 2 Ti 5.95 Al 0.05 O 14 , Example 1-3: Li 2 Na 2 Ti 5.9 Al 0.1 O 14 , Example 1-4: Li 2 Na 2 Ti 5.8 Al 0.2 O 14 , Example 1-5: Li 2 Na 2 Ti 5.5 Al 0.5 O 14 , Example 1-6: Lithium sodium titanium of Examples 1-2 to 1-6 in the same manner as in Example 1-1 except that it was weighed and mixed so as to be Li 2 Na 2 Ti 5 Al 1 O 14 ) A composite oxide powder was produced. The physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powders of Examples 1-2 to 1-6 are shown in Table 1 together with other examples and comparative examples.
  • Example 1-7 to 1-10 Nb 2 O 5 (Alfa Aesar (ALF) product instead of Al 2 (SO 4 ) 3 ⁇ 14-18H 2 O (Wako Pure Chemical Industries, product number: 010-02125) as a raw material for titanium site substitution element
  • Example 1-7 Li 2 Na 2 Ti 5.9 Nb 0.01 O 14
  • Example 1-8 Li 2 Na 2 Ti 5.95 Nb 0.05 O 14
  • Example 1-9 Li 2 Na 2 Ti 5.9 Nb 0.1 O 14
  • Example 1-10 Li 2 Na 2 Ti 5.8 Nb 0.2 O 14
  • Lithium sodium titanium composite oxide powders of Examples 1-7 to 1-10 were produced in the same manner as in Example 1-1 except that the raw material powders were weighed and mixed.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powders of Examples 1-7 to 1-10 are shown in Table 1 together with other examples and comparative examples.
  • Example 1-10 Using the lithium sodium titanium composite oxide powder of Example 1-10, a laminate battery was produced in the same manner as in Example 1-10.
  • Example 1-1 except that the charge potential and discharge potential with respect to the lithium reference electrode in each example were changed as shown in Table 1 in the charge / discharge cycle test and the gas generation amount measurement after the charge / discharge cycle.
  • the characteristics of the laminate type batteries of each example were evaluated. The results are shown in Table 1 together with other examples and comparative examples.
  • Example 1-14 to 1-16 The lithium sodium titanium composite oxide powder of Example 1-10 was used as the active material for the negative electrode, except that the active material shown in Table 1 was used instead of lithium manganate as the active material for the positive electrode.
  • laminated batteries of Examples 1-14 to 1-16 were produced. The characteristics of the laminate type battery of each example were evaluated in the same manner as in Example 1-1. The results are shown in Table 1 together with other examples and comparative examples.
  • Example 1-17 The lithium sodium titanium composite oxide powder of Example 1-10 was used as the active material for the negative electrode, except that only 5% by mass of acetylene black was used as the conductive agent for the negative electrode (no multi-walled carbon nanotubes were used).
  • a laminated battery was prepared in the same manner as in Example 1-10. The characteristics of the laminate type battery of each example were evaluated in the same manner as in Example 1-1. The results are shown in Table 1 together with other examples and comparative examples.
  • Example 1-18 and 1-19 Nb 2 O 5 (Alfa Aesar (ALF) product instead of Al 2 (SO 4 ) 3 ⁇ 14 to 18H 2 O (Wako Pure Chemical Industries, product number: 010-02125) as a raw material for the titanium site substitution element No. 011366), and the compositions of the examples shown in Table 1 (Example 1-18: Li 2 Na 2 Ti 5.5 Nb 0.5 O 14 , Example 1-19: Li 2 Na 2 Ti 5 Nb 1 O 14 )
  • the lithium sodium titanium composite oxide powders of Examples 1-18 and 1-19 were produced in the same manner as in Example 1-1 except that the raw material powders were weighed and mixed. did.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powders of Examples 1-18 and 1-19 are shown in Table 1 together with other examples and comparative examples.
  • Example 1-20 Instead of Al 2 (SO 4 ) 3 ⁇ 14 to 18H 2 O (manufactured by Wako Pure Chemical Industries, product number: 010-02125) as a raw material for the titanium site substitution element, V 2 O 5 (manufactured by Strem Chemicals, Inc.) No. 93-2321), and the raw material powder was weighed and mixed so as to be the composition of Example 1-20 shown in Table 1 (Li 2 Na 2 Ti 5.9 V 0.1 O 14 ) Produced the lithium sodium titanium composite oxide powder of Example 1-20 in the same manner as in Example 1-1. The physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Example 1-21 are shown in Table 1, together with other examples and comparative examples.
  • Example 1-21 Instead of Al 2 (SO 4 ) 3 ⁇ 14 to 18H 2 O (manufactured by Wako Pure Chemical Industries, product number: 010-02125), Ga 2 O 3 (manufactured by Strem Chemicals, Inc.) No. 93-3106), and the raw material powder was weighed and mixed so as to be the composition of Example 1-21 (Li 2 Na 2 Ti 5.9 Ga 0.1 O 14 ) shown in Table 1 Produced the lithium sodium titanium composite oxide powder of Example 1-21 in the same manner as in Example 1-1. The physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Example 1-21 are shown in Table 1, together with other examples and comparative examples.
  • Example 1-22 As a raw material for the titanium sites substitution elements, Al 2 (SO 4) 3 ⁇ 14 ⁇ 18H 2 O ( manufactured by Wako Pure Chemical Industries, product number: 010-02125) in place of In 2 O 3 (Chempur Feinchemikalien und Anlagens room GmbH made products No .: 004424-100), and the raw material powder was weighed and mixed so as to be the composition of Example 1-22 shown in Table 1 (Li 2 Na 2 Ti 5.9 In 0.1 O 14 ) Produced the lithium sodium titanium composite oxide powder of Example 1-22 in the same manner as in Example 1-1. The physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Example 1-22 are shown in Table 1, together with other examples and comparative examples.
  • Example 1-23 A lithium sodium titanium composite oxide powder of Example 1-23 was produced in the same manner as in Example 1-10, except that the holding time at the maximum temperature when firing the mixed powder was 24 hours.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Example 1-23 are shown in Table 1, together with other examples and comparative examples.
  • Comparative Example 1 Raw materials that do not contain raw materials for titanium site substitution elements, ie, Li 2 CO 3 (product number: Alfa Aesar (ALF), product number: 034418), Na 2 CO 3 (product number: Alfa Aesar (ALF), product number: L13098), and anatase TiO 2 (average particle size 0.6 ⁇ m) was the same as in Example 1-1 except that the composition (Li 2 Na 2 Ti 6 O 14 ) of Comparative Example 1 shown in Table 1 was weighed and mixed. The lithium sodium titanium composite oxide powder of Comparative Example 1 was produced by the method. The physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Comparative Example 1 are shown in Table 1 together with other examples and comparative examples.
  • Comparative Example 2 A comparative example shown in Table 1 was used instead of the sodium raw material Na 2 CO 3 (product number: L13098, manufactured by Alfa Aesar (ALF)) and barium raw material BaCO 3 (product number: 028-08761 manufactured by Wako Pure Chemical Industries, Ltd.).
  • the lithium barium titanium composite oxide powder of Comparative Example 2 was produced in the same manner as in Comparative Example 1, except that the raw material powder was weighed and mixed so as to become the composition of No. 2 (Li 2 Ba 2 Ti 6 O 14 ). did.
  • the physical properties of the obtained lithium barium titanium composite oxide powder were measured by the methods described in [Methods for measuring physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium barium titanium composite oxide powder of Comparative Example 2 are shown in Table 1 together with other examples and comparative examples.
  • Comparative Example 3 In place of the sodium raw material Na 2 CO 3 (manufactured by Alfa Aesar (ALF), product number: L13098), the magnesium raw material MgCO 3 (manufactured by Strem Chemicals, Inc., product number: 93-1220) was used, and the comparison shown in Table 1
  • the lithium magnesium titanium composite oxide powder of Comparative Example 3 was prepared in the same manner as in Comparative Example 1 except that the raw material powder was weighed and mixed so as to be the composition of Example 3 (Li 2 Mg 2 Ti 6 O 14 ). Manufactured.
  • the physical properties of the obtained lithium magnesium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium magnesium titanium composite oxide powder of Comparative Example 3 are shown in Table 1 together with other Examples and Comparative Examples.
  • Comparative Example 4 In place of sodium raw material Na 2 CO 3 (manufactured by Alfa Aesar (ALF), product number: L13098), calcium raw material CaCO 3 (manufactured by Chempur Feinchemien und Anlagensbedgarf GmbH, product number: 001089-1) is used for comparison shown in Table 1.
  • the lithium calcium titanium composite oxide powder of Comparative Example 4 was prepared in the same manner as in Comparative Example 1 except that the raw material powder was weighed and mixed so as to be the composition of Example 4 (Li 2 Ca 2 Ti 6 O 14 ). Manufactured. The physical properties of the obtained lithium calcium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the above comparative example 4 lithium calcium titanium composite oxide powder are shown in Table 1 together with other examples and comparative examples.
  • Comparative Example 5 As a raw material for the titanium site substitution element, instead of Al 2 (SO 4 ) 3 ⁇ 14 to 18H 2 O (manufactured by Wako Pure Chemical Industries, product number: 010-02125), MnO 2 (manufactured by Strem Chemicals, Inc., product number: 93-2510), except that the raw material powder was weighed and mixed so as to be the composition of Comparative Example 5 (Li 2 Na 2 Ti 5.9 Mn 0.1 O 14 ) shown in Table 1. The lithium sodium titanium composite oxide powder of Comparative Example 5 was produced in the same manner as in Example-1. The physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Comparative Example 5 are shown in Table 1 together with other examples and comparative examples.
  • Comparative Example 6 instead of Al 2 (SO 4 ) 3 ⁇ 14 to 18H 2 O (manufactured by Wako Pure Chemical Industries, product number 010-02125) as a raw material for the titanium site substitution element, Co 3 O 4 (product number manufactured by Alfa Aesar (ALF)) Example 1 except that the raw material powder was weighed and mixed so as to be the composition of Comparative Example 6 shown in Table 1 (Li 2 Na 2 Ti 5.9 Co 0.1 O 14 ). 1 was used to produce lithium sodium titanium composite oxide powder of Comparative Example 6. The physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Comparative Example 6 are shown in Table 1 together with other examples and comparative examples.
  • Comparative Example 7 A comparative example shown in Table 1 was used instead of the sodium raw material Na 2 CO 3 (product number: L13098, manufactured by Alfa Aesar (ALF)) and barium raw material BaCO 3 (product number: 028-08761 manufactured by Wako Pure Chemical Industries, Ltd.).
  • the raw material powder was weighed and mixed so as to be the composition of No. 7 (Li 2 Ba 2 Ti 5.95 Al 0.05 O 14 )
  • the lithium of Comparative Example 7 Barium titanium composite oxide powder was produced.
  • the physical properties of the obtained lithium barium titanium composite oxide powder were measured by the methods described in [Methods for measuring physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium barium titanium composite oxide powder of Comparative Example 7 are shown in Table 1 together with other examples and comparative examples.
  • Comparative Example 8 As a raw material for the titanium sites substitution elements, Al 2 (SO 4) 3 ⁇ 14 ⁇ 18H 2 O ( manufactured by Wako Pure Chemical Industries, product number: 010-02125) in place of In 2 O 3 (Chempur Feinchemikalien und Anlagens room GmbH made products No .: 004424-100), and comparison was made except that raw material powder was weighed and mixed so as to be the composition of Comparative Example 8 shown in Table 1 (Li 2 Ba 2 Ti 5.95 In 0.05 O 14 ). In the same manner as in Example 7, lithium sodium titanium composite oxide powder of Comparative Example 8 was produced. The physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Comparative Example 8 are shown in Table 1 together with other examples and comparative examples.
  • Comparative Example 9 In addition to the sodium raw material Na 2 CO 3 (product number: L13098, manufactured by Alfa Aesar (ALF)), K 2 CO 3 (manufactured by Wako Pure Chemical Industries, product number: 160-03491) was used as the raw material for the sodium site substitution element. In the same manner as in Comparative Example 1, except that the raw material powder was weighed and mixed so as to be the composition of Comparative Example 9 shown in Table 1 (Li 2 Na 1.5 K 0.5 Ti 6 O 14 ). The lithium sodium titanium composite oxide powder of Comparative Example 9 was produced. The physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • Example 1-1 a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Comparative Example 9 are shown in Table 1 together with other examples and comparative examples.
  • Comparative Example 10 In addition to the sodium raw material Na 2 CO 3 (manufactured by Alfa Aesar (ALF), product number: L13098), K 2 CO 3 (manufactured by Wako Pure Chemical Industries, product number: 160-03491) and Rb as the raw material for the sodium site substitution element Using 2 CO 3 (manufactured by Combi-Blocks, product number: QA-6120), the composition of Comparative Example 10 shown in Table 1 (Li 2 Na 1.4 K 0.25 Rb 0.35 Ti 6 O 14 ) was used. The lithium sodium titanium composite oxide powder of Comparative Example 10 was produced in the same manner as in Comparative Example 1 except that the raw material powder was weighed and mixed.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring various physical properties].
  • a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Comparative Example 10 are shown in Table 1 together with other examples and comparative examples.
  • Examples 2-1 to 2-5 The lithium sodium titanium composite oxide powder of Example 1-10 was used as the negative electrode active material, except that the nonaqueous solvent of the nonaqueous electrolyte used in the battery for evaluating the characteristics was changed as follows.
  • a laminated battery was produced in the same manner as in Example 1-10, and the characteristics of the laminated battery were evaluated in the same manner as in Example 1-1. The results are shown in Table 2.
  • Example 2-4; ethylene carbonate (EC): propylene carbonate (PC): diethyl carbonate (DEC) (volume ratio) 10: 20: 70
  • Examples 2-6 to 2-10) The lithium sodium titanium of Example 1-10, except that the type of electrolyte salt of the non-aqueous electrolyte used in the battery for evaluating characteristics and the concentration of each electrolyte salt in the non-aqueous electrolyte were changed as follows: A laminated battery was produced in the same manner as in Example 1-10 including using the composite oxide powder as the negative electrode active material, and the characteristics of the laminated battery were evaluated in the same manner as in Example 1-1. The results are shown in Table 2.
  • Example 2-6 LiPF 6 at a concentration of 1M Example 2-7; LiPF 6 at a concentration of 1M and LiBF 4 at a concentration of 0.05M Example 2-8; LiPF 6 at a concentration of 1M and lithium bisfluorosulfonylimide (LiFSI) at a concentration of 0.05M Example 2-9; LiPF 6 at a concentration of 1M and lithium bisoxalate borate (LiBOB) at a concentration of 0.05M Example 2-10; LiPF 6 at a concentration of 1M and LiBF 4 at a concentration of 0.5M
  • LiFSI lithium bisfluorosulfonylimide
  • LiBOB lithium bisoxalate borate
  • Example 2-11 and 2-12 The proportion of the conductive agent in the coating material used for the production of the negative electrode sheet was 3.0% by mass for acetylene black and 2.0% by mass for multi-walled carbon nanotubes in Example 2-11, and acetylene black in Example 2-12.
  • Example 1 including the use of the lithium sodium titanium composite oxide powder of Example 1-10 as the active material of the negative electrode except that 2.0% by mass and 3.0% by mass of the multi-walled carbon nanotube were used.
  • a laminated battery was produced in the same manner as in Example 10, and the characteristics of the laminated battery were evaluated in the same manner as in Example 1-1. The results are shown in Table 2.
  • Example 3-1 The lithium sodium titanium composite oxide powder of Example 1-10 was screened using a hammer mill (Dalton, AIIW-5 type) with a screen opening of 0.5 mm, a rotation speed of 8,000 rpm, and a powder feed rate. : Crushed under conditions of 25 kg / hr. To the powder obtained by pulverization, ion-exchanged water was added and stirred so that the solid content concentration of the slurry was 30% by mass to prepare a slurry. The obtained slurry was sprayed, dried and granulated using a spray dryer (L-8i, manufactured by Okawara Chemical Co., Ltd.) at an atomizer rotational speed of 25000 rpm and an inlet temperature of 210 ° C.
  • a spray dryer Li-8i, manufactured by Okawara Chemical Co., Ltd.
  • the powder that passed through the sieve was placed in an alumina sagger and heat-treated at 500 ° C. for 1 hour in a continuous conveyor furnace.
  • the obtained powder was sieved (mesh roughness: 53 ⁇ m), and the powder that passed through the sieve was collected to produce the lithium sodium titanium composite oxide powder of Example 3-1.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring physical properties].
  • a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Example 3-1 and the results of the evaluation of the characteristics of the laminate type battery are as follows. Table 3 also shows.
  • Example 3-2 and 3-3 The lithium of Example 3-2 and Example 3-3 was treated in the same manner as Example 3-1, except that the heat treatment temperature was 350 ° C. for Example 3-2 and 600 ° C. for Example 3-3. Sodium titanium composite oxide powder was produced.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring physical properties].
  • a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Example 3-2 and Example 3-3 and the results of the evaluation of the characteristics of the laminate type battery were compared with the physical properties and laminate of the lithium sodium titanium composite oxide powder of Example 1-10. It shows in Table 3 together with the characteristic evaluation result of the type battery.
  • Example 3-4 The slurry obtained by spraying and drying the slurry of lithium sodium titanium composite oxide powder using a spray dryer and granulating the powder obtained in Example 3-1, except that the powder was screened without heat treatment. Similarly, lithium sodium titanium composite oxide powder of Example 3-4 was produced.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring physical properties].
  • a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical property of the lithium sodium titanium composite oxide powder of Example 3-4 and the results of the evaluation of the characteristics of the laminate type battery are as follows. Table 3 also shows.
  • Example 3-5 To the mixed powder obtained in the same raw material preparation step as in Example 1-1, ion-exchanged water was added and stirred so that the solid content concentration of the slurry was 30% by mass to prepare a slurry. The obtained slurry was sprayed, dried and granulated using a spray dryer (L-8i, manufactured by Okawara Chemical Co., Ltd.) at an atomizer rotational speed of 25000 rpm and an inlet temperature of 210 ° C. The obtained powder was fired in the same manner as in Example 1-1, and then sieved (mesh roughness: 53 ⁇ m), and the powder that passed through the sieve was collected to obtain the lithium sodium titanium composite of Example 3-5. An oxide powder was produced.
  • a spray dryer Li-8i, manufactured by Okawara Chemical Co., Ltd.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring physical properties].
  • a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Example 3-5 and the results of the evaluation of the characteristics of the laminate type battery are the same as the physical properties of the lithium sodium titanium composite oxide powder of Example 1-10 and the results of the evaluation of the characteristics of the laminate type battery. Table 3 also shows.
  • Examples 3-6 and 3-7) Implementation was carried out in the same manner as in Example 3-1, except that the holding time at the maximum temperature (900 ° C.) during firing was changed to 24 hours in Example 3-6 and 3 hours in Example 3-7.
  • the lithium sodium titanium composite oxide powders of Example 3-6 and Example 3-7 were produced.
  • the physical properties of the obtained lithium sodium titanium composite oxide powder were measured by the methods described in [Methods for measuring physical properties].
  • a laminated battery was produced in the same manner as in Example 1-1, and a charge / discharge cycle test and a gas generation amount after the charge / discharge cycle were measured in the same manner as in Example 1-1.
  • the physical properties of the lithium sodium titanium composite oxide powder of Example 3-6 and the results of the evaluation of the characteristics of the laminate type battery are the same as the physical properties of the lithium sodium titanium composite oxide powder of Example 1-10 and the results of the evaluation of the characteristics of the laminate type battery. Table 3 also shows.
  • Example 4-1 to 4-5 The lithium sodium titanium composite oxide powder of Example 3-6 was used as the negative electrode active material, except that the nonaqueous solvent of the nonaqueous electrolyte used in the battery for evaluating the characteristics was changed as follows.
  • a laminated battery was produced in the same manner as in Example 3-6, and the characteristics of the laminated battery were evaluated in the same manner as in Example 1-1. The results are shown in Table 4.
  • Example 4-1; ethylene carbonate (EC): methyl ethyl carbonate (MEC): dimethyl carbonate (DMC) (volume ratio) 30: 20: 50
  • Example 4-2; ethylene carbonate (EC): propylene carbonate (PC): methyl ethyl carbonate (MEC): dimethyl carbonate (DMC) (volume ratio) 15: 15: 20: 50
  • Example 4-3; propylene carbonate (PC): methyl ethyl carbonate (MEC): dimethyl carbonate (DMC) (volume ratio) 30: 20: 50
  • Example 4-4; ethylene carbonate (EC): propylene carbonate (PC): diethyl carbonate (DEC) (volume ratio) 10: 20: 70
  • Example 4-5; ethylene carbonate (EC): propylene carbonate (PC): diethyl carbonate (DEC) (volume ratio) 17: 33: 50
  • Example 4-6 to 4-10 The lithium sodium titanium of Example 3-6, except that the type of electrolyte salt of the non-aqueous electrolyte used in the battery for evaluating the characteristics and the concentration of each electrolyte salt in the non-aqueous electrolyte were changed as follows: A laminated battery was produced in the same manner as in Example 3-6, including using the composite oxide powder as the negative electrode active material, and the characteristics of the laminated battery were evaluated in the same manner as in Example 1-1. The results are shown in Table 4.
  • Example 4-11 and 4-12 The proportion of the conductive agent in the coating material used for the production of the negative electrode sheet was 3.0 mass% for acetylene black and 2.0 mass% for multi-walled carbon nanotubes in Example 4-11, and acetylene black in Example 4-12.
  • Example 3- A laminated battery was produced in the same manner as in Example 6, and the characteristics of the laminated battery were evaluated in the same manner as in Example 1-1. The results are shown in Table 4.
  • the general formula of the present invention Li 2 + x Na 2 + y Ti 6-z M z O 14 (where M is at least one element selected from Al, Ga, In, V, Nb and Ta, and x -0.1 ⁇ x ⁇ 0.1, y is ⁇ 0.1 ⁇ y ⁇ 0.1, and z is 0 ⁇ z ⁇ 1.)
  • M is at least one element selected from Al, Ga, In, V, Nb and Ta, and x -0.1 ⁇ x ⁇ 0.1, y is ⁇ 0.1 ⁇ y ⁇ 0.1, and z is 0 ⁇ z ⁇ 1.
  • the non-aqueous electrolyte is obtained by dissolving an electrolyte salt in a non-aqueous solvent
  • the aqueous solvent contains at least one cyclic carbonate selected from ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, and 2,3-butylene carbonate, and propylene carbonate, 1,2-
  • the ratio of the cyclic carbonate having at least one alkylene chain selected from butylene carbonate and 2,3-butylene carbonate is 55% by volume or more and 100% by volume or less, the discharge capacity maintenance rate after a high-temperature cycle is further large, Furthermore, the amount of gas generated at high temperature is small .
  • the non-aqueous electrolyte is obtained by dissolving an electrolyte salt in a non-aqueous solvent
  • the aqueous solvent contains a chain ester having at least one methyl group selected from dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, methyl propionate, methyl acetate and ethyl acetate,
  • the total chain ester content in the solvent was 60% by volume or more and 90% by volume or less, the discharge capacity retention rate after the high-temperature cycle was further large, and the amount of gas generated at a high temperature was small.
  • the nonaqueous electrolytic solution is obtained by dissolving an electrolyte salt in a nonaqueous solvent, and the electrolyte At least LiPF 6 as a salt is contained in the non-aqueous electrolyte, and at least one lithium salt selected from LiBF 4 , LiPO 2 F 2 and LiN (SO 2 F) 2 is non-aqueous at a concentration of 0.001M to 1M.
  • the discharge capacity retention rate after the high temperature cycle was further large, and the amount of gas generated at a high temperature was small.
  • the negative electrode conductive agent includes at least one conductive agent selected from graphites and carbon blacks, When the ratio of the carbon nanotubes in the total conductive agent was 1% by mass or more and 49% by mass or less, the discharge capacity retention rate after the high-temperature cycle was further large, and the amount of gas generated at a high temperature was small.
  • D50 is 10 ⁇ m or more and 35 ⁇ m or less
  • the ratio D50 / D BET ( ⁇ m / ⁇ m) of D50 to D BET is 25 or more and 100 or less
  • the average circularity of secondary particles is In the case where the powder physical properties were 80% or more and the average compressive strength of the secondary particles was 0.3 MPa or more and 7 MPa or less, the discharge capacity retention rate after the high-temperature cycle was further large, and the amount of gas generated at high temperature was small.
  • the lithium sodium titanium composite oxide powder of the present invention is used, an energy storage device having a large energy density, excellent charge / discharge cycle characteristics in a high temperature environment, and a small amount of gas generated after the charge / discharge cycle can be obtained. Therefore, the lithium sodium titanium composite oxide powder of the present invention is particularly suitable as an electrode material for an electricity storage device that is mounted on HEV, PHEV, BEV or the like and whose performance is strongly required not to deteriorate over a long period of time.

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Abstract

La présente invention concerne une poudre d'oxyde complexe à base de lithium, de sodium et de titane pour un matériau actif d'électrode d'un dispositif de stockage, ladite poudre d'oxyde complexe à base de lithium, de sodium et de titane ayant, comme phase principale, un oxyde complexe à base de lithium, de sodium et de titane qui présente une structure cristalline appartenant à un groupe spatial Cmca ou à un groupe spatial Fmmm et qui est exprimée par la formule générale Li2 + xNa2 + yTi6 - zMzO14 (où x satisfait l'expression -0,1 ≤ x ≤ 0,1, y satisfait l'expression -0,1 ≤ y ≤ 0,1, z satisfait l'expression 0 < z ≤ 1, et M est au moins un élément choisi dans le groupe constitué par l'aluminium (Al), le gallium (Ga), l'indium (In), le vanadium (V), le niobium (Nb) et le tantale (Ta)).
PCT/JP2016/082161 2015-10-30 2016-10-28 Poudre d'oxyde complexe à base de lithium, de sodium et de titane pour une électrode d'un dispositif de stockage, matériau actif et feuille d'électrode et dispositif de stockage utilisant cette dernière WO2017073765A1 (fr)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017168320A (ja) * 2016-03-16 2017-09-21 株式会社東芝 活物質、非水電解質電池、電池パック、及び車両
JP2017168313A (ja) * 2016-03-16 2017-09-21 株式会社東芝 活物質、非水電解質電池、電池パック及び車両
JP2017168263A (ja) * 2016-03-15 2017-09-21 株式会社東芝 活物質、非水電解質電池、電池パック及び車両
US20180277905A1 (en) * 2017-03-24 2018-09-27 Kabushiki Kaisha Toshiba Electrode construct, electrode, secondary battery, battery module, battery pack, and vehicle
CN110364696A (zh) * 2018-03-26 2019-10-22 株式会社东芝 电极、二次电池、电池组和车辆
US10505186B2 (en) 2015-01-30 2019-12-10 Kabushiki Kaisha Toshiba Active material, nonaqueous electrolyte battery, battery pack and battery module
US10511014B2 (en) 2015-01-30 2019-12-17 Kabushiki Kaisha Toshiba Battery module and battery pack
US10516163B2 (en) 2015-03-13 2019-12-24 Kabushiki Kaisha Toshiba Active material, nonaqueous electrolyte battery, battery pack and battery module
US10553868B2 (en) 2014-12-02 2020-02-04 Kabushiki Kaisha Toshiba Negative electrode active material, nonaqueous electrolyte battery, battery pack and vehicle
KR20200041471A (ko) * 2018-10-12 2020-04-22 주식회사 엘지화학 P3 결정 구조를 갖는 나트륨 복합전이금속 산화물의 제조 방법, 나트륨 이차전지용 양극 활물질, 및 이를 포함하는 양극 및 나트륨 이차전지
WO2020202350A1 (fr) * 2019-03-29 2020-10-08 株式会社 東芝 Électrode, batterie et bloc-batterie
US10957906B2 (en) 2018-03-23 2021-03-23 Kabushiki Kaisha Toshiba Electrode, secondary battery, battery pack, and vehicle
JP2021522656A (ja) * 2018-04-25 2021-08-30 バイエリシエ・モトーレンウエルケ・アクチエンゲゼルシヤフト リチウムイオン電池の作動方法、リチウムイオン電池および自動車
WO2022035606A1 (fr) * 2020-08-12 2022-02-17 Cabot Corporation Compositions contenant du noir de carbone, du graphite et des nanotubes de carbone, électrodes associées et batteries associées
US11456449B2 (en) 2018-08-02 2022-09-27 Kabushiki Kaisha Toshiba Electrode for a secondary battery, secondary battery, battery pack and vehicle
WO2023108571A1 (fr) * 2021-12-16 2023-06-22 宁德时代新能源科技股份有限公司 Élément de batterie, batterie, appareil électrique, procédé de fabrication et dispositif de fabrication
CN116830315A (zh) * 2021-11-23 2023-09-29 宁德时代新能源科技股份有限公司 一种电极组件、二次电池、电池模块、电池包及用电装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012182077A (ja) * 2011-03-02 2012-09-20 Toshiba Corp 非水電解質電池及び電池パック
JP2012209031A (ja) * 2011-03-29 2012-10-25 Toray Ind Inc 金属化合物−導電剤複合体の製造方法、該方法により得られる金属化合物−導電剤複合体およびそれを用いてなるアルカリ金属二次電池用電極剤およびアルカリ金属二次電池
JP2014086164A (ja) * 2012-10-19 2014-05-12 Jgc Catalysts & Chemicals Ltd リチウムイオン二次電池用負極材、該負極材の製造方法ならびに該負極材を用いた二次電池
WO2014194996A1 (fr) * 2013-06-05 2014-12-11 Clariant Produkte (Deutschland) Gmbh Procédé de préparation d'un spinelle de lithium-titane et son utilisation
WO2015030192A1 (fr) * 2013-08-30 2015-03-05 宇部興産株式会社 Poudre de titanate de lithium, matière active et dispositif de stockage d'électricité l'utilisant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012182077A (ja) * 2011-03-02 2012-09-20 Toshiba Corp 非水電解質電池及び電池パック
JP2012209031A (ja) * 2011-03-29 2012-10-25 Toray Ind Inc 金属化合物−導電剤複合体の製造方法、該方法により得られる金属化合物−導電剤複合体およびそれを用いてなるアルカリ金属二次電池用電極剤およびアルカリ金属二次電池
JP2014086164A (ja) * 2012-10-19 2014-05-12 Jgc Catalysts & Chemicals Ltd リチウムイオン二次電池用負極材、該負極材の製造方法ならびに該負極材を用いた二次電池
WO2014194996A1 (fr) * 2013-06-05 2014-12-11 Clariant Produkte (Deutschland) Gmbh Procédé de préparation d'un spinelle de lithium-titane et son utilisation
WO2015030192A1 (fr) * 2013-08-30 2015-03-05 宇部興産株式会社 Poudre de titanate de lithium, matière active et dispositif de stockage d'électricité l'utilisant

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TORRES-MARTINEZ,L.M. ET AL.: "Phase formation and crystal structure of ternary compound Na2Li2Ti6O14", SOLID STATE SCIENCES, vol. 8, 17 October 2006 (2006-10-17), pages 1281 - 1289, XP028072654 *
WANG,P. ET AL.: "Improved lithium storage performance of lithium sodium titanate anode by titanium site substitution with aluminum", JOURNAL OF POWER SOURCES, vol. 293, 20 May 2015 (2015-05-20), pages 33 - 41, XP055285710 *

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