WO2008018634A1 - Manganate de lithium spinelle, procédé servant à produire celui-ci, matière active d'électrode positive utilisant le manganate de lithium spinelle et batterie à électrolyte non aqueux - Google Patents

Manganate de lithium spinelle, procédé servant à produire celui-ci, matière active d'électrode positive utilisant le manganate de lithium spinelle et batterie à électrolyte non aqueux Download PDF

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WO2008018634A1
WO2008018634A1 PCT/JP2007/065974 JP2007065974W WO2008018634A1 WO 2008018634 A1 WO2008018634 A1 WO 2008018634A1 JP 2007065974 W JP2007065974 W JP 2007065974W WO 2008018634 A1 WO2008018634 A1 WO 2008018634A1
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positive electrode
lithium manganate
manganese oxide
active material
electrode active
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PCT/JP2007/065974
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English (en)
Japanese (ja)
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Shinji Iizuka
Kumiko Sueto
Takeshi Shimada
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Kanto Denka Kogyo Co., Ltd.
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Publication of WO2008018634A1 publication Critical patent/WO2008018634A1/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
    • H01M4/50—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
    • 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
    • C01P2004/01—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
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 spinel type lithium manganate that is a positive electrode active material having low battery cost, high safety, excellent energy density, and high-speed battery power characteristics, and a method for producing the same.
  • the present invention relates to a nonaqueous electrolyte battery having a positive electrode.
  • Li C o 0 2 of layered rock ⁇ has been mainly used for the positive electrode active material of lithium secondary batteries.
  • L i C O_ ⁇ 2 charge-discharge characteristics, although superior in cycle characteristics, abundance of the raw material edge Noreto less, cost is expensive.
  • L i N i 0 2 and L i Co 1/3 N i 1/3 Mn 1/3 0 2 ; 03 ⁇ 4 ⁇ are used for small batteries.
  • New cathode materials combining these elements have been proposed, but materials that can be used as positive electrode active materials for large batteries, which are more demanding in terms of cost and safety, and at high rates are rare. I came. '
  • the particle diameter obtained by the industrial production method of the positive electrode active material of the lithium secondary battery reported so far was 0.5 m to l 0; m.
  • the coprecipitation method and aerosol method, which can obtain fine particles, can produce fine particles of 20 nm to 100 nm, but there are problems such as uneven distribution of the resulting positive electrode active material and high costs. It was inferior in nature.
  • this method achieves a BET value of 1 to: L 00m 2 / g, a distribution of 0.4 or less by adding 0.01 to 2.50 mol% of calcium or / and magnesium. Mn or Z and Li are substituted with Ca or / and TVtg.
  • This method focuses on the compositional unevenness of lithium and manganese oxide, and spinel-type lithium manganate after firing does not mention the particle size or distribution in the description of only the BET specific surface area.
  • spinel-type lithium manganate having sufficient battery characteristics, sufficient cycle characteristics, and a high charge / discharge rate cannot be obtained only by a combination of these methods.
  • Patent Document 1 Japanese Patent Laid-Open No. 4-198028
  • Patent Document 4 Japanese Patent Application Laid-Open No. 10-172569
  • Patent Document 7 JP 2002-151077 A
  • Patent Document 8 Japanese Patent Application Laid-Open No. 2003-229127
  • the present invention relates to a lithium manganate having a high charge / discharge rate that can be used as a positive electrode active material excellent in cost, safety, and reliability, a manufacturing method thereof, a positive electrode active material obtained by the method, and a non-use using the same.
  • An object is to provide a water electrolyte battery.
  • the present invention provides the following.
  • Average particle size is 10 ⁇ ! Spinel type lithium manganate having a BET specific surface area value of 1 to 50 m 2 / g and a particle size variation coefficient of 0.40 or less.
  • Manganese salt, alkali carbonate and alkali hydroxide are mixed under aqueous conditions, and the resulting aqueous liquid and oxygen-containing gas are mixed to obtain manganese oxide particles, and the manganic oxide particles are mixed with a lithium source. And an SSi method of spinel type lithium manganate characterized by firing.
  • a nonaqueous electrolyte battery having a positive electrode comprising the positive electrode active material according to [7].
  • the positive electrode active material according to the present invention it is possible to obtain a nonaqueous electrolyte battery that is not particularly deteriorated in discharge capacity during high-speed charge / discharge and excellent in cycle characteristics during high-speed charge / discharge.
  • FIG. 1 is a TEM image (magnification 30000) of the raw material manganese oxide of Example 1.
  • FIG. 2 is an XRD diagram of the raw material manganese oxide of Example 1.
  • Fig. 3 is a TEM image (magnification 30000) of the raw material manganese oxide of Difficult Example 3.
  • FIG. 4 is an XRD diagram of the raw material manganese oxide of Example 3.
  • FIG. 5 is a TEM image (magnification 30000) of the raw material manganese oxide of Comparative Example 2.
  • FIG. 6 is an XRD diagram of the raw material manganese oxide of Comparative Example 2.
  • FIG. 7 is a TEM image (magnification: 300,000) of the raw material manganese oxide of Comparative Example 5.
  • FIG. 8 is an XRD diagram of the raw material manganese oxide of Comparative Example 5.
  • FIG. 9 is a 3 £ image (magnification 1 5 0 0 0) of L ⁇ ⁇ 11 2 0 4 in Example 6.
  • FIG. 10 is an XRD diagram of Li Mn 2 0 4 of Example 6.
  • FIG. 11 is a diagram showing the configuration of the battery used in the example.
  • Figure 12 shows the charge / discharge profile determined for the lithium secondary battery fabricated in Example 6 under the 1 C condition.
  • FIG. 13 shows a charge / discharge profile of the lithium secondary battery fabricated in Example 6 measured under the condition of 20 C.
  • FIG. 14 is a graph showing the cycle characteristics of the lithium secondary battery fabricated in Example 6 under 1 C charge / discharge conditions.
  • FIG. 15 is a diagram showing the cyclile characteristics of the lithium secondary battery produced in Example 6 under 20 C charge / discharge conditions.
  • Figure 1 6 is an S EM images of L i Mn 2 ⁇ 4 of Comparative Example 1 (magnification 5 0 0 0).
  • FIG. 17 is an XRD diagram of Li Mn 2 0 4 of Comparative Example 1.
  • FIG. 18 is a charge / discharge profile measured under the 1 C condition of the lithium secondary battery fabricated with Li Mn 2 O 4 of Comparative Example 1.
  • FIG. 19 shows a charge / discharge profile measured under the condition of 20 C of the lithium secondary battery fabricated in Li Mn 20 4 of Comparative Example 1.
  • FIG. 20 is a diagram showing the cyclile characteristics of the lithium secondary battery manufactured in Li Mn 2 0 4 of Comparative Example 1 under 1 C charge / discharge conditions.
  • FIG. 21 is a graph showing the cycle characteristics of the lithium secondary battery fabricated with Li Mn 20 4 of Comparative Example 1 under 20 C charge / discharge conditions.
  • FIG. 22 is a cross-sectional view schematically showing the battery.
  • a method for producing spinel-type lithium manganate characterized by mixing manganese oxide particles and a lithium source and calcining fiTT.
  • oxidation man It is important that the gun is fine and has a uniform distribution of manganese oxide particles.
  • Manganese oxide particles are fine and can be prepared with precisely controlled wrinkle distribution.
  • the present inventors paid attention to this point, and by using manganese oxide particles as a manganese source, spinel-type lithium manganate having extremely fine particles and a controlled particle size distribution was obtained.
  • a positive electrode active material containing spinel type lithium manganate with a good i3 ⁇ 4 distribution we succeeded in producing a non-aqueous electrolyte battery with excellent performance.
  • the manganese oxide particles preferably have an average particle size of 1 m or less, more preferably 500 nm or less, more preferably 30 O nm or less, most preferably 100 nm or less, especially 10 to 1. It has an average particle size of 0 nm.
  • manganese oxide particles obtained by mixing a manganese salt, an alkali carbonate, and an alkali hydroxide under aqueous conditions and reversing the resulting aqueous liquid and acid-containing gas can be suitably used.
  • the equivalent ratio of alkali to manganese is preferably 0.7 to 3.0.
  • the equivalent ratio of alkali hydroxide Z alkali carbonate is preferably 0.6 to 2.95 / 0.05 to 0.5. If the alkali carbonate exceeds 0.5, manganese oxide or manganese carbonate may be mixed in the raw material, and if it is less than 0.05, the 3 ⁇ 4 * iJt distribution will be widened and obtained. Particles tend to be large.
  • alkali hydroxide examples include sodium hydroxide, potassium hydroxide, and aqueous ammonia.
  • examples of the alkali carbonate include sodium carbonate, potassium carbonate, and ammonium carbonate. Even if alkali metal alkali is used, most of the alkaline metal byproduct of the neutralization reaction can be
  • Examples of the manganese salt used in the present invention include manganese donation, manganese nitrate, manganous oxalate, manganese chloride, manganese acetate and the like, and these can be used as war worms or in combination of two or more. It is preferably used in the form of this manganese salt solution.
  • the manganese salt in the mixed aqueous solution with alkali is preferably about 0.2 to about L mol / L. If the manganese salt content is less than 0.2 mol ZL, the cost increases from the viewpoint of productivity, and if it exceeds 1.0 mol ZL, the desired particles can be obtained, but a large amount of energy is required for stirring. ⁇ Jt distribution may get worse.
  • the oxidation reaction is preferably 30 ° C to 60 ° C. 3 Below 0 ° C: If the control is too much in the process, you may need a machine. When the temperature exceeds 60 ° C, the particle size may increase, and when ammonia is used as the alkali, ammonia is diffused, and the particle size distribution increases due to changes in the ammonia concentration in the reaction solution. There are dogs allowed.
  • Manganese oxide particles that are fine and have a poor distribution as a starting material are, for example, an aqueous manganese salt solution and a mixed aqueous solution of carbonated aluminum and aluminum hydroxide in an equivalent ratio of 0.7 to 0.7. ⁇ 3.0, mixed in an inert atmosphere at an equivalent ratio of alkali hydroxide / alkali carbonate of 0.6 ⁇ 2.95 / 0.05 ⁇ 0.5, 30 ° C ⁇ 60 ° C Mn 2 + X by oxidizing the manganese salt by blowing an oxygen-containing gas (eg, oxygen, air, a mixture of oxygen and inert gas) in 3 ⁇ 43 ⁇ 4 of C ⁇ 3 + X (0 ⁇ x ⁇ D) is generated, and this can be S3 ⁇ 4i by filtering, washing with water and drying.
  • an oxygen-containing gas eg, oxygen, air, a mixture of oxygen and inert gas
  • the spinel-type lithium manganate is obtained by mixing Li source with the above manganese source and firing.
  • Li source include lithium carbonate, lithium hydroxide, and lithium acetate.
  • the mixing method is not particularly limited, and as a decoration suitable for either wet mixing or dry mixing, a mixer,
  • the mixing ratio (atomic ratio (L i / Mn at The ratio)) is preferably 0.5 to 0.7.
  • the mixing ratio is less than 0.5, the raw material manganese oxide is mixed in lithium manganate, and when a positive electrode is formed using this lithium-deficient lithium manganate, good charge / discharge characteristics and cycle There is a tendency that characteristics cannot be obtained.
  • the mixing ratio is less than 0.5, it is confirmed that particles and particles are sometimes bonded.
  • the mixing ratio exceeds 0.7, spinel by-products are generated, and the male electric capacity is lowered.
  • the process supplies thermal energy to the mixture of raw materials, which converts the mixture into a thermodynamically stable spinel-type lithium manganate compound, removes impurities, and produces fine particles of the positive electrode active material of the present invention. It is a process to do.
  • the process preferably comprises a two-stage process, a provisional process and a main process.
  • Presence or absence of « ⁇ and conditions are not particularly limited. In general, the formation is performed at 200 to 400 ° C.
  • the main temperature at 700 ° C. or higher, preferably from 70 ° to 90 ° C., more preferably from 70 ° to 80 ° C., in an oxidizing atmosphere. Also, this time: «Time failure 2 hours to 24 hours, preferably 4 hours to 12 hours.
  • the oxidizing atmosphere include air and oxygen gas whose partial pressure is adjusted with an inert gas.
  • the positive electrode active material of the present invention needs to contain spinel type lithium manganate as a main component, but can contain a conductive material such as carbon as other components other than spinel type lithium manganate. .
  • the blending ratio of other components is desirably 30% or less of the positive electrode active material.
  • the average 3 ⁇ 4 ⁇ of Li Mn 20 4 which is a positive electrode active material is preferably 10 to 50 O nm, more preferably 10 to 20 O nm, and particularly 10 to 15 50. nm.
  • the positive electrode active material Li Mn 2 0 4 has a standard deviation of 50 nm or less, especially 40 nm or less! ! It preferably has a 3 ⁇ 4J3 ⁇ 4 distribution and preferably has a coefficient of variation of particle size of 0.40 or less, particularly 0.30 or less, 1 to 50 m 2 / g, particularly 5 to 50 ra It is preferred to have a BET specific surface area value of g. [: Non-aqueous electrolyte battery]
  • FIG. 22 is a cross-sectional view showing a battery cage.
  • the nonaqueous electrolyte battery 1 is roughly composed of a negative electrode member 2 that functions as an external negative electrode of the battery, a positive electrode member 3 that functions as an external positive electrode of the battery, a negative electrode current collector 4, a negative electrode between both members An active material layer 5, a separate night 8, a positive electrode active material layer 7, and a positive electrode current collector 6 are provided in this order.
  • the negative electrode member 2 has a substantially cylindrical shape, and is configured so that the negative electrode current collector 4 and the negative electrode active material layer 5 can be accommodated therein.
  • the positive electrode member 3 also has a substantially cylindrical shape, and is configured to accommodate the positive electrode current collector 6 and the E electrode active material layer 7 therein.
  • the radial dimension of the positive electrode member 3 and the separator plate 8 is set to be slightly larger than that of the negative electrode member 2, and the peripheral edge of the negative electrode member 2 overlaps the circumference of the separator plate 8 and the positive electrode member 3. It ’s like that.
  • the space inside the battery is filled with a non-aqueous electrolyte 9, and a sealing material 10 is applied to the overlapping portion of the peripheral edge of the negative electrode member 2, the separator 8, and the negative electrode member 3, so that the inside of the battery is airtight. It is kept.
  • the negative electrode is formed by using a negative electrode member 2 as an external negative electrode, a negative electrorefractor 4 in contact therewith, and a negative electrode active material layer 5 on the negative electrode current collector.
  • a negative electrode current collector for example, nickel foil, copper foil or the like is used.
  • negative electrode active material dope lithium / de-fed.
  • lithium metal foils, lithium alloys, lithium-doped conductive materials, layered compounds (carbon materials such as graphite and activated carbon fibers, metal oxides, etc.) Etc. are used.
  • the binder contained in the negative electrode active material layer a known resin material or the like that is usually used as a binder for the negative electrode active material layer of this type of nonaqueous electrolyte battery can be used.
  • the metal lithium foil can be used not only as the negative electrode active material layer but also as the negative electrode current collector, the battery Pit can be simplified by using a metal lithium foil as the negative electrode.
  • the positive electrode comprises a positive electrode member 3 as an external positive electrode, and a positive electrode body 6 in contact with the positive electrode member 3 and a positive electrode active material layer 7 on the positive electrode current collector.
  • the positive electrode active material the above-described positive electrode active material of the present invention is used.
  • an aluminum foil or the like is used as the positive electrode current collector.
  • a binder contained in the positive electrode active material layer a positive electrode active material layer of this type of non-aqueous electrolyte battery such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE) is used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • a conductive material can be blended in the positive electrode active material layer in order to improve conductivity. Examples of the conductive material include graphite and acetylene black.
  • the separator 8 separates the positive electrode and the negative electrode, and a known material that is usually used as a separator for a non-aqueous electrolyte battery of this type can be used.
  • a known material that is usually used as a separator for a non-aqueous electrolyte battery of this type can be used.
  • high-pressure materials such as polypropylene can be used. Liver film, polyethylene-strength porous membrane, etc. are used.
  • the thickness of the separation evening is preferably 50 m or less, for example.
  • the sealing material 10 a known resin material or the like that is usually used as a sealing material for the positive electrode active material layer of this type of nonaqueous electrolyte battery can be used.
  • non-aqueous electrolyte not only a liquid electrolyte but also a solid electrolyte and a gel electrolyte containing a solvent can be used.
  • liquid electrolyte a solution in which an electrolyte is dissolved in an aprotic nonaqueous solvent is used.
  • Non-aqueous solvents include, for example, ethylene force monoponate, propylene carbonate, butylene force monoponate, vinylene force monoponate, and the like, moss, dimethyl carbonate, jetyl pone, and ethyl.
  • Ethers such as methyl carbonate, dipropyl carbonate chain carbonates, alkyl lactone, sulfolane, 1,2-dimethoxyshetane, 1,2-jetixane, 2-methyltetrahydrofuran, 3-methyl Examples include 1,3-dioxolan, methyl propionate, and methyl butyrate.
  • cyclic forces such as ethylene strength, propylene carbonate, vinylene carbonate, dimethyl carbonate, jet carbonate, It is preferable to use chain carbonates such as dipropylene and pone.
  • one kind of non-aqueous solvent may be used in battle, or two or more kinds may be used in combination.
  • the electrolyte for example, L i PF 6, L i C 10 4, L iAsF 6, L iBF 4, L i CF 3 S_ ⁇ 3, L iN (CF 3 S0 2) to the shelf lithium salt of 2, etc. I can do it.
  • Li PF 6 and Li BF 4 are preferably used.
  • the solid electrolyte include inorganic solid electrolytes such as lithium nitride and lithium iodide; organic polymer electrolytes such as poly (ethylene oxide), poly (methacrylate), and poly (acrylate).
  • the liquid electrolyte Any material that can gel and absorb water can be used without any particular limitation.
  • fluorine-containing materials such as poly (vinylidene fluoride) and vinylidene fluoride Z-hexafluoropropylene copolymer. A polymer is mentioned.
  • the nonaqueous electrolyte battery using the positive electrode active material of the present invention is, for example, as follows. First, the i3 ⁇ 4i method for the negative electrode will be described. A negative electrode active material and a binder are dispersed in a solvent to prepare a slurry. The obtained slurry is uniformly applied on a current collector and dried to form a negative electrode active material layer. The obtained laminate comprising the negative electrode current collector and the negative electrode active material layer is accommodated in the negative electrode member so that the negative electrode and the inner surface of the negative electrode member are in contact with each other to form a negative electrode. Further, as described above, the metal lithium foil can be used as it is as the negative electrode active material and the negative electrode active material.
  • the positive electrode active material, conductive material and binder of the present invention are dispersed in a solvent to prepare a slurry.
  • the slurry is uniformly applied on the current collector and dried to form a positive electrode active material layer.
  • the obtained laminate including the positive electrode and the positive electrode active material layer is accommodated in the positive electrode member so that the electric electrode and the inner surface of the positive electrode member are in contact with each other, thereby forming a positive electrode.
  • a nonaqueous electrolyte When a nonaqueous electrolyte is used, it is prepared by dissolving an electrolyte salt in a nonaqueous solvent.
  • the negative electrode and the positive electrode manufactured as described above are overlapped so that a separator is interposed between the negative electrode active material layer and the positive electrode active material layer, filled with a nonaqueous electrolyte, and sealed with a sealing material. By sealing the battery, a non-aqueous electrolyte battery is completed.
  • the shape of the nonaqueous electrolyte battery of the present invention is not particularly limited, and can be a cylindrical shape, a square shape, a coin shape, a button shape, or the like. Can be sized. Further, the present invention can be used for both a primary battery and a secondary battery.
  • the specific surface area was measured using a fully automatic surface area measuring device Multisoap 12 (Yuasa Ionics ⁇ ) according to the BET method. '
  • composition analysis was measured by I C ⁇ emission spectroscopic analysis (IC ⁇ emission analyzer SPS1500VR Seiko Instruments Inc.) and calculated by the ratio of mo 1 to Mn.
  • the resulting suspension was filtered, washed with 10 L of deionized water (hereinafter referred to as “10 L / mo 1 of deionized water”) per manganese lmo, and then dried to obtain finely divided manganese oxide. .
  • the BET specific surface area of the sample was measured by the nitrogen adsorption method.
  • the BET value of the obtained sample was 26.0 m 2 Zg.
  • Table 1 shows the synthesis conditions of manganese oxide and the characteristics of the reaction products.
  • the obtained sample was subjected to scanning electron microscopy and a TEM photograph is shown in Fig. 1.
  • Example 2 The particle size was 73 nm, the standard deviation was 23 nm, and the coefficient of variation was 0.32. Child: X-ray diffraction diagram. From the X-ray diffraction pattern, it was confirmed that it was manganese oxide.
  • Example 2 X-ray diffraction diagram. From the X-ray diffraction pattern, it was confirmed that it was manganese oxide.
  • Fine particulate manganese oxide was obtained in the same manner as in Example 1 except that the oxidation reaction temperature was changed to 40 ° C.
  • Table 1 shows the synthesis conditions of manganese oxide and the characteristics of the reaction products.
  • the BET value of the obtained sample was 35.7 ml g.
  • the average particle size of the obtained sample was 39 nm, the standard difference was 15 nm, and the coefficient of variation was 0.38.
  • Table 1 shows the synthesis conditions of manganese oxide and the characteristics of the reaction products.
  • the BET value of the obtained sample was 45.9 m 2 Zg.
  • Table 1 shows the synthesis conditions of manganese oxide and the characteristics of the reaction products. The obtained sample is examined with a thigh electron microscope, and a TEM photograph is shown in FIG. The average particle size of the obtained sample was 80 nm, the standard deviation was 28 nm, and the coefficient of variation was 0.35.
  • Figure 4 shows the X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be manganese oxide.
  • Example 4 shows the X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be manganese oxide.
  • the Nyuita 3 reaction vessel 40L 1. 350mo lZL, (NH 4 ) 2 C0 3 g of a 0. 09 Omo 1 / L aqueous solution containing 14L, and substituted by a stream of nitrogen gas, 0. 5 hr holding at 40 I had it.
  • the obtained suspension was filtered, washed with 1 OL / mo 1 deionized water, and dried to obtain fine-particle manganese oxide.
  • the BET value of the obtained sample was 62.5 m 2 / g.
  • the sample obtained had an average particle size of 5 Onm, a standard deviation of 14 nm, and a coefficient of variation of 0.28.
  • Table 1 shows the synthesis conditions of manganese oxide and the characteristics of the reaction products.
  • Example 5 2007/065974 Fine manganese oxide was obtained in the same manner as in Example 4 except that the oxidation reaction temperature was changed to 55 ° C.
  • the B ET value of the obtained sample was 33.4 m 2 / g.
  • the average particle diameter of the obtained sample was 81 nm, the standard difference was 25 nm, and the coefficient of variation was 0.31.
  • Table 1 shows the synthesis conditions of oxidized mangan and the characteristics of the reaction products.
  • Electrolytic manganese dioxide 80 g, lithium hydroxide monohydrate 2 0.3 g and pure water 10 OmL are put into a 2 5 OmL planetary pole mill container, and pure water 10 OmL is further added, and 2 5 0 r p.m. and mixed for 12 hours. 3 ⁇ 4 ⁇
  • Fig. 16 shows the SEM image of Li Mn 2 0 4 generated
  • Fig. 1 7 shows the XRD of Li Mn 2 0 4 generated.
  • a 60 L reaction vessel was charged with 40 L of an aqueous solution containing 0.99 mol ZL of NaOH, purged with nitrogen gas and replaced with 0.5 hri at 70 ° C.
  • ⁇ gas, with stirring by addition of Mn S_ ⁇ 4 aqueous 2 0 L of 0. 9 mo 1 ZL, and the suspension was mixed 7 0 6 0 min.
  • air was vented at 5 LZmin and the oxidation reaction was performed for 5 hours.
  • the resulting suspension was filtered, washed with 10 LZmo 1 deionized water, and dried to obtain manganese oxide.
  • the B ET value of the obtained sample was 8.5 m 2 / g.
  • Table 1 shows the synthesis conditions of manganese oxide and the characteristics of the reaction products.
  • FIG. Fig. 6 shows the X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be manganese oxide.
  • Manganese oxide was obtained in the same manner as in Comparative Example 2 except that the equivalent ratio of sodium hydroxide to manganese was changed from 1.1 to 2.0. Table 1 shows the synthesis conditions of manganese oxide and the characteristics of the reaction products.
  • Manganese oxide was obtained in the same manner as in Comparative Example 2 except that the reaction St was changed to 40. Table 1 shows the synthesis conditions of manganese oxide and the characteristics of the reaction products. 4 Comparative Example 5
  • a 60 L reaction vessel was charged with 40 L of an aqueous solution containing 0.54 mol 1 ZL of NaOH and 0.27 mol lL of Na 2 CO 3 , and was purged with nitrogen gas.
  • nitrogen aeration, stirring was added to MnS_ ⁇ 4 aqueous 20L of 0. 9mo 1ZL, and the suspension was mixed for 60 minutes at ⁇ 0 ° C.
  • air was passed through 1 OLZmin and the oxidation reaction was carried out for 5 hours.
  • the resulting suspension was filtered and washed with 1 OLZmo 1 deionized water to obtain particles.
  • the BET value of the obtained sample was 16.6m 2 Zg.
  • FIG. Figure 8 shows the X-ray diffraction pattern of the particles obtained. From the X-ray diffraction pattern, it was confirmed that it was a mixture of manganese oxide and manganese carbonate.
  • Particles were obtained in the same manner as in Comparative Example 5 except that the reaction was carried out at 40 ° C.
  • the BET value of the obtained particles was 25.5 m 2 / g, and the X-ray diffraction measurement result was a mixture of manganese oxide and manganese carbonate.
  • the particle size 200 particles were randomly measured from a TEM photograph, and the average value and the standard deviation of the measured values were calculated.
  • the average particle diameter of the obtained sample was 10 8 nm, the standard deviation was 30 nm, and the coefficient of variation was 0.28.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction products, and the characteristics.
  • X-ray diffraction measurement was performed on the obtained particles.
  • Fig. 10 shows the X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed that the phase was Li Mn 2 0 4 .
  • conductive material acetylene black
  • binder polyvinylidene fluoride
  • a simple lithium secondary battery was fabricated by using a solution in which 6 was dissolved and metal lithium punched into a negative electrode with a diameter of 16 mm and a thickness of 0.2 mm. An outline of the simple lithium secondary battery used in this example is shown in FIG.
  • Figure 18 shows initial charge / discharge characteristics at 1 C.
  • Figure 19 shows initial charge / discharge characteristics at 20 C.
  • PT / JP2007 / 065974 is shown.
  • Figure 20 shows the cycle characteristics at 1 C at 25 ° C, and
  • Figure 21 shows the cycle characteristics at 20 C.
  • Example 6 Was changed combined weight of hydroxide Richiumufu opening was 2 4. 2 2. 9 g of 3 g was obtained microparticles L i M n 2 0 4 in the same manner as in Example 6. The BET value of the obtained sample was 9.6 mV g. The average particle size of ⁇ 1 ⁇ obtained was 10 l nm, the difference was 28 nm, and the coefficient of variation was 0.28. Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition and powderiness of the reaction product, and Table 3 shows the charge / discharge characteristics and cycle characteristics measured at each rate.
  • Fine particles Li Mn 2 0 4 were obtained in the same manner as in Example 6 except that the main firing temperature was changed to 800 ° C.
  • the BET value of the obtained sample was 5.7m 2 Zg.
  • the average particle size of the obtained sample was 1 29 nm, the standard difference was 38 nm, and the coefficient of variation was 0.29.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction product, and the powder characteristics.
  • Table 3 shows the charge / discharge characteristics and cycle characteristics measured at each level.
  • the raw material manganese oxide was changed from the fine manganese oxide obtained in Example 1 to the fine manganese oxide obtained in Example 2, and the firing time was set to 12 hours. L i M n 2 O 4 was obtained.
  • the BET value of the obtained sample was 8.4 m 2 g.
  • the average particle size of the obtained sample was 79 nm, standard deviation 21 nm, and coefficient of variation 0.27.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction product, and the powder characteristics.
  • Table 3 shows the charge / discharge characteristics and cycle durability measured at each level.
  • fine particle lithium manganate was obtained in the same manner as in Example 6.
  • the BET value of the obtained sample was 13.4m 2 Zg.
  • the average particle diameter of the obtained sample was 106 nm, the difference between the standard and 24 nm, and the coefficient of variation of 0.23.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction product, and the powder characteristics.
  • Table 3 shows the charge / discharge characteristics and cycle characteristics measured at each rate.
  • Example 1 1 The raw material manganese oxide was the fine manganese oxide obtained in Example 4! ⁇ Obtained fine-particle lithium manganate in the same manner as in Example 6.
  • the B ET value of the obtained sample was 14.8 m 2 Zg.
  • the average particle diameter of the obtained sample was 55 nm, the standard difference was 14 nm, and the coefficient of variation was 0.25.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction product, and the powder characteristics.
  • Table 3 shows the charge / discharge characteristics and cycle characteristics measured at each rate.
  • Example 4 The manganese oxide obtained in Example 4 was used as the raw material manganese oxide, the mixed weight of lithium hydroxide monohydrate and silica was changed from 24.3 g to 22.9 g, and the main firing temperature was set to 8 Fine particle lithium manganate was obtained in the same manner as in Example 6 except that the temperature was 0 ° C.
  • the B ET value of the obtained sample was 7.8 m 2 Zg.
  • the average particle size of the obtained sample was 1450 nm, the difference was 45 nm, and the coefficient of variation was 0.31.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction product, and powder characteristics.
  • Table 3 shows the charge / discharge characteristics and cycle characteristics measured at each rate.
  • Example 1 3
  • Fine particle lithium manganate was obtained in the same manner as in Example 6 while using the raw material manganese oxide as the fine particle manganese oxide obtained in Example 5.
  • the BET value of the obtained sample was 9.8 m 2 / g.
  • the average particle size of the obtained sample was 115 nm, the difference was 31 nm, and the coefficient of variation was 0.27.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction product, and the powder characteristics.
  • Table 3 shows the charge / discharge characteristics and cycle JVif properties measured at each rate.
  • Example 6 Was replaced by manganese oxide obtained in Comparative Example 2 the manganese oxide of the raw materials to obtain fine particles L i M n 2 0 4 in the same manner as in Example 6.
  • the BET value of the obtained sample was 4.7 m 2 Z g.
  • the average particle size of the obtained sample was 950 nm, the difference was 4 3 2 nm, and the coefficient of variation was 0.45.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction product, and the powder characteristics.
  • Table 3 shows the charge / discharge characteristics and cycle retention measured at each level.
  • Fine particles LiMn 2 0 4 were obtained in the same manner as in Example 6 except that the raw material manganese oxide was replaced with the acid manganese obtained in Comparative Example 3.
  • the BET value of the obtained sample was 2.1 m 2 Z g.
  • the average particle size of the obtained powder is 1800 nm, the difference between the standard particle size is 930 nm, and the coefficient of variation is 0 I got it.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate and the characteristics of the reaction product.
  • Table 3 shows the charge / discharge characteristics and cycle characteristics measured at each rate.
  • the raw material manganese oxide was replaced with the manganese oxide identified in Comparative Example 4] to obtain fine particles Li M n 2 O 4 in the same manner as in Example 6.
  • the BET value of the obtained sample was 1.6 m 2 Z g.
  • the average particle size of the obtained sample was 2300 nm, the difference was 1100 nm, and the coefficient of variation was 0.48.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction product, and the powder characteristics.
  • Table 3 shows the electrical characteristics and cyclability measured at each of the plates.
  • the manganese oxide of the raw material was changed to manganese oxide obtained in Comparative Example 5] ⁇ got microparticles L i M n 2 ⁇ 4 in the same manner as in Example 6.
  • the BET value of the orchid obtained was 2.7 m 2 / g.
  • the obtained sample had an average particle size of 1 1550 nm, a difference of 5900 nm, and a coefficient of variation of 0.51.
  • Table 2 shows the preparation conditions of spinel-type lithium manganate, the composition of the reaction product, and the powder characteristics.
  • Table 3 shows the charge / discharge characteristics and cycle characteristics measured at each rate.
  • the manganese oxide of the raw material was changed to manganese oxide obtained in Comparative Example 7 was obtained microparticles L i Mn 2 ⁇ 4 in the same manner as in Example 6.
  • the B ET value of the obtained sample was 5.5 m 2 Zg.
  • the average particle size of the obtained sample was 2 80 nm, the standard difference was 180 nm, and the coefficient of variation was 0.64.
  • Table 2 shows the preparation conditions of spinel type lithium manganate, the composition of the reaction product, and the powder characteristics.
  • Table 3 shows the charge / discharge characteristics and cycle retention measured at each of the plates.
  • the average particle size of the positive electrode material $ 3 ⁇ 4t according to the present invention is 10 ⁇ ! ⁇ 50 0 nm
  • BE lower value is 1 ⁇ 50 m 2 / g
  • coefficient of variation of particle size is 0
  • Spinel type lithium manganate of 50 or less is very fine and has a uniform rice daughter distribution. Therefore, the amount of discharge during high M ⁇ discharge using this positive electrode material, and the rapid charge / discharge It can be seen that the cycle characteristics at the time are very good.
  • nonaqueous electrolyte battery using the positive electrode active material of the present invention examples include lithium secondary batteries such as metal lithium batteries, lithium ion batteries, and lithium polymer batteries.

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Abstract

L'invention concerne un manganate de lithium spinelle de faible coût et tout à fait sans danger, lequel peut être une matière active d'électrode positive ayant une excellente densité d'énergie et d'excellentes caractéristiques de batterie. L'invention concerne également un procédé servant à produire un tel manganate de lithium spinelle et une batterie à électrolyte non aqueux ayant une électrode positive contenant le manganate de lithium spinelle. L'invention concerne précisément un procédé servant à produire un manganate de lithium spinelle qui est caractérisé en ce qu'on mélange dans des conditions aqueuses un manganate de lithium spinelle ayant un diamètre moyen des particules de 10-500 nm, une valeur de surface spécifique BET de 1-50 m2/g et un coefficient de variation de la taille des particules inférieur ou égal à 0,40, un sel de manganèse, un carbonate de métal alcalin et un hydroxyde de métal alcalin ; en ce que l'on met la solution aqueuse ainsi obtenue en contact avec un gaz contenant de l'oxygène, ce par quoi on obtient des particules d'oxyde de manganèse ; et en ce que l'on mélange ensuite les particules d'oxyde de manganèse avec une source de lithium et calcine celles-ci.
PCT/JP2007/065974 2006-08-09 2007-08-08 Manganate de lithium spinelle, procédé servant à produire celui-ci, matière active d'électrode positive utilisant le manganate de lithium spinelle et batterie à électrolyte non aqueux WO2008018634A1 (fr)

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KR101092400B1 (ko) 2009-03-26 2011-12-09 한국과학기술원 스피넬 결정구조 및 나노구조를 갖는 리튬 망간 산화물 및 리튬 망간 금속 산화물의 제조방법
KR101170095B1 (ko) * 2010-02-18 2012-07-31 한국과학기술원 상압 저온 공정을 이용한 나노 구조 감마 망간 산화물 분말의 합성방법과 이를 이용한 리튬망간 산화물의 제조방법
US9318741B2 (en) 2010-04-28 2016-04-19 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material of power storage device, power storage device, electrically propelled vehicle, and method for manufacturing power storage device
JP6443675B2 (ja) * 2015-03-04 2018-12-26 株式会社豊田自動織機 スピネル型結晶構造のＬｉａＭｘＭｎｙＯ４粉末を含む正極及びリチウムイオン二次電池、並びにこれらの製造方法
JP6351524B2 (ja) * 2015-03-04 2018-07-04 株式会社豊田自動織機 スピネル型結晶構造のＬｉａＭｘＭｎｙＯ４粉末並びにその製造方法

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