WO2013129423A1 - Poudre particulaire de titanate de lithium, poudre particulaire de matière active d'électrode négative pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux - Google Patents

Poudre particulaire de titanate de lithium, poudre particulaire de matière active d'électrode négative pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux Download PDF

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WO2013129423A1
WO2013129423A1 PCT/JP2013/055013 JP2013055013W WO2013129423A1 WO 2013129423 A1 WO2013129423 A1 WO 2013129423A1 JP 2013055013 W JP2013055013 W JP 2013055013W WO 2013129423 A1 WO2013129423 A1 WO 2013129423A1
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lithium titanate
particle powder
active material
lithium
secondary battery
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藤田　和也
一路 古賀
亮尚 梶山
森　幸治
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戸田工業株式会社
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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
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium titanate particle powder that exhibits excellent initial discharge capacity and excellent gas generation suppression as a negative electrode active material for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte using the material as a negative electrode active material A secondary battery is provided.
  • lithium titanate As a negative electrode active material.
  • Lithium titanate Li 4 Ti 5 O 12 is known as a highly reliable negative electrode active material with high structural stability because the crystal structure change in the lithium ion insertion / extraction reaction due to charge / discharge is very small. .
  • Li 4 Ti 5 O 12 As a manufacturing method for obtaining lithium titanate (Li 4 Ti 5 O 12 ), a mixed powder in which a lithium salt and a titanium oxide are dry or wet mixed so that a Li / Ti ratio is approximately 0.80.
  • a so-called solid phase reaction method (hereinafter referred to as a dry method) is known in which Li 4 Ti 5 O 12 is obtained by heating and baking (these are simply a mixture of a lithium salt and a titanium oxide) (patented) References 1, 2).
  • a liquid phase reaction + solid phase reaction method (hereinafter referred to as a wet method) is known, in which a mixture of titanium and lithium is hydrothermally treated and then heated and fired to obtain Li 4 Ti 5 O 12 (Patent Patent) References 3, 4).
  • lithium titanate particle powder made of Li 4 Ti 5 O 12 with high purity by reducing the impurity phase is used, a negative electrode active material having a high initial discharge capacity, excellent output characteristics, and capable of suppressing gas generation has not yet been obtained. It is not done. In particular, in a laminate type cell, contact failure occurs due to gas generation, and battery characteristics deteriorate. Therefore, lithium titanate that generates extremely little gas is desired.
  • the inventors of the present invention focused on the abundance of TiO 2 and Li 2 TiO 3 contained in the target product Li 4 Ti 5 O 12, and as a result of earnest and examination, as a result of the conventional knowledge, that is, Li 4 Ti Rather than increasing the purity of 5 O 12 , both Li 2 TiO 3 is present in a specific range, and the specific surface area by the BET method is adjusted to a specific range, so both initial discharge capacity and gas generation suppression are excellent. It was also found that the negative electrode active material can be obtained. Furthermore, the inventors have found that a negative electrode active material excellent in output characteristics can be obtained by making the crystal distortion below a specific range, and the present invention has been achieved.
  • lithium titanate particles having a spinel structure when lithium titanate particles having a spinel structure are indexed with Fd-3m by XRD, the amount of TiO 2 by Rietveld analysis is 1.5% or less, and the amount of Li 2 TiO 3 is In the range of 1% to 6%, the amount of Li 4 Ti 5 O 12 is 94% to 99%, the crystal distortion is 0.0015 or less, and the specific surface area by the BET method is 2 m 2 / g to 7 m 2.
  • Lithium titanate particle powder characterized by being in a range of not more than / g (Invention 1).
  • the present invention is the lithium titanate particle powder according to the present invention 1 having a Li / Ti ratio (molar ratio) in the range of 0.801 to 0.83 (present invention 2).
  • the present invention is a negative electrode active material particle powder comprising the lithium titanate particle powder according to the present invention 1 or the present invention 2 (Invention 3).
  • the initial discharge capacity is 165 mAh / g or more when the direction in which lithium is inserted is charged.
  • the present invention is a non-aqueous electrolyte secondary battery using the negative electrode active material particle powder according to the present invention 3 or 4 (invention 5).
  • the lithium titanate particle powder according to the present invention exhibits excellent initial discharge capacity and output characteristics when used in a non-aqueous electrolyte secondary battery as a negative electrode active material particle powder, and has a balance in which gas generation is suppressed. Since good battery characteristics are obtained, it is suitable as an active material particle powder for a non-aqueous electrolyte secondary battery.
  • FIG. 2 is an XRD pattern of lithium titanate particle powder obtained in Example 1.
  • FIG. 2 is a scanning electron micrograph of lithium titanate particle powder obtained in Example 2.
  • the lithium titanate particle powder according to the present invention has at least a spinel structure, is a compound that can be expressed as Li 4 Ti 5 O 12 in a general chemical formula, and contains at least Li 2 TiO 3 .
  • the presence state of Li 2 TiO 3 in the lithium titanate particle powder according to the present invention may be in a state of being coated on the particle surface or in an island shape as long as it is in an amount specified by the present invention, Any shape may be present in the grains.
  • diffraction between 10 to 90 degrees (2 ⁇ / ⁇ ) can be indexed with Fd-3m in XRD.
  • Fd-3m XRD
  • the abundance of TiO 2 is 1.5% or less, and the abundance of Li 2 TiO 3 is in the range of 1.0 to 6.0%.
  • the abundance of TiO 2 exceeds 1.5%, the output characteristics are deteriorated.
  • the abundance of Li 2 TiO 3 is less than 1.0%, the initial discharge capacity and output characteristics of the secondary battery produced using this lithium titanate particle powder as the negative electrode active material particle powder are good, but the gas Occurrence increases.
  • the abundance of TiO 2 is 1.0% or less, the abundance of Li 2 TiO 3 is 1.5 to 5.0%, more preferably the abundance of TiO 2 is 0.5% or less.
  • the abundance of Li 2 TiO 3 is 2.0 to 4.0%.
  • BET specific surface area of the lithium titanate particles according to the present invention is in the range of less 2m 2 / g or more 7m 2 / g. If the specific surface area is smaller than this range, the battery capacity becomes small and the practicality is lacking. If it is larger than this range, gas is likely to be generated and the battery swells significantly.
  • the lithium titanate particle powder is subjected to XRD measurement, and the crystal distortion of the lithium titanate particle powder can be obtained by Rietveld analysis.
  • the XRD measurement condition was 2 ⁇ / ⁇ , and a range of 10 to 90 degrees was scanned 0.02 degrees.
  • the range of crystal distortion in the present invention is suitable.
  • the crystal strain exceeds 0.0015, the output characteristics deteriorate.
  • a preferable range of crystal distortion is 0.0014 or less, and a more preferable range is 0.0001 to 0.0013.
  • the following effects are brought about by satisfying the conditions defined in the present invention by various characteristics such as Li 2 TiO 3 abundance, specific surface area and crystal distortion of the lithium titanate particle powder. Conceivable.
  • an active material can suppress gas generation due to its small specific surface area.
  • the specific surface area is too small, the initial capacity is also reduced.
  • the present inventors have found that it is also related to the amount of Li 2 TiO 3 in the lithium titanate powder. Although this effect is not clear, when Li 2 TiO 3 is present in the lithium titanate particles or in the surface layer, when lithium titanate becomes Li 7 Ti 5 O 12 by full charge, not Li The existence point of 2 TiO 3 remains, and as a result, gas generation is considered to be small.
  • a prescription for increasing the specific surface area for example, a method for making fine particles
  • damage to the particles occurs when making fine particles.
  • distortion remains in the particles. It has been found that when this distortion is larger than the range of the present invention, the output characteristics deteriorate rapidly.
  • Li 2 TiO 3 abundance, specific surface area, and crystal distortion of the lithium titanate particle powder within a specific range a balance can be obtained when used as an active material particle powder for a non-aqueous electrolyte secondary battery. Battery characteristics can be obtained.
  • the Li / Ti ratio (molar ratio) of the lithium titanate particles according to the present invention is preferably 0.801 to 0.83.
  • a more preferable Li / Ti ratio (molar ratio) is 0.803 to 0.828, more preferably 0.805 to 0.827, and still more preferably 0.807 to 0.826.
  • the production method of the lithium titanate particle powder according to the present invention is not particularly limited, and can be synthesized by a method such as a wet method / dry method.
  • lithium titanate particle powder is produced by a dry method.
  • lithium titanate particle powder is obtained.
  • the lithium compounds that can be used in the present invention include lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, and lithium oxide, but inexpensive lithium carbonate is preferable.
  • TiO 2 used in the present invention is not particularly limited, water hydrates can also be used.
  • the TiO 2 to be used preferably has a crystallite size of 10 to 100 nm. In the case of TiO 2 hydrate, the thickness is preferably 1 to 20 nm. If it is larger than the crystallite size, a large amount of heterogeneous phase is generated in the synthesis, making it difficult to obtain the target lithium titanate particle powder of the present invention.
  • TiO 2 that can be used in the present invention has an anatase type, a rutile type, and a mixed phase thereof, and an anatase type is preferable.
  • the lithium compound and TiO 2 used for producing the lithium titanate particle powder according to the present invention are preferably adjusted and mixed so that the Li / Ti ratio after firing is 0.801 to 0.83.
  • it can be done by adjusting the mixing ratio of the lithium compound and TiO 2.
  • the reason why Li / Ti is made larger than the theoretical ratio of 0.80 is to obtain lithium titanate having higher crystallinity and to leave Li 2 TiO 3 after firing. If it is larger than the above range, the initial discharge capacity is decreased, and the lithium titanate particles obtained by further increasing the Li 2 TiO 3 residue have a large residual alkali, resulting in gelation of the paint.
  • the mixture is fired at 700 to 900 ° C. to obtain the lithium titanate particle powder according to the present invention. If the firing temperature is less than 700 ° C., a large amount of TiO 2 remains. If the firing temperature is too high, the amount of lithium evaporation increases and a large amount of TiO 2 phase is generated.
  • the firing temperature is preferably 700 to 880 ° C. However, since the progress of the reaction varies depending on the characteristics of the TiO 2 used (BET specific surface area, crystallite diameter, etc.), the preferred temperature range of the firing temperature varies.
  • the atmosphere in firing may be an oxidizing atmosphere or a reducing atmosphere.
  • the lithium titanate particle powder obtained in the present invention may have oxygen deficiency or oxygen excess within the range of known techniques.
  • the particle size distribution can be adjusted by pulverizing the lithium titanate particle powder obtained by firing.
  • the shape of the particle size distribution may be sharp, broad, or bimodal.
  • a ball mill, a bead mill, a hammer mill or the like can be used for pulverization.
  • the target lithium titanate particle powder can be obtained by combining the Li / Ti ratio, firing temperature and firing time, and pulverization conditions of the raw material mixed powder. For example, when heat treatment is performed at a relatively high temperature, a product having a low specific surface area tends to be obtained, and when the pulverization time is increased, crystal strain tends to increase.
  • the lithium titanate particle powder according to the present invention can be used as a negative electrode active material particle powder for a non-aqueous electrolyte secondary battery.
  • a conductive agent and a binder are added and mixed according to a conventional method.
  • the conductive agent acetylene black, carbon black, graphite and the like are preferable
  • the binder polytetrafluoroethylene, polyvinylidene fluoride and the like are preferable.
  • the secondary battery manufactured using the negative electrode containing the negative electrode active material particle powder according to the present invention includes a positive electrode, a negative electrode, and an electrolyte.
  • lithium cobaltate lithium manganate, lithium nickelate or the like, which is a positive electrode material for a general non-aqueous electrolyte secondary battery, can be used.
  • an organic solvent containing at least one of carbonates such as propylene carbonate and dimethyl carbonate and ethers such as dimethoxyethane can be used as the solvent for the electrolytic solution.
  • At least one lithium salt such as lithium perchlorate and lithium tetrafluoroborate can be dissolved in the above solvent and used.
  • the non-aqueous electrolyte secondary battery manufactured using the electrode containing the negative electrode active material particle powder according to the present invention has an initial discharge capacity of 1.0 V or higher by an evaluation method described later of 165 mAh / g or higher.
  • the gas generation amount was 1.0 cc / cm 3 according to the evaluation method described later. Is less than.
  • the lithium titanate particle powder according to the present invention can also be used as a positive electrode active material.
  • the non-aqueous electrolyte secondary battery is composed of the above electrode, counter electrode and electrolyte, and the counter electrode (negative electrode) is metallic lithium, lithium alloy, or graphite. Carbonaceous materials such as coke are used.
  • the most important point in the present invention is the use of a lithium titanate particle powder having a specific surface area and crystal distortion within the range of the present invention, in which a specific amount of Li 2 TiO 3 according to the present invention is present. It is possible to obtain a non-aqueous electrolyte secondary battery that has excellent initial discharge capacity and output characteristics and can suppress gas generation.
  • the impurity phase has been reduced to obtain lithium titanate particle powder made of Li 4 Ti 5 O 12 having high purity.
  • simply making it high purity does not sufficiently satisfy the characteristics that the initial discharge capacity is high and gas generation can be suppressed.
  • the present inventors have quantified the impurity phase by Rietveld analysis, which can be more accurately quantified than the quantification by the peak intensity ratio of X-ray diffraction, the presence of a very small amount of Li 2 TiO 3 , and the BET specific surface area. By controlling the crystal strain, it is possible to obtain a negative electrode active material exhibiting high battery characteristics.
  • a typical embodiment of the present invention is as follows.
  • the BET specific surface area was measured by using a Macsorb HM Model-1208 manufactured by Mountech Co., Ltd. after drying and deaeration of the sample under nitrogen gas at 120 ° C. for 45 minutes.
  • the Li / Ti ratio was determined by preparing an adjustment liquid and quantifying each element using ICAP6500 Thermo Fisher Scientific Co., Ltd. for ICP measurement.
  • the X-ray diffraction of the sample was measured using a SmartLab manufactured by Rigaku Corporation (10 to 90 degrees, 0.02 degree step scan).
  • the amount of TiO 2 and the amount of Li 2 TiO 3 and the calculation of crystal distortion and crystallite size were calculated by performing Rietveld analysis using X-ray diffraction data.
  • Rietan2000 was used for Rietveld analysis.
  • the negative electrode active material particle powder according to the present invention was subjected to battery evaluation using a 2032 type coin cell.
  • lithium titanate which is an active material particle powder for a negative electrode according to the present invention
  • the amount of active material is 90% by weight
  • acetylene black is 2.5% by weight as a conductive material
  • graphite is 2%.
  • 5% by weight and 5% by weight of polyvinylidene fluoride dissolved in N-methylpyrrolidone as a binder were mixed, applied to an Al metal foil, and dried at 120 ° C. The sheet was punched out to 16 mm ⁇ , and then pressure-bonded at 3.0 t / cm 2 was used for the positive electrode.
  • the counter electrode was made of metallic lithium with a thickness of 500 ⁇ m punched to 16 mm ⁇ , and the electrolyte was a 2032 type coin cell using a solution in which EC and DMC in which 1 mol / L LiPF 6 was dissolved was mixed at a volume ratio of 1: 2. .
  • Charging / discharging characteristics were as follows: charging was performed at a current density of 0.1 C up to 1.0 V when charging was performed in a direction where Li was desorbed in an environment of a constant temperature bath at 25 ° C. (CC-CC operation) Thereafter, discharging was performed at a current density of 0.1 C up to 3.0 V (CC-CC operation).
  • the first charge capacity (1st-CH) and discharge capacity (1st-DCH) of this operation were measured. The measurement results are shown in Table 2. In Table 2, when the initial charge capacity was 165 mAh / g or more, “ ⁇ ”, and less than 165 mAh / g, “ ⁇ ”.
  • the output characteristics were as follows: discharging was performed at a current density of 0.1 C up to 1.0 V in a constant temperature bath at 25 ° C. (CC-CC operation), and charging was performed at a current density of 0.1 C up to 3.0 V (CC-CC operation). Let the discharge capacity at this time be a. Next, discharging was performed at a current density of 4 C up to 1.0 V (CC-CC operation), and charging was performed at a current density of 0.1 C up to 3.0 V (CC-CC operation). When the discharge capacity at this time is b, the output characteristic is (b / a ⁇ 100 (%)). The measurement results are shown in Table 2. In Table 2, when the output characteristic is 80 or more, “ ⁇ ” is set, and when the output characteristic is less than 80%, “X” is set.
  • the gas generation amount was evaluated by producing a laminate cell by the following method.
  • Li 1.07 Mn 1.83 Al 0.1 O 4 was 92% by weight, acetylene black was 2.5% by weight as a conductive material, graphite was 2.5% by weight, and dissolved in N-methylpyrrolidone as a binder. 3% by weight of polyvinylidene fluoride was mixed, applied to an Al metal foil, dried at 120 ° C., cut into a 40 mm ⁇ 100 mm square, and then consolidated at 3.0 t / cm 2 . It was.
  • a laminate cell was prepared by combining two sets of these electrodes so as to face each other.
  • the initial charge / discharge was performed at room temperature, and then charged to 2.7 V, and the volume of the laminate cell at this voltage was measured.
  • the volume of the laminate cell was measured again, and the amount of gas generated was evaluated from the volume change before and after high-temperature storage.
  • the measurement results are shown in Table 2.
  • the gas generation amount of 1.0 cc / g or less was designated as “ ⁇ ”, and the gas generation amount exceeding 1.0 cc / g was designated as “x”.
  • Example 1 TiO 2 having a specific surface area of 50 m 2 / g and lithium carbonate were adjusted to a molar ratio of Li / Ti ratio of 0.85, and mixed for 1 hr with Reiki.
  • the mixed powder was put into an alumina crucible and fired in a muffle furnace at a temperature of 850 ° C. for 6 hours in an air atmosphere to obtain lithium titanate particle powder.
  • This lithium titanate was pulverized with a ball mill for 1.5 hours to obtain a lithium titanate powder.
  • Comparative Example 1 Except having changed the molar ratio of Li / Ti ratio into 0.80, it processed similarly to Example 1 and obtained lithium titanate particle powder.
  • Example 2 A lithium titanate particle powder was obtained in the same manner as in Example 1 except that the pulverization time in the ball mill was changed to 3 hours.
  • Comparative Example 2 A lithium titanate particle powder was obtained in the same manner as in Example 1 except that the pulverization time in the ball mill was changed to 6 hours.
  • Example 3 TiO 2 having a specific surface area of 330 m 2 / g and lithium carbonate were adjusted to 0.82 at a molar ratio of Li / Ti ratio, and mixed for 1 hr with Reiki.
  • the mixed powder was put into an alumina crucible and fired in a muffle furnace at a temperature of 750 ° C. for 4 hours in an air atmosphere to obtain lithium titanate particle powder.
  • This lithium titanate was pulverized with a ball mill for 0.5 hours to obtain a lithium titanate powder.
  • Comparative Example 3 A lithium titanate particle powder was obtained in the same manner as in Example 3 except that the molar ratio of Li / Ti ratio was changed to 0.90.
  • Example 4 TiO 2 having a specific surface area of 8 m 2 / g and lithium carbonate were adjusted to a molar ratio of Li / Ti ratio of 1.00, and mixed for 1 hr with Reiki.
  • the mixed powder was put into an alumina crucible and fired in an air atmosphere at a temperature of 880 ° C. for 10 hours in a muffle furnace to obtain lithium titanate particle powder.
  • This lithium titanate was pulverized with a ball mill for 4 hours to obtain a lithium titanate powder.
  • Comparative Example 4 A lithium titanate particle powder was obtained in the same manner as in Example 4 except that the firing temperature was changed to 750 ° C.
  • Example 5 TiO 2 having a specific surface area of 90 m 2 / g and lithium carbonate were adjusted to a molar ratio of Li / Ti ratio of 0.83, and mixed for 1 hr with Reiki.
  • the mixed powder was put into an alumina crucible, and baked in an air atmosphere at a temperature of 840 ° C. for 4 hours in a muffle furnace to obtain lithium titanate particle powder.
  • This lithium titanate was pulverized with a ball mill for 1.5 hours to obtain a lithium titanate powder.
  • Comparative Example 5 A lithium titanate particle powder was obtained in the same manner as in Example 5 except that the pulverization time in the ball mill was changed to 5 hours.
  • Example 6 TiO 2 having a specific surface area of 285 m 2 / g and lithium carbonate were adjusted to a molar ratio of Li / Ti ratio of 0.83, and mixed for 1 hr by Reiki.
  • the mixed powder was put into an alumina crucible and fired in an air atmosphere at a temperature of 800 ° C. for 3 hours in a muffle furnace to obtain lithium titanate particle powder.
  • This lithium titanate was pulverized with a ball mill for 1.5 hours to obtain a lithium titanate powder.
  • Comparative Example 6 A lithium titanate particle powder was obtained in the same manner as in Example 6 except that the firing temperature was changed to 850 ° C. and the firing time was changed to 4 hours. In Comparative Example 6, since the raw material TiO2 had a large BET specific surface area of 285 m 2 / g, the reaction was likely to proceed. By baking at 850 ° C., a low BET specific surface area was obtained.
  • Comparative Example 7 Except having changed the molar ratio of Li / Ti ratio into 0.82, it processed like Example 5 and obtained lithium titanate particle powder.
  • Tables 1 and 2 show characteristics and conditions of lithium titanate obtained in Examples and Comparative Examples.
  • the lithium titanate particle powder according to the present invention has an initial discharge capacity of 165 mAh / g or more and an output characteristic of 80% or more, and gas generation is suppressed to 1.0 cc / g or less. Therefore, it is suitable as an active material for a non-aqueous electrolyte secondary battery.
  • the lithium titanate particle powder according to the present invention exhibits excellent initial discharge capacity and output characteristics when used in a non-aqueous electrolyte secondary battery as a negative electrode active material particle powder, and has a balance in which gas generation is suppressed. Since good battery characteristics are obtained, it is suitable as an active material particle powder for a non-aqueous electrolyte secondary battery.

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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention porte sur une poudre particulaire de titanate de lithium qui a une capacité de décharge initiale élevée utilisée comme matière active pour une batterie secondaire à électrolyte non aqueux, qui permet de réduire au minimum la production de gaz et qui conduit à des caractéristiques de batterie bien équilibrées. La poudre particulaire de titanate de lithium de la présente invention a une structure spinelle et, lorsqu'un indice est appliqué par Fd-3m en diffraction des rayons X, le volume de TiO2 par analyse de Rietveld est inférieur ou égal à 1,5 %, le volume de Li2TiO3 est dans la plage de 1-6 %, le volume de Li4Ti5O12 est de 94-99 %, la distorsion cristalline est inférieure ou égale à 0,0015 et la surface spécifique BET est dans la plage de 2-7 m2/g.
PCT/JP2013/055013 2012-02-29 2013-02-26 Poudre particulaire de titanate de lithium, poudre particulaire de matière active d'électrode négative pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux WO2013129423A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106847543A (zh) * 2016-12-27 2017-06-13 宁波中车新能源科技有限公司 一种纳米Li4Ti5O12/Li2TiO3复合电极材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011113796A (ja) * 2009-11-26 2011-06-09 Nippon Chem Ind Co Ltd リチウム二次電池用活物質およびこれを用いたリチウム二次電池
JP2012006816A (ja) * 2010-06-28 2012-01-12 Hitachi Ltd チタン酸リチウム粒子およびその製造方法、リチウムイオン電池用負極、ならびにリチウム電池
JP2012214362A (ja) * 2011-03-31 2012-11-08 Toda Kogyo Corp チタン酸リチウム粒子粉末及びその製造方法、非水電解質二次電池用負極活物質粒子粉末並びに非水電解質二次電池
JP2013051104A (ja) * 2011-08-31 2013-03-14 Toda Kogyo Corp チタン酸リチウム粒子粉末、非水電解質二次電池用負極活物質粒子粉末並びに非水電解質二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011113796A (ja) * 2009-11-26 2011-06-09 Nippon Chem Ind Co Ltd リチウム二次電池用活物質およびこれを用いたリチウム二次電池
JP2012006816A (ja) * 2010-06-28 2012-01-12 Hitachi Ltd チタン酸リチウム粒子およびその製造方法、リチウムイオン電池用負極、ならびにリチウム電池
JP2012214362A (ja) * 2011-03-31 2012-11-08 Toda Kogyo Corp チタン酸リチウム粒子粉末及びその製造方法、非水電解質二次電池用負極活物質粒子粉末並びに非水電解質二次電池
JP2013051104A (ja) * 2011-08-31 2013-03-14 Toda Kogyo Corp チタン酸リチウム粒子粉末、非水電解質二次電池用負極活物質粒子粉末並びに非水電解質二次電池

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AKIHISA KAJIYAMA ET AL.: "Koshutsuryoku Li4Ti5012 no Funmatsu Oyobi Denchi Tokusei", ABSTRACTS, BATTERY SYMPOSIUM IN JAPAN, vol. 52, 17 October 2011 (2011-10-17), pages 200 *
G. Q. LIU ET AL.: "Synthesis and electrochemical properties of Li4Ti5012", J. ALLOY. COMPD., vol. 509, no. 22, 2 June 2011 (2011-06-02), pages 6427 - 6432 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106847543A (zh) * 2016-12-27 2017-06-13 宁波中车新能源科技有限公司 一种纳米Li4Ti5O12/Li2TiO3复合电极材料及其制备方法

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