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WO2012002122A1 - Procédé de production de titanate de lithium poreux, titanate de lithium poreux et batterie au lithium l'utilisant - Google Patents

Procédé de production de titanate de lithium poreux, titanate de lithium poreux et batterie au lithium l'utilisant Download PDF

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Publication number
WO2012002122A1
WO2012002122A1 PCT/JP2011/063210 JP2011063210W WO2012002122A1 WO 2012002122 A1 WO2012002122 A1 WO 2012002122A1 JP 2011063210 W JP2011063210 W JP 2011063210W WO 2012002122 A1 WO2012002122 A1 WO 2012002122A1
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Prior art keywords
lithium titanate
porous
lithium
porous lithium
titanate
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English (en)
Japanese (ja)
Inventor
伸樹 糸井
隆寛 三島
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Otsuka Chemical Co Ltd
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Otsuka Chemical Co Ltd
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Priority to CN2011800290973A priority Critical patent/CN102958844A/zh
Publication of WO2012002122A1 publication Critical patent/WO2012002122A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • 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
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • 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

Definitions

  • the present invention relates to a method for producing porous lithium titanate, porous lithium titanate, and a lithium battery using the same.
  • lithium titanate When lithium titanate is used as the electrode active material for lithium batteries, lithium titanate does not show any change in crystal structure due to charge / discharge, so lithium titanate is a battery material with excellent stability and safety. As a result, various developments have been made.
  • Patent Document 1 proposes a dense lithium titanate having a flaky or plate-like particle shape in which lithium ions are rapidly doped and dedoped.
  • the lithium titanate described in Patent Document 1 has a flake shape or a plate shape, the slurry using this lithium titanate has poor fluidity and is difficult to apply on the current collector. .
  • the lithium titanate described in Patent Document 1 has poor handling properties when mixed with a conductive agent or a binder during electrode production, and it is difficult to uniformly mix with the conductive agent or the binder.
  • the lithium titanate described in Patent Document 1 has a dense structure, there is also a problem that the impregnation property of the nonaqueous electrolyte is poor.
  • Patent Document 2 proposes increasing the battery capacity per unit volume of the battery by increasing the tap density of lithium titanate used as the electrode active material.
  • Patent Document 2 since a mixture having a low reaction activity obtained by drying and granulating a slurry containing a titanium compound and a lithium compound is baked, secondary particles in which primary particles are closely bonded are formed. . For this reason, the lithium titanate described in Patent Document 2 has a problem that the impregnation property of the nonaqueous electrolyte is poor.
  • Patent Document 3 proposes lithium-titanium composite oxide particles having a good non-aqueous electrolyte impregnation property and an average pore diameter of 5 nm to 50 nm.
  • the method for producing lithium titanate composite oxide particles described in Patent Document 3 since the powder strength decreases, the average pore diameter cannot be 50 nm or more, and the particle diameter is 1 ⁇ m or more, Lithium titanium composite oxide particles having sufficient nonaqueous electrolyte impregnation properties cannot be produced. Further, the method for producing lithium titanate composite oxide particles described in Patent Document 3 has a problem that the tap density cannot be increased because the particle diameter cannot be increased.
  • the prior art documents 1 to 3 have a problem that the impregnation property of the nonaqueous electrolyte cannot be sufficiently improved.
  • An object of the present invention is to provide a method for producing porous lithium titanate that is excellent in impregnation of a nonaqueous electrolyte and can enhance charge / discharge cycle characteristics when used as an electrode active material of a lithium battery, and porous titanate
  • the object is to provide lithium and a lithium battery using the same.
  • the production method of the present invention is a method for producing porous lithium titanate, a step of obtaining a pulverized mixture by mixing a raw material containing a titanium source and a lithium source while pulverizing them into mechanochemicals, and firing the pulverized mixture And a step of performing.
  • porous lithium titanate when used as an electrode active material of a lithium battery, porous lithium titanate that is excellent in nonaqueous electrolyte impregnation and can improve charge / discharge cycle characteristics can be produced. .
  • the temperature for firing the pulverized mixture is preferably in the range of 800 ° C. to 1000 ° C., and more preferably in the range of 800 to 950 ° C. By baking within such a temperature range, porous lithium titanate can be produced more effectively.
  • the firing temperature is less than 800 ° C., titanium dioxide is precipitated, and the content of lithium titanate is lowered. Therefore, when used in a lithium battery, the cycle characteristics may be deteriorated.
  • the firing temperature exceeds 1000 ° C., ramsdellite type lithium titanate is generated, and the cycle characteristics may be deteriorated when used for a lithium battery.
  • the time for firing the pulverized mixture is not particularly limited, but is preferably in the range of 0.5 hours to 10 hours, and more preferably in the range of 1 hour to 6 hours.
  • the pulverized mixture can be fired using various firing means such as an electric furnace, a rotary kiln, a tubular furnace, a fluidized firing furnace, and a tunnel kiln.
  • the obtained fired product may be coarsely pulverized and finely pulverized using a hammer mill, a bin mill, a jaw crusher, or the like, and subjected to a sieving treatment as necessary.
  • the mechanochemical pulverization includes a method of pulverizing while giving a physical impact.
  • an example of mechanochemical pulverization includes pulverization by a vibration mill. It is considered that a metastable phase is obtained as a result of simultaneous disruption of atomic arrangement and reduction of interatomic distance due to shear stress due to the grinding of the mixed powder, and atomic movement of the contact portion of different particles. As a result, a pulverized mixture having a high reaction activity is obtained. By firing the pulverized mixture having a high reaction activity, porous lithium titanate excellent in nonaqueous electrolyte impregnation can be produced.
  • the mechanochemical pulverization in the present invention is preferably performed as a dry process without using water or a solvent.
  • the mixing treatment time by mechanochemical pulverization is not particularly limited, but it is generally preferably in the range of 0.1 hour to 2.0 hours.
  • the raw materials used for the production of porous lithium titanate include a titanium source and a lithium source.
  • the titanium source one containing titanium oxide or one that generates a compound containing titanium oxide by heating can be used.
  • Specific examples of the titanium source include titanium oxide, rutile ore, titanium hydroxide wet cake, hydrous titania, and the like.
  • the lithium source a compound that generates lithium oxide by heating can be used.
  • the lithium source include lithium carbonate, lithium hydroxide, and lithium chloride. Among these, lithium carbonate is particularly preferably used.
  • the average pore diameter of the porous lithium titanate produced by the production method of the present invention is preferably in the range of 100 nm to 1000 nm, and more preferably in the range of 100 nm to 700 nm.
  • the impregnation property of the non-aqueous electrolyte can be further improved when the porous lithium titanate is used as an electrode active material of a lithium battery.
  • the charge / discharge cycle characteristics of the lithium battery can be further improved.
  • the porous lithium titanate is preferably formed by fusing particles having a shape in which a plurality of protrusions extend in irregular directions. That is, the porous lithium titanate is preferably a porous particle in which particles having an amoeba shape in which a plurality of protrusions extend in irregular directions are fused with each other.
  • the porous lithium titanate preferably contains spinel type lithium titanate.
  • battery characteristics such as charge / discharge cycle characteristics can be enhanced.
  • the first porous lithium titanate according to the present invention is manufactured by the method of the present invention.
  • the second porous lithium titanate according to the present invention is formed by fusing particles having a shape in which a plurality of protrusions extend irregularly, has an average pore diameter of 100 nm to 1000 nm, and spinel type titanate. It contains lithium.
  • the oil absorption amount of the second porous lithium titanate according to the present invention is preferably 0.5 ml / g or more. In this case, the impregnation property of the nonaqueous electrolyte is further improved, and the charge / discharge cycle characteristics of the lithium battery can be further improved.
  • the upper limit of the oil absorption is not particularly limited, but is generally 5 ml / g or less.
  • the third porous lithium titanate according to the present invention has an oil absorption of 0.5 ml / g or more, an average pore diameter of 100 nm to 1000 nm, and contains spinel type lithium titanate.
  • the lithium titanate contained in the porous lithium titanate of the present invention is represented by the general formula Li x Ti y O 4 (0.8 ⁇ x ⁇ 1.4, 1.6 ⁇ y ⁇ 2.2). Is preferred.
  • the tap density of the porous lithium titanate particles of the present invention is preferably in the range of 1.0 g / ml to 2.0 g / ml, and preferably in the range of 1.0 g / ml to 1.4 g / ml. It is more preferable. In this case, since the filling property of the porous lithium titanate particles is improved, the battery capacity per unit volume of the battery can be increased when used as an electrode active material of a lithium battery.
  • the median diameter (average particle diameter) of the porous lithium titanate particles of the present invention is preferably in the range of 1 ⁇ m to 200 ⁇ m, more preferably in the range of 3 ⁇ m to 40 ⁇ m, and in the range of 20 ⁇ m to 40 ⁇ m. More preferably. According to this configuration, the filling property of the porous lithium titanate particles is improved, and when used as an electrode active material of a lithium battery, the battery capacity per unit volume of the battery can be increased.
  • the lithium battery of the present invention is characterized by containing the porous lithium titanate of the present invention as an electrode active material.
  • the porous lithium titanate of the present invention is used as a positive electrode active material
  • the negative electrode active material for example, metallic lithium, a lithium alloy, or a carbon-based material such as graphite or coke can be used.
  • lithium-containing manganese oxide, lithium manganate, lithium cobaltate, lithium nickelate, vanadium pentoxide, or the like can be used as the positive electrode active material.
  • An electrode using the porous lithium titanate of the present invention as an electrode active material is produced by adding a conductive agent such as carbon black and a binder such as a fluororesin to porous lithium titanate particles, and forming or coating appropriately. can do.
  • solvent used for the non-aqueous electrolyte those conventionally used for lithium batteries can be used, and for example, propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, and the like can be used.
  • a lithium salt conventionally used in a lithium battery can be used.
  • a lithium salt such as LiPF 6 can be used.
  • porous lithium titanate when used as an active material of a lithium battery, it is possible to produce porous lithium titanate that has excellent nonaqueous electrolyte impregnation properties and can improve charge / discharge cycle characteristics.
  • porous lithium titanate of the present invention When used as an electrode active material of a lithium battery, it has excellent nonaqueous electrolyte impregnation properties and can improve charge / discharge cycle characteristics.
  • the lithium battery of the present invention contains the porous lithium titanate of the present invention, the charge / discharge cycle characteristics can be improved.
  • FIG. 1 is a SEM photograph (left side: 10000 times magnification, right side: 2000 times magnification) showing porous lithium titanate produced in Example 1 according to the present invention.
  • FIG. 2 is an SEM photograph (left side: 10000 times magnification, right side: 2000 times magnification) showing porous lithium titanate produced in Example 2 according to the present invention.
  • FIG. 3 is an SEM photograph (left side: 10000 times magnification, right side: 2000 times magnification) showing porous lithium titanate produced in Example 3 according to the present invention.
  • FIG. 4 is a SEM photograph (left side: 10000 times magnification, right side: 2000 times magnification) showing porous lithium titanate produced in Example 4 according to the present invention.
  • FIG. 1 is a SEM photograph (left side: 10000 times magnification, right side: 2000 times magnification) showing porous lithium titanate produced in Example 1 according to the present invention.
  • FIG. 2 is an SEM photograph (left side: 10000 times magnification, right side
  • FIG. 5 is an SEM photograph (left side: 10000 times magnification, right side: 2000 times magnification) showing porous lithium titanate produced in Example 5 according to the present invention.
  • FIG. 6 is an SEM photograph (left side: 10000 times magnification, right side: 2000 times magnification) showing the porous lithium titanate produced in Comparative Example 1.
  • FIG. 7 is a diagram showing an X-ray diffraction chart of porous lithium titanate manufactured in Example 1 according to the present invention.
  • FIG. 8 is an X-ray diffraction chart of porous lithium titanate manufactured in Example 2 according to the present invention.
  • FIG. 9 is a diagram showing an X-ray diffraction chart of porous lithium titanate manufactured in Example 3 according to the present invention.
  • FIG. 10 is a diagram showing an X-ray diffraction chart of porous lithium titanate manufactured in Example 4 according to the present invention.
  • FIG. 11 is an X-ray diffraction chart of porous lithium titanate manufactured in Example 5 according to the present invention.
  • FIG. 12 is a diagram showing an X-ray diffraction chart of porous lithium titanate manufactured in Comparative Example 1.
  • Example 1 584.0 g of titanium oxide and 216.0 g of lithium carbonate were mixed for 2.0 hours while being pulverized with a vibration mill. 500 g of the obtained pulverized mixture was filled in a crucible and baked at 950 ° C. for 4 hours in an electric furnace.
  • the obtained fired product was pulverized with a hammer mill and processed with a sieve having an opening of 250 ⁇ m.
  • the obtained product had a crystal phase of Li 1.33 Ti 1.66 O 4 and was a spinel type. Moreover, the crystallite diameter was 100 nm or more.
  • the obtained lithium titanate has a median diameter (average particle diameter) of 38.6 ⁇ m, an average pore diameter of 620 nm, a tap density of 1.2 g / ml, and a specific surface area of 0.55 m 2 / g.
  • the oil absorption was 0.55 ml / g.
  • X-ray diffraction was measured with “RINT2000” manufactured by Rigaku Corporation.
  • the crystallite size was determined from the Scherrer equation.
  • the median diameter (average particle diameter) was measured using a “SALD-2100 laser diffraction particle size distribution analyzer” manufactured by Shimadzu Corporation.
  • the average pore diameter was measured by a mercury intrusion method using “Autopore 9510” manufactured by Shimadzu Corporation.
  • the tap density was measured by “Powder Tester PT-S” manufactured by Hosokawa Micron.
  • the specific surface area was measured by the BET method using “GEMINI 2360” manufactured by Shimadzu Corporation.
  • the oil absorption was measured according to JISK 5101-13-1.
  • the obtained lithium titanate particles were observed with a scanning electron microscope (SEM).
  • FIG. 1 shows an SEM photograph of the obtained lithium titanate particles.
  • the photo on the left is 10000 times magnification, and the photo on the right is 2000 times magnification.
  • the obtained lithium titanate particles have a shape in which particles having a shape in which a plurality of protrusions extend in irregular directions are fused. That is, it turns out that it becomes the porous body particle
  • Example 2 Lithium titanate was synthesized in the same manner as in Example 1 except that the firing temperature was 900 ° C.
  • the obtained lithium titanate had a crystal phase of Li 1.33 Ti 1.66 O 4 .
  • the crystallite diameter is 100 nm or more, the median diameter is 25.2 ⁇ m, the average pore diameter is 390 nm, the tap density is 1.4 g / ml, the specific surface area is 1.00 m 2 / g, The oil absorption was 0.65 ml / g.
  • FIG. 2 is an SEM photograph showing the obtained lithium titanate particles.
  • the photo on the left is 10000 times magnification, and the photo on the right is 2000 times magnification.
  • the obtained lithium titanate particles have a shape in which particles having a shape in which a plurality of protrusions extend in an irregular direction are fused. That is, it turns out that it becomes the porous body particle
  • Example 3 Lithium titanate was synthesized in the same manner as in Example 1 except that the firing temperature was 850 ° C.
  • the obtained lithium titanate had a crystal phase of Li 1.33 Ti 1.66 O 4 .
  • the crystallite diameter is 100 nm or more, the median diameter is 23.7 ⁇ m, the average pore diameter is 250 nm, the tap density is 1.4 g / ml, the specific surface area is 1.22 m 2 / g, The oil absorption was 0.65 ml / g.
  • FIG. 3 is an SEM photograph showing the obtained lithium titanate particles.
  • the photo on the left is 10000 times magnification, and the photo on the right is 2000 times magnification.
  • the obtained lithium titanate particles have a shape in which particles having a shape in which a plurality of protrusions extend in an irregular direction are fused. That is, it turns out that it becomes the porous body particle
  • Example 4 Lithium titanate was synthesized in the same manner as in Example 1 except that the firing temperature was 800 ° C.
  • the obtained lithium titanate had a crystal phase of Li 1.33 Ti 1.66 O 4 .
  • the crystallite diameter is 100 nm or more, the median diameter is 22.7 ⁇ m, the average pore diameter is 140 nm, the tap density is 1.3 g / ml, the specific surface area is 1.60 m 2 / g, The oil absorption was 0.70 ml / g.
  • FIG. 4 is an SEM photograph showing the obtained lithium titanate particles.
  • the photo on the left is 10000 times magnification, and the photo on the right is 2000 times magnification.
  • the obtained lithium titanate particles have a shape in which particles having a shape in which a plurality of protrusions extend in an irregular direction are fused. That is, it turns out that it becomes the porous body particle
  • Example 5 Lithium titanate was synthesized in the same manner as in Example 1 except that the firing temperature was 1000 ° C.
  • the obtained lithium titanate had a crystal phase of Li 1.33 Ti 1.66 O 4 and a crystal phase of ramsdellite type Li 2 Ti 3 O 7 .
  • the crystallite diameter is 100 nm or more, the median diameter is 31.5 ⁇ m, the average pore diameter is 810 nm, the tap density is 1.3 g / ml, the specific surface area is 0.40 m 2 / g, The oil absorption was 0.55 ml / g.
  • FIG. 5 is an SEM photograph showing the obtained lithium titanate particles.
  • the photo on the left is 10000 times magnification, and the photo on the right is 2000 times magnification.
  • the obtained lithium titanate particles have a shape in which particles having a shape in which a plurality of protrusions extend in an irregular direction are fused. That is, it turns out that it becomes the porous body particle
  • Comparative Example 1 588.0 g of titanium oxide and 141.0 g of lithium hydroxide were added to 1353.0 g of water, and mixed by stirring in a wet manner. This mixture was spray-dried at 110 ° C., and 500 g of the dried mixture was charged in a crucible and baked at 850 ° C. for 4 hours in an electric furnace.
  • the obtained lithium titanate had a crystal phase of Li 1.33 Ti 1.66 O 4 .
  • the crystallite diameter is 100 nm or more, the median diameter is 19.8 ⁇ m, the average pore diameter is 50 nm, the tap density is 1.5 g / ml, the specific surface area is 2.13 m 2 / g, The oil absorption was 0.35 ml / g.
  • FIG. 6 is an SEM photograph showing the obtained lithium titanate particles. The photo on the left is 10000 times magnification, and the photo on the right is 2000 times magnification.
  • the size of the primary particles is smaller in this comparative example than the porous lithium titanate particles obtained in Example 3 fired at 850 ° C.
  • Electrodes were produced using the lithium titanates of Examples 1 to 5 and Comparative Example 1 obtained as described above as electrode active materials. Specifically, 90 parts by weight of lithium titanate, 5 parts by weight of carbon black and 5 parts by weight of fluororesin were kneaded to form pellets having a thickness of 0.8 mm and a diameter of 17.0 mm. The formed pellets were vacuum dried at 250 ° C. and dehydrated, and then used as a positive electrode.
  • a metal lithium plate was used as the negative electrode, and a polypropylene nonwoven fabric was used as the separator.
  • an electrolytic solution an electrolytic solution in which 1 mol / liter of LiPF 6 was dissolved in a mixed solvent of polypropylene carbonate (PC) and dimethyl ether (DEM) was used.
  • a coin-type lithium battery (lithium secondary battery) having an outer diameter of about 23 mm and a height of about 3.0 mm was produced using the above positive electrode, negative electrode, separator, and electrolytic solution.
  • the battery was charged to 3.0 V at a constant current of a current density of 0.4 mA / cm 2 and then discharged to 1.0 V, and the initial discharge capacity was measured. Thereafter, the above charge / discharge was repeated up to 100 cycles, and the capacity retention rate was calculated by the following equation. Table 1 shows the initial discharge capacity and capacity retention rate.
  • Capacity retention rate (%) (discharge capacity after 100 cycles / initial discharge capacity) ⁇ 100
  • the initial discharge capacity and capacity retention rate of the lithium batteries using the porous lithium titanates of Examples 1 to 5 produced according to the present invention as the positive electrode active material are the same as those of Comparative Example 1. High values are obtained as compared with the initial discharge capacity and capacity retention rate of lithium batteries using lithium. In particular, when the porous lithium titanate of Examples 1 to 4 having an average pore diameter in the range of 100 nm to 700 nm is used, a higher capacity retention rate is obtained.
  • the porous lithium titanates of Examples 1 to 5 have an average pore diameter larger than that of Comparative Example 1 and an increased amount of oil absorption. It is considered that by using the porous lithium titanate, the impregnation property of the nonaqueous electrolyte could be improved, and as a result, the charge / discharge cycle characteristics could be improved.
  • the porous lithium titanate particles according to the present invention as an electrode active material of a lithium battery, the impregnation property of the nonaqueous electrolyte is excellent and the charge / discharge cycle characteristics can be enhanced.

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Abstract

Cette invention concerne : un procédé de production d'un titanate de lithium poreux, qui manifeste une excellente imprégnabilité par un électrolyte non aqueux et est capable d'améliorer les caractéristiques des cycles de charge/décharge quand il est utilisé à titre de matériau actif d'électrode pour batterie au lithium ; un titanate de lithium poreux ; et une batterie au lithium l'utilisant. Plus spécifiquement, un mélange broyé est obtenu par broyage mécano-chimique et mélange d'un matériau de départ qui contient une source de titane et une source de lithium, et ledit mélange broyé est soumis à cuisson.
PCT/JP2011/063210 2010-07-02 2011-06-09 Procédé de production de titanate de lithium poreux, titanate de lithium poreux et batterie au lithium l'utilisant Ceased WO2012002122A1 (fr)

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CN2011800290973A CN102958844A (zh) 2010-07-02 2011-06-09 多孔质钛酸锂的制造方法、多孔质钛酸锂和使用其的锂电池

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JP2010151589A JP2012012261A (ja) 2010-07-02 2010-07-02 多孔質チタン酸リチウムの製造方法、多孔質チタン酸リチウム及びそれを用いたリチウム電池
JP2010-151589 2010-07-02

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Cited By (4)

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WO2012086557A1 (fr) * 2010-12-24 2012-06-28 京セラ株式会社 Batterie rechargeable au lithium
US20180090749A1 (en) * 2016-09-29 2018-03-29 GM Global Technology Operations LLC Making channeled electrodes for batteries and capacitors
EP3210941A4 (fr) * 2014-10-24 2018-07-04 Otsuka Chemical Co., Ltd. Particules de composé de titanate poreux et procédé de production associé
US20180237310A1 (en) * 2015-09-24 2018-08-23 Otsuka Chemical Co., Ltd. Porous titanate compound particles and method for producing same

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