WO2014077274A1 - 正極活物質及びその製造方法、並びに非水電解質二次電池用正極、非水電解質二次電池 - Google Patents

正極活物質及びその製造方法、並びに非水電解質二次電池用正極、非水電解質二次電池 Download PDF

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WO2014077274A1
WO2014077274A1 PCT/JP2013/080667 JP2013080667W WO2014077274A1 WO 2014077274 A1 WO2014077274 A1 WO 2014077274A1 JP 2013080667 W JP2013080667 W JP 2013080667W WO 2014077274 A1 WO2014077274 A1 WO 2014077274A1
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particle
positive electrode
active material
particles
lithium
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English (en)
French (fr)
Japanese (ja)
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吉則 風間
陽介 平山
耕二 幡谷
智洋 権田
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古河電気工業株式会社
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Priority to CN201380059410.7A priority Critical patent/CN104781966B/zh
Priority to KR1020157005638A priority patent/KR101649082B1/ko
Priority to JP2014547001A priority patent/JP5847329B2/ja
Publication of WO2014077274A1 publication Critical patent/WO2014077274A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0072—Mixed oxides or hydroxides containing manganese
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
    • C01P2006/40—Electric properties
    • 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
    • C01P2006/42—Magnetic properties
    • 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
    • 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 lithium transition metal phosphate based positive electrode active material and the like used in a non-aqueous electrolyte secondary battery.
  • lithium cobalt oxide uses cobalt, which is a rare metal, it has large resource limitations, is expensive, and has problems with price stability.
  • lithium cobaltate releases a large amount of oxygen when the temperature reaches 180 ° C. or higher, and therefore, an explosion may occur at the time of abnormal heat generation or a short circuit of the battery.
  • lithium phosphate transition metal having an olivine structure such as lithium iron phosphate (LiFePO 4 ) or manganese lithium phosphate (LiMnPO 4 ), which is more excellent in thermal stability than lithium cobaltate, is resource aspect and cost.
  • LiFePO 4 lithium iron phosphate
  • LiMnPO 4 manganese lithium phosphate
  • solid phase method As a method of synthesizing lithium iron phosphate, a method called solid phase method is known.
  • the outline of the solid phase method is a method in which powders of a lithium source, an iron source and a phosphorus source are mixed and subjected to a baking treatment under an inert atmosphere. This method has a problem that the composition of the product does not become as intended if the calcination conditions are not properly selected, and control of the particle size is difficult.
  • a hydrothermal synthesis method using hydrothermal synthesis in a liquid phase is also known.
  • the hydrothermal synthesis is carried out in the presence of high temperature and pressure hot water. A much purer product is obtained at a much lower temperature than solid phase methods.
  • the control of the particle size is performed depending on the preparation conditions such as the reaction temperature and time, the reproducibility of the control of the particle size is poor and the control of the particle size is difficult (see Patent Document 1).
  • a fine mist is generated from a mixed solution of a carbon-containing compound, a lithium-containing compound, an iron-containing compound and a phosphorus-containing compound, and thermal decomposition is performed by heating while flowing the generated fine mist.
  • a fine powder comprising a lithium iron phosphate precursor containing the above is formed, and the fine powder thus produced is heated and fired in an inert gas-hydrogen mixed gas atmosphere to produce a lithium iron phosphate powder containing carbon. It is a method of generating a body (see Patent Document 2).
  • lithium iron phosphate remains at 3.4 V while the potential of lithium cobaltate is 3.9 V
  • LiCoPO 4 and LiNiPO 4 (wherein Ni and Co are substituted by one or more of Ni, Co, Mn, Fe, Mg, Cu, Cr, V, Li, Nb, Ti and Zr other than the elements)
  • Li 1-x FePO 4 (however, part of Fe is Co, Ni, Mn, Fe, Mg, Cu, Cr, V, Li, etc.) around the first positive electrode active material which may be
  • a positive electrode for a secondary battery comprising a second positive electrode active material, which may be substituted with one or more of Nb, Ti and Zr, and x represents a number of 0 or more and less than 1).
  • a core-shell type positive electrode active material particle is disclosed in which the core particle and the shell layer contain an olivine type phosphoric acid compound containing Fe and / or Mn and Li (see Patent Document 6).
  • lithium manganese phosphate has a smaller electron conductivity and a smaller diffusion coefficient of lithium ions than lithium iron phosphate, and furthermore, it is difficult to sufficiently cover the surface with carbon, so lithium manganese phosphate is used.
  • the used positive electrode active material has a problem that a sufficient discharge capacity can not be obtained.
  • the surface of large lithium manganese phosphate particles is coated with lithium iron phosphate.
  • the diffusion coefficient of lithium ion of lithium manganese phosphate is smaller than that of lithium iron phosphate, there is a problem that the lithium ion is not deintercalated to the center of large lithium manganese phosphate particles during charge and discharge.
  • lithium iron phosphate (LiFe x Mn 1 -x PO 4 ) in which iron atoms in lithium iron phosphate crystals are replaced with manganese atoms in a solid phase method or a hydrothermal synthesis method is manufactured or
  • a lithium transition metal phosphate having an olivine structure using iron and manganese has been obtained by simply mixing lithium iron phosphate and lithium manganese phosphate.
  • these lithium transition metal phosphates are different from the structure in which lithium manganese phosphate particles are attached to the surface of lithium iron phosphate particles as in the present invention.
  • the positive electrode active material described in Patent Document 5 is not intended to utilize lithium manganese phosphate, and the second positive electrode active material particles in the periphery of the first positive electrode active material are lithium iron phosphate. is there. Moreover, the positive electrode active material described in Patent Document 5 can also have a configuration that does not contain manganese.
  • the positive electrode active material described in Patent Document 6, above containing metal phosphate that Me m P n O p as essential, the core particle and the shell layer in each embodiment is using the same material.
  • the present invention has been made in view of the above-mentioned problems, and its object is to provide a positive electrode active material containing lithium manganese phosphate and having a large discharge capacity and energy density.
  • the inventors of the present invention have an energy density by arranging lithium manganese phosphate having a small particle diameter and a low diffusion coefficient but high potential on the surface of lithium iron phosphate excellent in electron conductivity and diffusion coefficient of lithium ions. It has been found that an excellent positive electrode active material can be obtained. It has also been found that such a positive electrode active material can be obtained by mixing a precursor of lithium iron phosphate and a precursor of lithium manganese phosphate and then calcining the mixture.
  • a second particle mainly containing lithium manganese phosphate smaller in particle diameter than the first particle is attached to at least a part of the surface of the first particle mainly containing lithium iron phosphate
  • a positive electrode for a non-aqueous electrolyte secondary battery comprising a current collector and an active material layer containing the positive electrode active material described in (3) on at least one surface of the current collector.
  • a lithium ion according to (4) including the positive electrode for a non-aqueous electrolyte secondary battery, a negative electrode capable of absorbing and desorbing lithium ions, and a separator disposed between the positive electrode and the negative electrode, A non-aqueous electrolyte secondary battery comprising the positive electrode, the negative electrode, and the separator in a conductive electrolyte.
  • the third particle is manufactured by a method of supplying a solution containing lithium, iron and phosphorus into a flame together with a combustion supporting gas and a flammable gas as droplets in the form of mist
  • the particles of the present invention are characterized in that they are produced by a method of supplying a solution containing lithium, manganese and phosphorus in the form of atomized droplets into a flame together with a combustion supporting gas and a flammable gas (6)
  • the manufacturing method of the positive electrode active material as described.
  • BRIEF DESCRIPTION OF THE DRAWINGS The schematic sectional drawing which shows the particle
  • BRIEF DESCRIPTION OF THE DRAWINGS The schematic of the microparticles
  • BRIEF DESCRIPTION OF THE DRAWINGS The schematic sectional drawing of the non-aqueous electrolyte secondary battery using the positive electrode active material which concerns on this Embodiment. (A) to (c) SEM photographs of particles before firing according to an example.
  • FIG. 1 is a view showing a particle 1 according to the present embodiment.
  • the particle 1 is a particle formed by attaching the second particle 5 to the surface of the first particle 3. Note that the entire surface of the first particle 3 may be covered by the plurality of second particles 5, or only a part of the surface of the first particle 3 is covered by the second particle 5. Also good.
  • grains 1 gathered can be used as a positive electrode active material of a non-aqueous electrolyte secondary battery.
  • the first particles 3 are particles mainly containing lithium iron phosphate (LiFePO 4 ).
  • the first particles 3 preferably have a particle size of 100 nm to 10 ⁇ m. If the first particles 3 are smaller than 100 nm, the packing density of the powder when used as an electrode does not increase, and the energy density of the electrode is inferior. If the first particles 3 are larger than 10 ⁇ m, the power density as an electrode is inferior. Also, in order for the second particle to have a structure covering the surface of the first particle as in the present invention, the particle diameter of the second particle covering the surface of the first particle is the particle size of the first particle It needs to be smaller than the diameter.
  • the average particle diameter of the first particles 3 is preferably 100 nm to 10 ⁇ m, and more preferably 200 nm to 2 ⁇ m.
  • the second particles 5 are particles mainly containing lithium manganese phosphate (LiMnPO 4 ).
  • the second particles 5 preferably have a particle size of 200 nm or less. If the size of the second particle 5 is too large, the lithium can not be deintercalated to the center of the particle, so the power density as an electrode is inferior.
  • the particle diameter of the second particles is not a problem to be small for obtaining the effect of the present invention, and the lower limit of the particle diameter is not particularly defined. However, it is preferably 5 nm or more because it is often about 5 nm at the minimum in consideration of the limit from the process of precursor production and the convenience of the operation of mixing with the first particles.
  • the average particle diameter of the second particles 5 is preferably 5 nm to 200 nm, and more preferably 10 nm to 100 nm.
  • containing mainly means that the ratio of lithium iron phosphate contained in the first particles 3 is 80% by mass or more with respect to the first particles 3. Furthermore, the proportion of lithium iron phosphate is preferably 90% by mass or more. The same applies to the proportion of lithium manganese phosphate contained in the second particles 5.
  • the ratio of lithium iron phosphate to lithium phosphate transition metal contained in the first particles 3 is preferably 80% by mass or more, and more preferably 90% by mass or more.
  • the surface of particle 1 may be coated with carbon. That is, at least a part of the surface of either or both of the first particle 3 and the second particle 5 constituting the particle 1 may be coated with carbon.
  • the electric conductivity of the particle 1 becomes high, a conductive path to lithium iron phosphate fine particles or lithium manganese phosphate fine particles is obtained, and when using the particle 1 as a positive electrode active material, high speed
  • the electrode characteristics can be improved, for example, by
  • the particles containing lithium manganese phosphate (LiMnPO 4 ) of the second particles 5 attached to the particles containing LiFePO 4 ) may not be attached to the entire surface of the first particles 3.
  • fine particles containing lithium manganese phosphate which is hard to be carbon-coated on the surface are also easily carbon-coated.
  • the particles including the first particles 3 come into direct contact with the electrolytic solution during charge and discharge, and the particles 1 become a positive electrode active material. The electrode characteristics when used are improved.
  • a part of PO 4 can be replaced by another anion.
  • the powder in which the particles 1 or a plurality of particles 1 are collected can be used as a positive electrode active material used for a positive electrode for a non-aqueous electrolyte secondary battery.
  • the positive electrode active material according to the present embodiment adheres lithium manganese phosphate excellent in potential and energy density to the surface of lithium iron phosphate particles excellent in electron conductivity and lithium ion diffusion, phosphoric acid Manganese lithium can be sufficiently utilized for charge and discharge reactions.
  • a conductive auxiliary such as carbon black is further added to the positive electrode active material, and polytetrafluoroethylene, polyvinylidene fluoride, Aluminum containing at least 95% by weight of aluminum containing a binder such as polyimide, a dispersant such as butadiene rubber, and a thickener such as carboxymethylcellulose and cellulose derivatives, and adding it to an aqueous solvent or an organic solvent to form a slurry
  • the solution is applied on one side or both sides on a current collector such as an alloy foil and fired to evaporate the solvent to dryness.
  • the adhesion between the current collector and the active material layer, and the current collecting property it was granulated and fired by a spray dry method using a positive electrode active material and a carbon source.
  • the following particles can be used by being contained in the slurry.
  • the agglomerated secondary particle mass becomes a large mass of about 0.5 to 20 ⁇ m, which improves the slurry coatability and further improves the characteristics and life of the battery electrode.
  • the slurry used in the spray drying method may be either an aqueous solvent or a non-aqueous solvent.
  • the surface roughness of the current collector surface of the active material layer is determined according to Japanese Industrial Standard (JIS B 0601-1994). It is desirable that the defined ten-point average roughness Rz be 0.5 ⁇ m or more.
  • JIS B 0601-1994 Japanese Industrial Standard
  • Rz the defined ten-point average roughness
  • Non-aqueous electrolyte secondary battery In order to obtain a high-capacity secondary battery using the positive electrode of the present embodiment, various materials such as a negative electrode using a conventionally known negative electrode active material, an electrolytic solution, a separator, and a battery case are used without particular limitations. Can.
  • the non-aqueous electrolyte secondary battery 31 shown in FIG. 3 can be exemplified.
  • the positive electrode 33 and the negative electrode 35 are stacked and arranged in the order of separator-negative electrode-separator-positive electrode via the separator 37, and wound so that the positive electrode 33 is inside.
  • the electrode plate group is constructed and inserted into the battery can 41.
  • the positive electrode 33 is connected to the positive electrode terminal 47 via the positive electrode lead 43
  • the negative electrode 35 is connected to the battery can 41 via the negative electrode lead 45, and chemical energy generated inside the non-aqueous electrolyte secondary battery 31 is used as electrical energy. To be able to take out.
  • the battery can 41 is filled with the electrolyte 39 so as to cover the electrode plate group, and the upper end (opening) of the battery can 41 is composed of a circular cover plate and a positive electrode terminal 47 on the top thereof. It can manufacture by attaching the sealing body 49 which incorporated the through the annular insulation gasket.
  • the secondary battery using the positive electrode according to the present embodiment has a high capacity and good electrode characteristics can be obtained, the non-aqueous solvent containing fluorine in the electrolytic solution using the non-aqueous solvent constituting the secondary battery When or is added, the capacity is unlikely to decrease even after repeated charging and discharging, and the life is extended.
  • the electrolytic solution may contain fluorine or fluorine in order to suppress large expansion and contraction due to doping and de-doping of Li ions. It is desirable to use an electrolytic solution containing a non-aqueous solvent having as a substituent.
  • the fluorine-containing solvent relaxes the volume expansion of the silicon-based film due to the alloying with Li ions at the time of charge, particularly at the first charge treatment, so that the capacity decrease due to charge and discharge can be suppressed.
  • fluorine-containing nonaqueous solvent fluorinated ethylene carbonate, fluorinated linear carbonate, etc. can be used.
  • Mono-tetrafluoro-ethylene carbonate (4-fluoro-1,3-dioxolan-2-one, FEC) for fluorinated ethylene carbonate, methyl 2,2,2-trifluoroethyl carbonate for fluorinated linear carbonate And ethyl 2,2,2-trifluoroethyl carbonate, etc., which may be used singly or in combination of two or more in combination with the electrolytic solution. Since the fluorine group easily bonds to silicon and is strong, it is believed that the film can be stabilized and contributed to the suppression of expansion even in the case of expansion due to charge alloying with Li ions.
  • the particles according to the present embodiment can be obtained by mixing a third particle, which is a precursor of lithium iron phosphate, and a fourth particle, which is a precursor of lithium manganese phosphate, and then firing the mixture. .
  • the third particle and the fourth particle are a precursor particle of lithium iron phosphate and a precursor particle of lithium manganese phosphate, which are synthesized by a spray combustion method such as a flame hydrolysis method or a thermal oxidation method. .
  • FIG. 2 An example of a production apparatus for producing precursor particles by the spray combustion method is shown in FIG.
  • the particle synthesis nozzle 13 is disposed in the container, and the flammable gas, the combustion supporting gas, and the raw material solution are supplied into the flame generated from the nozzle 13.
  • an exhaust pipe 19 for exhausting the generated particulates and reaction products is provided, and the precursor particles 17 in the exhaust gas are recovered by the particulate collection filter 15.
  • the constituent material is supplied into the flame together with the combustion supporting gas and the flammable gas by a method of supplying a raw material gas such as chloride or a method of supplying a raw material liquid or a raw material solution through a vaporizer.
  • a method of supplying a raw material gas such as chloride or a method of supplying a raw material liquid or a raw material solution through a vaporizer.
  • VAD Vapor-phase Axial Deposition
  • the temperature of these flames varies depending on the mixing ratio of the flammable gas and the combustion supporting gas, and the addition ratio of the constituent materials, but is usually between 1000 and 3000 ° C., especially around 1500 to 2500 ° C.
  • the temperature be about 1500 to 2000.degree. If the flame temperature is low, fine particles may come out of the flame before the reaction in the flame is completed. In addition, when the flame temperature is high, the crystallinity of the particles to be generated becomes too high, and a phase which is a stable phase but is not preferable as a positive electrode active material is easily generated in the subsequent firing step.
  • the flame hydrolysis method is a method in which a constituent material is hydrolyzed in a flame.
  • an oxyhydrogen flame is generally used as a flame.
  • the target material is obtained by simultaneously supplying the constituent materials of the positive electrode active material and the flame raw materials (oxygen gas and hydrogen gas) to the base of the flame where hydrogen gas as combustible gas and oxygen gas as combustion supporting gas are supplied simultaneously. Synthesize.
  • the flame hydrolysis method it is possible to obtain nanoscale ultrafine particles of an objective substance consisting mainly of an amorphous substance in an inert gas filled atmosphere.
  • the thermal oxidation method is a method in which a constituent material is thermally oxidized in a flame.
  • a hydrocarbon flame is generally used as the flame.
  • the target material is synthesized while supplying the constituent raw material and the flame raw material (for example, propane gas and oxygen gas) simultaneously from the nozzle to the source of the flame to which hydrocarbon-based gas is supplied as combustible gas and air is supplied as combustion-supporting gas.
  • hydrocarbon gas paraffin hydrocarbon gas such as methane, ethane, propane and butane, or olefin hydrocarbon gas such as ethylene, propylene and butylene can be used.
  • the constituent materials for obtaining the precursor particles of the present embodiment are a lithium source, a transition metal source, and a phosphorus source.
  • the raw material is solid, it is supplied as a powder, dispersed in a liquid, or dissolved in a solvent to form a solution, and is supplied to the flame through a vaporizer.
  • the vapor pressure can be increased and vaporized and supplied by heating or depressurization and bubbling in front of the supply nozzle.
  • lithium inorganic acid salts such as lithium chloride, lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium nitrate, lithium bromide, lithium phosphate, lithium sulfate, lithium oxalate, lithium acetate, lithium naphthenate and the like
  • Lithium organic acid salts lithium alkoxides such as lithium ethoxide, organic lithium compounds such as ⁇ -diketonato compounds of lithium, lithium oxide, lithium peroxide and the like can be used.
  • Naphthenic acid is a mixture of different carboxylic acids in which a plurality of acidic substances in petroleum are mainly mixed, and the main component is a carboxylic acid compound of cyclopentane and cyclohexane.
  • ferric chloride iron oxalate, iron acetate, ferrous sulfate, iron nitrate, iron hydroxide, 2-ethylhexanoate Diiron, iron naphthenate and the like
  • organic metal salts of iron such as stearic acid, dimethyldithiocarbamic acid, acetylacetonate, oleic acid, linoleic acid, linolenic acid, iron oxide, etc. are also used depending on the conditions.
  • a transition metal source manganese chloride, manganese oxalate, manganese acetate, manganese sulfate, manganese nitrate, manganese oxyhydroxide, manganese 2-hydroxy-2-oxide, Manganese naphthenate, manganese hexoate and the like can be used. Furthermore, stearic acid, dimethyldithiocarbamic acid, acetylacetonate, organometallic salts of manganese such as oleic acid, linoleic acid and linolenic acid, manganese oxide and the like are also used depending on the conditions.
  • phosphoric acid As a phosphorus source of the precursor, phosphoric acid, phosphoric acid such as orthophosphoric acid or metaphosphoric acid, pyrophosphoric acid, ammonium hydrogen phosphate such as ammonium hydrogen phosphate such as ammonium hydrogen phosphate or ammonium hydrogen phosphate, ammonium phosphate
  • phosphoric acid such as orthophosphoric acid or metaphosphoric acid
  • pyrophosphoric acid As a phosphorus source of the precursor, phosphoric acid, phosphoric acid such as orthophosphoric acid or metaphosphoric acid, pyrophosphoric acid, ammonium hydrogen phosphate such as ammonium hydrogen phosphate such as ammonium hydrogen phosphate or ammonium hydrogen phosphate, ammonium phosphate
  • ammonium hydrogen phosphate such as ammonium hydrogen phosphate such as ammonium hydrogen phosphate or ammonium hydrogen phosphate
  • Various phosphates such as sodium or pyrophosphates, and phosphates of introduced transition metals such as ferr
  • a raw material of an oxide of transition metal and boric acid is added as an anion source.
  • borates such as diboron, sodium metaborate, sodium tetraborate and borax can be used depending on the desired anion source and synthesis conditions.
  • the generated precursor particles can be recovered from the exhaust with a filter. Also, it can be generated around the core rod as follows.
  • a silica or silicon core rod (also called a seed rod) is installed in the reactor, and a lithium source, transition metal source, and phosphorus source are supplied together with the flame raw material in the oxyhydrogen flame and propane flame sprayed thereto.
  • a lithium source, transition metal source, and phosphorus source are supplied together with the flame raw material in the oxyhydrogen flame and propane flame sprayed thereto.
  • fine particles of mainly nano order form and adhere to the surface of the core rod.
  • These generated fine particles are recovered and optionally filtered or sieved to remove impurities and coarse aggregates.
  • the precursor particles thus obtained are composed of fine particles that are mainly amorphous and have an extremely small particle size of nanoscale.
  • precursor particles that can be produced are amorphous, and the particle size is also small. Furthermore, in the spray combustion method, a large amount of synthesis can be performed in a short time as compared with the conventional hydrothermal synthesis method or the solid phase method, and homogeneous precursor particles can be obtained at low cost.
  • the positive electrode active material can be obtained by mixing the third particles and the fourth particles as precursors, mixing with a reducing agent, and calcining.
  • the precursor in this embodiment is a material capable of obtaining crystals of transition metal phosphate by firing.
  • the precursor in the present embodiment has trivalent iron and manganese and is amorphous, but the valence of iron and manganese changes from trivalent to bivalent by mixing with a reducing agent and firing. Do.
  • the composition of the particles containing lithium iron phosphate and lithium manganese phosphate constituting the precursor particles satisfy the stoichiometric composition, but if the composition is very small, the ideal stoichiometry due to the inclusion of impurities etc. Deviations from the theoretical composition are acceptable. It is preferable that the spatial distribution of the elements in the microparticles constituting the precursor particles is uniform. In particular, it is preferable that the spatial distribution of the transition metal and phosphorus in the fine particles be uniform.
  • the precursor particles have a substantially spherical shape, and the average aspect ratio (long diameter / short diameter) of the particles is 1.5 or less, preferably 1.2 or less, and more preferably 1.1 or less.
  • the particles are approximately spherical does not mean that the particle shape is geometrically strictly spherical or elliptical, and even if there are slight protrusions, the surface of the particle is a roughly smooth curved surface It should just be comprised.
  • carbon is burned in the flame, and thus the obtained precursor particles do not contain carbon. Even if the carbon component is mixed, it is a very small amount, which is not a sufficient amount as a conductive aid at the time of using the positive electrode.
  • the mixing ratio of the third particles to the fourth particles is preferably 60:40 to 90:10 by weight, and more preferably 70:30.
  • the mixture of the amorphous compound and the oxide form contained in the precursor particles is converted to a compound of the crystal form of a lithium transition metal phosphate based on the olivine structure mainly by firing.
  • a mixed crystal phase represented by LiFe 1-x Mn x PO 4 (0 ⁇ x ⁇ 1) may be included in the vicinity of the interface of the particles.
  • the lattice strain at the bonding interface is relaxed compared to the case where the bonding interface of the third particle and the fourth particle directly constitutes the heterogeneous interface.
  • the bonding strength at the bonding interface can be stabilized.
  • the particle size of the third particles is preferably 100 nm to 10 ⁇ m, and the particle size of the fourth particles is preferably 200 nm or less. Also, the fourth particles have a smaller particle size than the third particles.
  • the particle diameter of the fourth particle is not a problem to be small for obtaining the effect of the present invention, and the lower limit of the particle diameter is not particularly defined. However, due to the limit from the process of precursor production, the convenience of the operation of mixing with the first particle, etc., it is often at least about 5 nm at the minimum. In the precursor particles and the positive electrode active material, the particle diameter does not substantially change before and after the firing, and by firing the precursor, the particle diameter can be maintained without causing fusion or particle growth. is there.
  • the average particle diameter of the third particles is preferably 100 nm to 10 ⁇ m, and more preferably 200 nm to 2 ⁇ m. Furthermore, in the powder in which a large number of fourth particles are collected, the average particle diameter of the fourth particles 5 is preferably 5 nm to 200 nm, and more preferably 10 nm to 100 nm.
  • the carbon source in the atmosphere filled with an inert gas, can be prevented from burning at the time of firing and the positive electrode active material can be prevented from being oxidized.
  • an inert gas nitrogen gas, argon gas, neon gas, helium gas, carbon dioxide gas, etc. can be used.
  • Organic compounds that are conductive carbon sources such as polyalcohols such as polyvinyl alcohol, polymers such as polyvinyl pyrrolidone, carboxymethyl cellulose, acetyl cellulose, saccharides such as sucrose, saccharides such as carbon black, in order to increase the conductivity of the product after heat treatment
  • the compound is added to the powder in which the third and fourth particles are mixed before heat treatment, and the mixture is calcined.
  • polyvinyl alcohol is particularly preferable because it can reduce iron and manganese during firing.
  • Coating with carbon or supporting treatment is carried out in the same firing step together with crystallization of precursor particles.
  • the heat treatment conditions can be a combination of a temperature of 300 to 900 ° C. and a treatment time of 0.5 to 10 hours to obtain a fired product of desired crystallinity and particle size as appropriate. Excessive heat load due to heat treatment at high temperature or long time should be avoided as it can generate coarse single crystals, and should be under heating conditions such that the desired crystalline or microcrystalline lithium transition metal lithium compound can be obtained. And heat treatment conditions that can suppress the size of the crystallite as small as possible.
  • the temperature of the heat treatment is preferably about 400 to 700.degree.
  • the fourth particle does not have to be attached to the entire surface of the third particle, and the exposed portion is present on the surface of the third particle containing lithium iron phosphate which is easily carbon-coated.
  • the particles of 4 are also well coated with carbon.
  • the obtained positive electrode active material is often aggregated in the firing step, it can be made into fine particles again by being subjected to a grinding means such as a mortar or a ball mill.
  • the positive electrode active material can be synthesized continuously and on a large scale.
  • the positive electrode active material according to the present embodiment adheres lithium manganese phosphate excellent in electric potential and energy density to the surface of lithium iron phosphate particles excellent in electron conductivity and lithium ion diffusivity, Lithium manganese phosphate can be sufficiently utilized for charge and discharge reaction.
  • the lithium metal transition metal phosphate based positive electrode active material according to the present embodiment can ensure the migration path of lithium ions, and efficiently use the active material constituting the particles. Can.
  • the flame temperature was about 2000 ° C.
  • the method for producing precursor particles by the spray combustion method is as follows. First, a predetermined amount of N 2 gas was supplied to make the inside of the reaction vessel an inert gas atmosphere. Under such conditions, a solution in which the lithium source, the iron source and the phosphoric acid source were respectively mixed was made into droplets of 20 ⁇ m through an atomizer and supplied to a flame together with propane gas and air. Precursor particles which are a mixture of lithium oxide, iron oxide, fine particles of phosphorus oxide and the like, fine particles of lithium iron phosphate compound and the like generated in a flame were collected by a fine particle collection filter. The obtained precursor particles are precursor particles a. The average particle size of the primary particles of the precursor particles a confirmed by the electron microscope was about 500 nm.
  • Synthesis example 2 (spray combustion method) (Preparation of lithium manganese phosphate precursor particles by spray combustion method) Further, as in Synthesis Example 1, the precursor particles b are synthesized by supplying propane gas, air, and a raw material solution having a predetermined concentration described below into a flame of propane gas by a spray combustion method, and thermally oxidizing the raw material solution. Collected. The average particle diameter of the primary particles of the precursor particles b confirmed by the electron microscope was about 100 nm.
  • the positive electrode active material B is a powder in which a large number of lithium iron phosphate particles are collected.
  • the positive electrode active material C is a powder in which a large number of particles of lithium manganese phosphate are collected.
  • a precursor particle d of lithium cobalt phosphate is obtained by the same spray combustion method as in Synthesis Example 1 except that cobalt (II) 2-ethylhexanoate is used instead of iron (II) 2-ethylhexanoate as the raw material solution.
  • the average particle size of the primary particles of the precursor particles d confirmed by the electron microscope was about 500 nm.
  • lithium iron phosphate precursor particles a ′ were obtained by the same spray fuel method as in Synthesis Example 2 except that manganese sulfate is used as the raw material solution and iron sulfate is used.
  • the average particle size of the primary particles of the precursor particles a ′ confirmed by the electron microscope was about 100 nm.
  • the polyvinyl alcohol After mixing precursor particle d of lithium cobalt phosphate and precursor particle a 'of lithium iron phosphate smaller in particle diameter at a weight ratio of 70:30, the polyvinyl alcohol will be 10 wt% of the powder The mixture was added to and mixed, and then fired and pulverized in the same manner as in the example to obtain a positive electrode active material D.
  • the positive electrode active material D is a powder in which a large number of particles in which small lithium iron phosphate particles are attached to the periphery of lithium cobalt phosphate particles are collected.
  • a precursor particle e of lithium nickel phosphate is obtained by the same spray combustion method as in Synthesis Example 1 except that nickel (II) 2-ethylhexanoate is used instead of iron (II) 2-ethylhexanoate as the raw material solution.
  • the average particle size of the primary particles of the precursor particles e confirmed by the electron microscope was about 500 nm.
  • After mixing precursor particle e of lithium nickel phosphate and precursor particle a 'of lithium iron phosphate smaller in particle diameter at a weight ratio of 70:30, make the polyvinyl alcohol 10 wt% of the powder The mixture was added to and mixed, and then fired and pulverized in the same manner as in the example to obtain a positive electrode active material E.
  • the positive electrode active material E is a powder in which a large number of particles in which small particles of lithium iron phosphate adhere to the periphery of lithium lithium phosphate particles.
  • a precursor particle f of lithium manganese phosphate is obtained by the same spray combustion method as in Synthesis Example 1 except that manganese (II) 2-ethylhexanoate is used instead of iron (II) 2-ethylhexanoate as the raw material solution.
  • the average particle size of the primary particles of the precursor particles f confirmed by the electron microscope was about 500 nm.
  • the positive electrode active material F is a powder in which a large number of particles in which small lithium iron phosphate particles are attached around the lithium manganese phosphate particles.
  • the particles constituting the powder before firing were particles of about 50 to 200 nm, and some coarse particles of 500 nm or more existed.
  • FIG.5 (a) is a HAADF-STEM image of the particle
  • FIG.5 (b) is an EDS map of the manganese atom in the same observation location
  • FIG.5 (c) is the same.
  • 5 (c) is an EDS map of oxygen atom at the same observation point
  • FIG. 5 (d) is an EDS map of phosphorus atom at the same observation point. is there.
  • FIG. 5A it can be seen that minute particles exist around the approximately spherical particles having a particle diameter of about 500 nm. Furthermore, in FIG. 5 (b) to (e), although the large particles having a substantially spherical shape contain iron, oxygen and phosphorus, manganese is hardly detected from the large particles, and manganese is present from the fine particle part at the bottom of the observation field of view. was detected.
  • FIGS. 6A to 6D are STEM images and EDS maps in fields of view different from those in FIG. Assemblage of small particles with a particle size of about 100 nm was observed, iron was not detected in this field of view, and manganese, phosphorus and oxygen were detected. In each particle, the elements are uniformly distributed.
  • FIG.7 (a) is a HAADF-STEM image of the positive electrode active material of an Example
  • FIG.7 (b) is an EDS map of the manganese atom in the same observation location
  • FIG.7 (c) is the same.
  • FIG. 7 (d) is an EDS map of iron atom at the observation site
  • FIG. 7 (d) is an EDS map of oxygen atom at the same observation site
  • FIG. 7 (e) is an EDS map of phosphorus atom at the same observation site .
  • the positive electrode active material A of the example has a structure in which lithium manganese phosphate particles having a particle diameter of about 50 to 200 nm adhere to lithium iron phosphate particles having a particle diameter of about 1 ⁇ m.
  • lithium manganese phosphate particles do not cover the entire surface of lithium iron phosphate particles, and a part of the surface of lithium iron phosphate particles is exposed.
  • the positive electrode slurry was applied at a coating amount of 50 g / m 2 to a 15 ⁇ m thick aluminum foil current collector, and dried at 120 ° C. for 30 minutes. Thereafter, the resultant was rolled to a density of 2.0 g / cm 3 by a roll press, and punched into a disc shape of 2 cm 2 to obtain a positive electrode.
  • a lithium secondary battery is prepared by dissolving LiPF 6 at a concentration of 1 M in a mixed solvent in which the positive electrode and the negative electrode are mixed with metal lithium in the negative electrode and ethylene carbonate and diethyl carbonate in the electrolyte at a volume ratio of 1: 1. Made. Note that the dew point was set to ⁇ 50 ° C. or less for the preparation atmosphere. Each electrode was crimped to a battery can with a current collector. A coin-type lithium secondary battery having a diameter of 25 mm and a thickness of 1.6 mm was formed using the positive electrode, the negative electrode, the electrolyte, and the separator.
  • test evaluation of the electrode characteristics of the positive electrode active material was performed as follows using the coin-type lithium secondary battery described above. At a test temperature of 25 ° C. or 60 ° C., at a current rate of 0.1 C, charging is performed to a predetermined potential (vs. Li / Li + ) at which the charge curve becomes a plateau by CC-CV method. After dropping to 01C, charging was stopped. Thereafter, the battery was discharged to 2.5 V (same as above) by the CC method at a 0.1 C rate, and the initial charge and discharge capacity was measured. Moreover, charge and discharge were repeated, the discharge capacity after that was measured, and the capacity retention rate was measured.
  • the initial charge / discharge curve of a lithium ion secondary battery using the positive electrode active material according to the example is shown in FIG. 8 (a).
  • the charge went to 4.5V.
  • (a-1) shows a charge curve
  • (a-2) shows a discharge curve.
  • the value of the horizontal axis at the right end of the discharge curve is the discharge capacity.
  • the lithium ion secondary battery according to the example has an initial discharge capacity of about 120 mAh / g at 25 ° C. and an energy density of 438 Wh / kg.
  • transition of the discharge capacity at the time of repeating charging / discharging in FIG.8 (b) is shown.
  • the charge went to 4.5V.
  • the lithium ion secondary battery using the positive electrode active material according to the example has a discharge capacity of 110 mAh / g, and the 100 cycle capacity retention rate is about 92%.
  • the first time charge / discharge curve at 60 ° C. of a lithium ion secondary battery using the positive electrode active material A according to the example is shown in FIG.
  • the charge went to 4.5V.
  • (a-1) shows a charge curve
  • (a-2) shows a discharge curve.
  • the value of the horizontal axis at the right end of the discharge curve is the discharge capacity.
  • the lithium ion secondary battery according to the example has an initial discharge capacity of about 140 mAh / g at 60 ° C. and an energy density of 520 Wh / kg.
  • the initial charge / discharge curve at 25 ° C. of a lithium ion secondary battery using the positive electrode active material B according to Comparative Example 1 is shown in FIG. Also in this case, charging was performed up to 4.5V.
  • FIG. 10 (a-1) shows a charge curve, and (a-2) shows a discharge curve.
  • the initial discharge capacity of a lithium ion secondary battery using a positive electrode active material containing only lithium iron phosphate according to Comparative Example 1 is about 120 mAh / g at 25 ° C., which is substantially the same value as the Example, but the energy density is about It was 395 Wh / kg, which was a lower value than in the example.
  • the first time charge / discharge curve at 25 ° C. of a lithium ion secondary battery using the positive electrode active material C according to Comparative Example 2 is shown in FIG. Also in this case, charging was performed up to 4.5V.
  • FIG. 11 (a-1) shows a charge curve, and (a-2) shows a discharge curve.
  • the initial discharge capacity of a lithium ion secondary battery using a positive electrode active material containing only lithium manganese phosphate according to Comparative Example 2 is about 30 mAh / g at 25 ° C., and the energy density is about 97 Wh / kg. Was significantly lower.
  • the initial discharge capacity of the lithium ion secondary battery using the positive electrode active material D according to Comparative Example 3 was about 59 mAh / g at 25 ° C., and the energy density was about 217 Wh / kg, which were significantly lower than those of Examples. .
  • charge was performed to 4.8V which the charge curve of lithium cobalt phosphate becomes a plateau.
  • the initial discharge capacity of the lithium ion secondary battery using the positive electrode active material E according to Comparative Example 4 was about 48 mAh / g at 25 ° C., and the energy density was about 168 Wh / kg, which were significantly lower than those of Examples. .
  • charging was performed up to 5.0 V at which the charge curve of lithium nickel phosphate became a plateau.
  • the initial discharge capacity of the lithium ion secondary battery using the positive electrode active material F according to Comparative Example 5 was about 66 mAh / g at 25 ° C., and the energy density was about 235 Wh / kg, which were significantly lower than those of Examples. . Also in Comparative Example 4, charging was performed to 4.5 V.
  • the positive electrode for a non-aqueous electrolyte secondary battery in which the positive electrode active material of the present invention is coated on a predetermined current collector is a charge and discharge including a lithium ion secondary battery using a non-aqueous electrolyte
  • the spray combustion method which is a method for producing the precursor particles of the present invention, is excellent in mass productivity and can provide a product at low cost.

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