WO2008093551A1 - Composé ayant une structure d'olivine, son procédé de fabrication, matière active d'électrode positive utilisant un composé ayant une structure d'olivine et batterie a électrolyte non aqueux - Google Patents

Composé ayant une structure d'olivine, son procédé de fabrication, matière active d'électrode positive utilisant un composé ayant une structure d'olivine et batterie a électrolyte non aqueux Download PDF

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WO2008093551A1
WO2008093551A1 PCT/JP2008/050650 JP2008050650W WO2008093551A1 WO 2008093551 A1 WO2008093551 A1 WO 2008093551A1 JP 2008050650 W JP2008050650 W JP 2008050650W WO 2008093551 A1 WO2008093551 A1 WO 2008093551A1
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Prior art keywords
positive electrode
compound
active material
electrode active
particle size
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PCT/JP2008/050650
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English (en)
Japanese (ja)
Inventor
Kumiko Sueto
Shinji Iizuka
Takeshi Shimada
Yuan Gao
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Kanto Denka Kogyo Co., Ltd.
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Priority to JP2008556048A priority Critical patent/JP5385616B2/ja
Publication of WO2008093551A1 publication Critical patent/WO2008093551A1/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
    • H01M4/58—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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • 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 an olivine-type positive electrode active material that is a low-cost, high-safety, battery property having excellent energy density, and a method for producing the same, and a nonaqueous electrolyte battery having a positive electrode including the same About.
  • lithium secondary batteries are widely used as power sources for electronic devices such as mobile phones, video cameras, and laptop computers.
  • electronic devices such as mobile phones, video cameras, and laptop computers.
  • the development of large-sized lithium secondary batteries that are inexpensive and highly safe for electric vehicles and nighttime power is also underway.
  • a layered rock salt type LiCoO 2 has been mainly used as a positive electrode active material of a lithium secondary battery.
  • L i C O_ ⁇ 2 is superior in charge-discharge cycle characteristics, abundance of raw Der Ru cobalt is small, cost is expensive. Therefore, as a positive electrode active material of an alternative, although L i N i 0 2 Ya spinel L i M n 2 0 4 of layered rock-salt type have been studied, L i N I_ ⁇ 2 safety problems of the state of charge Li M n 2 0 4 has a problem in chemical stability at high temperatures.
  • New cathode materials combining these elements have been proposed for small batteries, but new alternative materials have been proposed as positive electrode active materials for large batteries, which are more demanding in terms of cost and safety. It has been desired.
  • L i F e P 0 4 a positive electrode active material of olivine type, cost, safety 'j raw, in recent years developed a superior material in reliability have become active.
  • the olivine-type L i F e P 0 4 has a very high safety and stability, and because it is inexpensive, but that have been noted, electron conductivity low as a problem to practical use There is.
  • As methods for improving this mainly fine particles for increasing the reaction surface area, carbon coating for imparting conductivity, etc. are well known (for example, Non-Patent Document 1). It has been reported that battery characteristics can be improved by using fine particles, especially when the particles are uniform (Non-patent Documents 2 and 3). In addition, regarding the addition of Kibon There are numerous reports (for example, Patent Document 3 and Non-Patent Document 4).
  • Patent Document 1 a solid phase method (Patent Document 1, Non-Patent Document 5) using iron oxalate or iron acetate as a starting material has been generally used as a method for producing olipine-type lithium iron phosphate.
  • Patent Document 2 solid-phase methods using iron phosphate as a raw material
  • sol-gel methods for obtaining finer particles sol-gel methods for obtaining finer particles
  • hydrothermal methods Non-Patent Documents 6 and 7
  • the raw materials are expensive, equipment for preventing the oxidation of divalent iron is necessary, and it is difficult to obtain a target product with uniform and good crystallinity. Therefore, by either method, it is difficult to industrially produce uniform fine particles with inexpensive raw materials and simple manufacturing equipment, and low lithium olivine phosphate with practical battery characteristics is reduced. Manufacturing methods that can be realized at low cost are needed.
  • Patent Document 1 Japanese Patent No. 3484003
  • Patent Document 2 Japanese Patent No. 3319258
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2001-1511
  • Non-patent document 1 A. Yamada; Electrochemistry 71, o.3, 717-722 (2003)
  • Non-patent document 2 A. Singhal, G. Skandan, G. Amatucci, F. Badway, N. Ye,
  • Non-Patent Document 3 K. Striebel, J. Shim, V. Srinivasan, and J. Newman
  • Non-Patent Document 4 N. Ravet, Y. Chouinard,]. F. Magnan, S. Besner, M. Gauthier, M. Armand
  • Non-Patent Document 5 A. K. Padhi, ⁇ . S. Nanjundaswamy, and J.B. Goodenough,
  • Non-Patent Document 6 S. Yang, P.Y. Zavalji, M. S. Whit tinghain
  • Non Patent Literature 7 J. Yang and J. J. Xu
  • the present invention provides a positive electrode active material that is excellent in cost, safety, and reliability, enables inexpensive industrial production of a high-capacity non-electrolyte battery, a method for producing the same, and a non-aqueous electrolyte battery using the same. For the purpose.
  • the present invention provides the following.
  • a method for producing a compound having an olivine structure comprising mixing an iron source containing iron oxide particles having an average particle size of 500 nm or less, a lithium source, and a phosphorus source, followed by firing.
  • a compound having an olipine structure characterized by mixing an iron source containing iron oxide particles having an average particle size of 500 nm or less, a lithium source and a phosphorus source and carbon or / and a carbon precursor, followed by firing. Production method.
  • a compound having an olivine structure having an average particle size of 1000 nm or less obtained by any one of the methods [1 :) to [9].
  • a positive electrode active material comprising a compound having an olivine structure obtained by any method of [1] to [9] or a compound having an olivine structure of [10] or [11].
  • a nonaqueous electrolyte battery having a positive electrode comprising the positive electrode active material according to [12].
  • FIG. 1 is a TEM photograph of the iron oxide particles produced in Example 1.
  • FIG. 2 is an X-ray diffraction pattern of the iron oxide particles produced in Example 1.
  • FIG. 3 is a SEM photograph of the lithium iron phosphate produced in Example 1.
  • FIG. 4 is an X-ray diffraction pattern of the lithium iron phosphate produced in Example 1.
  • FIG. 5 is a schematic diagram of the lithium secondary battery (coin cell) used in the examples.
  • FIG. 6 is a graph showing the results of a charge / discharge test for the coin cell produced in Example 1. ,
  • FIG. 7 is a S EM photograph of the lithium iron phosphate produced in Example 2.
  • FIG. 8 is an X-ray diffraction pattern of lithium iron phosphate produced in Example 2.
  • FIG. 9 is a TEM photograph of the iron oxide particles produced in Example 3.
  • FIG. 10 is a SEM photograph of the lithium iron phosphate produced in Example 3.
  • FIG. 11 is an SEM photograph of lithium iron phosphate produced in Example 4.
  • FIG. 12 is a TEM photograph of the hematite particles used in Comparative Example 1.
  • FIG. 13 is an SEM photograph of the lithium iron phosphate produced in Comparative Example 1.
  • FIG. 14 is a TEM photograph of the lithium iron phosphate produced in Comparative Example 1.
  • FIG. 15 is a SEM photograph of the lithium iron phosphate produced in Comparative Example 2.
  • FIG. 16 is a schematic diagram of a coin cell.
  • FIG. 17 is a TEM photograph of the iron oxide particles produced in Example 5.
  • FIG. 18 is a SEM photograph of lithium iron phosphate produced in Example 5.
  • FIG. 19 is an X-ray diffraction pattern of the lithium iron phosphate produced in Example 5.
  • a method for producing a compound having an olipine structure, particularly an olipine-type lithium iron phosphate characterized in that an iron source, a lithium source and a phosphorus source are mixed and calcined.
  • the iron source contains iron oxide particles.
  • the iron oxide particles are fine and can be prepared with precisely controlled particle size distribution.
  • the present inventors pay attention to this point, and by including iron oxide particles as an iron source, a compound having an olipine structure, particularly an olipine-type iron phosphate, having extremely fine particles and a controlled particle size distribution.
  • the iron source used in the present invention includes iron oxide particles.
  • the iron oxide particles preferably have an average particle size of not more than 500 nm, more preferably not more than 300 nm, especially 5 to 300 nm. From an iron oxide particle having an average particle diameter of about 5 nm, a compound having an olivine structure of about 5 to 50 nm is obtained, and from an iron oxide particle having an average particle diameter of about 300 nm is formed from 100 to 50 A compound having an olivine structure of about 0 nm is obtained.
  • the iron oxide particles preferably also have a particle size distribution with a standard deviation ⁇ of 50 or less, particularly 30 or less, and a coefficient of variation [-(standard deviation ⁇ average particle diameter)] of particle diameter of 0.5 or less. Preferably, it has a BET specific surface area value of .10 to 150 m 2 / g.
  • triiron tetroxide (F e 30 4 ) is particularly preferable. Since triiron tetroxide (F e 3 0 4 ) can be prepared as a fine particle and with a precisely controlled particle size distribution by a wet process, using relatively inexpensive materials and equipment, the olivine of the present invention It is useful for producing type iron phosphate.
  • iron oxide is produced by reacting an iron salt with an alkali and mixing, for example, an iron salt and an alkaline water solution, in particular, alkali hydroxide and / or alkali carbonate, to produce iron hydroxide.
  • Fe 3 0 4 obtained by heating (oxidation synthesis) a reaction product containing iron hydroxide to a temperature of 30 to 90 ° C in an oxygen-containing atmosphere (for example, under atmospheric pressure) is preferable.
  • iron salts include iron sulfate, iron acetate, and iron chloride.
  • alkali hydroxide examples include sodium hydroxide, potassium hydroxide, and aqueous ammonia.
  • alkali carbonate examples include sodium carbonate, potassium carbonate, and ammonium carbonate. Even if an alkali metal is used as the alkali, most of the alkali metal generated as a by-product of the neutralization reaction can be removed by washing with water. However, in order to extremely reduce the alkali metal contamination, an ammonium salt is used. It is appropriate. In addition, fine particles can be obtained with only alkali hydroxide, but in order to obtain finer particles, it is effective to use a mixture with alkali carbonate.
  • the neutralization rate is 0.8 to 3.0 (where the neutralization rate is the alkali source used for neutralization with respect to the molar equivalent of the acid source before neutralization.
  • Li source and P source are mixed with the above iron source and calcined to obtain olivine type iron phosphate lithium.
  • Li sources include lithium carbonate, lithium hydroxide, lithium phosphate, etc.
  • P sources include phosphoric acid, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, lithium phosphate, etc. Can be mentioned.
  • the mixing method is not particularly limited, and wet mixing or dry mixing may be used.
  • a device it is appropriate to use a planetary pole mill, a jet mill, a magnetic stirrer or the like. (Baking process)
  • the firing step by supplying thermal energy to the mixture of raw materials, the mixture is converted to a thermodynamically stable olivine-type lithium iron phosphate compound, and impurities are vaporized and removed. This is a step of generating fine particles of an active material.
  • Firing is performed in an inert gas atmosphere or a reducing atmosphere.
  • the inert gas include nitrogen, helium, neon, and argon.
  • the reducing atmosphere include hydrogen, lower alcohols, for example, reducing compounds such as methanol and ethanol, mixtures of reducing compounds and inert gases, and the like.
  • the mixing ratio (volume ratio) of the reducing compound and the inert gas is not particularly limited.
  • the firing temperature is preferably 400 to 800 ° C. Sufficient crystallinity can be obtained even by one-step firing, but crystallinity can be further improved by performing a two-step firing step including a temporary firing step and a main firing step.
  • the pre-baking is usually performed at a temperature of 200 to 500 ° C
  • the main baking is usually performed at a temperature of 400 to 80 ° C, preferably 5 ° 0 to 80 ° C. C, more preferably at a temperature of 500 to 75 ° C. It is also possible to change the gas atmosphere for pre-baking and main baking.
  • various conductive materials for example, carbon
  • various conductive materials for example, carbon
  • inert gas atmosphere or a reducing atmosphere so that the surface of the olivine type lithium iron phosphate particles is treated as such. It is possible to obtain a very fine positive electrode active material in which a conductive material is present.
  • a carbon source when a carbon source is mixed, a single-phase olivine-type lithium iron phosphate can be obtained using only N 2 , for example, without using a reducing gas.
  • the conductive substance include carbon.
  • carbon is advantageous in terms of easy availability and handling.
  • the amount of carbon source added is not limited, but it goes without saying that the carbon content remaining after firing does not become excessive as the positive electrode, preferably 20% by weight or less based on the weight of the positive electrode active material, particularly 3 to It is desirable to add in the range of 20% by weight, and more preferably 5 to 15% by weight.
  • the carbon source is made up of at least carbon particles and carbon precursors that turn into conductive carbon upon firing. Including one.
  • a carbon precursor is used as a carbon source, the particle surface can be covered flat with carbon, and a positive electrode active material having a relatively low surface area can be produced.
  • carbon particles known particles can be used without limitation, and examples thereof include carbon black such as acetylene black; fullerene; carbon nanotubes and the like.
  • carbon precursors include polyvinyl alcohol, polyolefins, polyacrylonitrile, saccharides such as cellulose, starch, glucose, and granulated sugar, and natural organic polymer compounds (especially water-soluble compounds); acrylonitrile, divinylbenzene And polymerizable monomers such as vinyl acetate (particularly, unsaturated organic compounds having a carbon-carbon double bond).
  • the carbon source may be added to the raw material at any stage of the firing process.
  • the carbon source may be added before the pre-firing, or may be added after the pre-firing and before the main firing. It may be added before and at both levels.
  • by adding a carbon source it is possible to obtain an olivine single phase by firing only with an inert gas.
  • the feature of this method is to synthesize uniform iron oxide fine particles and perform solid phase synthesis using this as a raw material, thereby reducing the fine and uniform olivine type material with excellent battery characteristics. It is easy to manufacture industrially at a low cost.
  • the positive electrode active material of the present invention needs to contain olivine-type lithium iron phosphate as a main component.
  • a conductive material such as carbon is included. be able to.
  • the blending ratio of the other components must be 30% or less of the positive electrode active material.
  • the average particle size of the positive electrode active material is preferably 5 to 500 nm, more preferably 30 to 300 nm. In the case of an olivine-type positive electrode active material with low conductivity, if the average particle diameter is too large, sufficient capacity cannot be obtained.
  • the positive electrode active material or the standard deviation ⁇ preferably has a particle size distribution of 50 or less, particularly 30 or less, and the variation coefficient of the particle diameter is preferably 0.6 or less, particularly preferably 0.5 or less, It preferably has a BET specific surface area value of 5 to 50 m 2 Z g.
  • FIG. 16 is a cross-sectional view schematically showing the battery.
  • 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 the two members
  • the active material layer 5, the separator 8, the positive electrode active material layer 7, and the positive electrode current collector 6 are provided in this order.
  • the negative electrode member 2 has a substantially cylindrical shape, and is configured to accommodate the negative electrode current collector 4 and the negative electrode active material 5 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 positive 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 portion of the negative electrode member 2 and the peripheral edge portion of the separator member 8 and positive electrode member 3 are Are overlapping.
  • the space inside the battery is filled with a non-aqueous electrolyte 9, and a sealing material 10 is applied to the overlapping portions of the negative electrode member 2, the separator 8 and the peripheral edge of the positive electrode member 3, so that the inside of the battery is airtight. It is kept.
  • the negative electrode comprises a negative electrode member 2 as an external negative electrode, a negative electrode current collector 4 in contact therewith, and a negative electrode active material layer 5 on the negative electrode current collector.
  • the negative electrode current collector for example, nickel foil, copper foil or the like is used.
  • the negative electrode active material layer a layer that can be doped with lithium is used. Specifically, metallic lithium, a lithium alloy, a conductive polymer doped with lithium, a layered compound (a carbon material or a metal oxide) Etc.)
  • 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 but also as the negative electrode current collector, the battery structure can be simplified by using the metal lithium foil for the negative electrode.
  • the positive electrode comprises a positive electrode member 3 as an external positive electrode, a positive electrode current collector 6 in contact therewith, and a positive electrode active material layer 7 on the positive electrode current collector.
  • the positive electrode active material of the present invention described above is used as the positive electrode active material.
  • As the positive electrode current collector for example, an aluminum foil or the like is used.
  • the As a binder contained in the positive electrode active material layer as a binder for a positive electrode active material layer of this type of non-aqueous electrolyte battery such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE). Commonly used known resin materials can be used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • a conductive material can be blended in the positive electrode active material layer in order to improve conductivity.
  • the conductive material examples include graphite and acetylene black.
  • the separator 8 is for separating the positive electrode and the negative electrode, and a known material that is usually used as a separator for this type of non-aqueous electrolyte battery can be used, for example, a polymer such as polypropylene. A film, a polyethylene-strength porous membrane, etc. are used. Also, from the relationship between lithium ion conductivity and energy density, it is desirable that the thickness of the separation evening be as thin as possible.
  • sealing material 10 a known resin material or the like that is normally 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 various forms such as a solid electrolyte and a gel electrolyte containing a solvent can be used.
  • liquid electrolyte a solution in which the electrolyte is dissolved in an aprotic non-aqueous solvent is used.
  • Non-aqueous solvents include, for example, cyclic carbonates such as ethylene carbonate, propylene strength, butylene strength, vinylene carbonate, and chain carbonates such as dimethyl carbonate, jetyl carbonate, and dipropyl carbonate.
  • cyclic force monoponates such as ethylene carbonate, propylene force monoponate, and vinylene force monoponate
  • chain force monoponates such as dimethyl carbonate, jetyl carbonate, and dipropyl carbonate are used. It is preferable to use it.
  • non-aqueous solvents may be used alone or in combination of two or more.
  • the electrolyte for example, the L i PF 6, L i C 10 4, L i As F 6, L i BF 4, L i CF 3 S0 3, L i N (CF 3 S0 2) 2 and lithium salt of Can be used.
  • Li PF 6 or Li BF 4 examples include inorganic solid electrolytes such as lithium nitride and lithium iodide; organic polymer electrolytes such as poly (ethylene oxide), poly (methacrylate), and poly (acrylate).
  • any material that can be gelled by absorbing the liquid electrolyte can be used without particular limitation.
  • poly (vinylidene fluoride), vinylidene fluoride can be used.
  • fluorine-containing polymers such as / hexafluoropropylene copolymer.
  • a nonaqueous electrolyte battery using the positive electrode active material of the present invention is produced, for example, as follows.
  • 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 including the negative electrode current collector and the negative electrode active material layer is accommodated in the negative electrode member so that the negative electrode current collector and the inner surface of the negative electrode member are in contact with each other to form a negative electrode.
  • the metal lithium foil can be used as it is as the negative electrode current collector 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 current collector and the positive electrode active material layer is accommodated in the positive electrode member so that the positive electrode current collector 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 superposed so that a separate layer 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, a non-aqueous electrolyte battery is completed.
  • the shape of the nonaqueous electrolyte battery of the present invention is not particularly limited, and may be a cylindrical shape, a square shape, a coin shape, a button shape, or the like. Can be of various sizes. Further, the present invention can be applied to both a primary battery and a secondary battery.
  • iron oxide, positive electrode active material, and nonaqueous electrolyte battery were analyzed by the following method.
  • the specific surface area was measured using a fully automatic surface area measuring device Multisoap 12 (manufactured by Yuasa Ionics Co., Ltd.) according to the BET method.
  • the metal composition analysis was measured by ICP emission spectroscopic analysis (ICP emission spectrophotometer SPS 1500 VR Seiko Instr umen ts Inc.) and calculated by the mo 1 ratio to Fe.
  • Example 1 For the particle size, we randomly selected 200 particles observed with TEM (Transmission Electron Microscope H-7600 manufactured by Hitachi) or SEM (Scanning Electron Microscope DS 130, manufactured by Topcon Electron Beam Service Co., Ltd.) The particle diameter of the particles was measured, the average value and standard deviation of the measured values were calculated, and this average value was taken as the particle diameter. The variation coefficient of the particle diameter is a value obtained by dividing the standard deviation thus obtained by the average particle diameter.
  • TEM Transmission Electron Microscope H-7600 manufactured by Hitachi
  • SEM Sccanning Electron Microscope DS 130, manufactured by Topcon Electron Beam Service Co., Ltd.
  • a 60 L reaction vessel was charged with 40 L of an aqueous solution containing 23 mol of NaOH and 11 mol of Na 2 C0 3 , and was replaced by aeration of nitrogen gas and kept at 60 ° C. Where nitrogen aeration, stirring, 1 81110 1? 630 ⁇ 1 and 0. 9] 10 1? 6 2 20 L of an aqueous solution containing (S0 4 ) 3 was added to form a suspension containing iron hydroxide particles, and mixed at 60 ° C. for 60 minutes. Next, the air was passed through 1 OLZmin at 60 ° C, and the oxidation reaction was performed for 2 hours. The obtained suspension was filtered, washed and dried to obtain fine-particle magnetite (Fe 3 0 4 ).
  • the specific surface area of the sample was measured by the BET method.
  • the BET value of the obtained sample was 27.4 m 2 / g.
  • Figure 1 shows a TEM photograph of the sample obtained. The particle size was calculated as an average value by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 65 nm and a coefficient of variation of 0.32.
  • X-ray diffraction measurement was performed on the obtained particles.
  • Figure 2 shows the X-ray diffraction pattern of the particles obtained. From the X-ray diffraction pattern, it was confirmed to be Fe 3 0 4 single phase.
  • Li FeP0 4 was synthesized from the magnetite cake (Fe 3 4 ) obtained in (1) above. Iron oxide obtained in (1) 0.05 mol 1, Li 2 C 0 3 0.083 mol, (NH 4 ) 2 HP0 4 0.15 mol 1 and dalcose 5 g 8 OmL planetary pole mill container In addition, 2 OmL of pure water was added and mixed at 25 Or. Pm for 12 hours. After drying, powdered in an agate mortar and mixed with hydrogen (H 2 ) and nitrogen (N 2 ) in a volume ratio of 2: 5 at 450 ° C for 2 hours and N 2 atmosphere at 600 ° C for 15 hours. firing to obtain a positive electrode active material L i F e P0 4.
  • H 2 hydrogen
  • N 2 nitrogen
  • the BET value of the obtained sample was 33.8 m 2 /.
  • Figure 3 shows an SEM photograph of the sample obtained.
  • the particle size was calculated as an average value by randomly measuring 200 particles from a TEM photograph.
  • the obtained sample had an average particle size of 52 nm and a coefficient of variation of 0.39.
  • Figure 4 shows the X-ray diffraction pattern of the particles obtained. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
  • Table 1 shows the results of composition analysis by ICP analysis.
  • positive electrode active material obtained in (2) Using the positive electrode active material obtained in (2), a lithium secondary battery was produced.
  • positive electrode active material: conductive material: binder 70:25 (total amount of C, ie, pre-treated The amount of acetylene black added to the amount of bonbon (derived from glucose) ): After mixing at a weight ratio of 5 and kneading in an agate mortar, it was punched out into a disk with a diameter of 1.0 cm and a thickness of 0.2 mm using a cork poller, and this was taken as the positive electrode pellet. Used.
  • a coin cell was produced using the positive electrode pellet.
  • a lithium foil having a diameter of 1.5 cm and a thickness of 0.15 mm was used.
  • a separator a porous polyethylene sheet having a diameter of 22 mm and a thickness of 02 mm was used.
  • the non-aqueous electrolyte solution is Li PF 6 dissolved in a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) at a volume ratio of 1: 1 at a concentration of about 1 mol Z liter. It was used.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • a charge / discharge test was conducted on the simple lithium secondary battery thus obtained.
  • the charge / discharge test was performed at 25 ° C, with a potential range of 2000 to 4500 mV, a rate of 1 C, and C. C. — C. V.
  • the initial charge / discharge characteristics are shown in Fig. 6 ("Chg.” Represents charge and "Dis.” Represents discharge).
  • Table 2 shows the initial charge / discharge capacity.
  • Example 1 Magnetite obtained in Example 1 (Fe 3 0 4) was synthesized L i FeP0 4 as a raw material. Put the iron oxide obtained in Example 1 0.05 mol, Li 2 C 0 3 0 083 mol 1, (NH 4 ) 2 HP0 4 0.15 mol, 3 g glucose into an 80 mL planetary pole mill container. Further, 2 OmL of pure water was added and mixed at 25 Or.pm for 5 hours. After drying, was ground in an agate mortar, N 2 atmosphere, 65 O: 3 hours, and calcined, to obtain a positive electrode active material L i F e ⁇ 0 4. The BET value of the obtained sample was 13.8 m 2 // g.
  • Figure 7 shows a SEM photograph of the sample obtained. The particle size was calculated from an average value of 200 particles randomly measured from a TEM photograph. The average particle size of the obtained sample is 6
  • the variation coefficient was 0 nm and 0 nm.
  • Figure 8 shows the X-ray diffraction pattern of the particles obtained. From the X-ray diffraction pattern, it was confirmed to be an olipine-type lithium iron phosphate single phase. Table 1 shows the composition analysis results by ICP analysis.
  • Example 2 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
  • the BET value of the obtained sample was 13.5 m 2 Zg.
  • Figure 9 shows a TEM photograph of the obtained sample. The particle size was calculated as an average value by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 107 nm and a coefficient of variation of 0.28.
  • Magunetai Bok obtained above in (1) to (Fe 3 0 4) was form if the L i F e P_ ⁇ 4 as a raw material.
  • Positive electrode active material Li F e P0 Got 4 was formed if the L i F e P_ ⁇ 4 as a raw material.
  • the BET value of the obtained sample was 5.3 m 2 Zg.
  • Figure 10 shows a SEM photograph of the obtained sample. The particle size was calculated from an average value of 200 particles randomly measured from a TEM photograph. The obtained sample had an average particle size of 11 nm and a coefficient of variation of 0.39.
  • Table 1 shows the composition analysis results by ICP analysis.
  • Example 2 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
  • Example 3 Magne evening Ito obtained in Example 3 (Fe 3 ⁇ 4) was synthesized L i F e P0 4 in the raw material. Put the iron oxide obtained in Example 3 0.05 mol, Li 2 C0 3 0.086 mol 1, (NH 4 ) 2 HP0 4 0.15 mol, 5 g glucose into an 80 mL planetary pole mill container, Further, 2 OmL of pure water was added and mixed for 12 hours at 25 Or.pm. After drying, Kona ⁇ in an agate mortar, N 2 atmosphere, for 3 hours at 650 ° C, and fired to obtain a positive electrode active material L i Fe P_ ⁇ 4. The BET value of the obtained sample was 27.7m 2 Zg. Figure 11 shows an SEM photograph of the sample obtained. The particle size was calculated from an average value of randomly measured 200 particles from a TEM photograph. The obtained sample had an average particle size of 66 nm and a coefficient of variation of 0.36.
  • Table 1 shows the results of composition analysis by ICP analysis.
  • Example 2 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
  • Fig. 13 shows an S-photograph of the obtained sample
  • Fig. 14 shows a photo.
  • the obtained particles were also amorphous. From the X-ray diffraction pattern of the obtained particles, it was confirmed that it was a single phase olivine type lithium iron phosphate. confirmed.
  • Table 1 shows the results of composition analysis by ICP analysis.
  • Example 2 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
  • Synthesized magnetic evening site (BET value 2. 6 m 2 Zg, average particle size 520 nm, coefficient of variation 0.53) was synthesized L i F e P0 4 in the raw material. Put the above magnetite 0.05 mol, Li 2 C0 3 0.083 mol 1, (NH 4 ) 2 HP 0 4 0.15 mol, glucose 5 g into an 8 OmL planetary pole mill container, and then add 2 OmL of pure water. Add and mix at 25 Or. Pm for 5 hours. After drying, was ground in an agate mortar, under N 2 Kiri ⁇ air, 4 hours at 650 ° C, and fired to obtain a positive electrode active material L i FeP_ ⁇ 4. The BET value of the obtained sample was 25. Yn ⁇ Zg.
  • Figure 15 shows an SEM photograph of the sample obtained.
  • the particle size was calculated as an average value by randomly measuring 200 particles from a TEM photograph.
  • the obtained sample had an average particle size of 109 nm and a coefficient of variation of 0.62. From the obtained particle X-ray diffraction pattern, it was confirmed to be an olivine-type lithium iron phosphate single phase.
  • Table 1 shows the results of composition analysis by ICP analysis.
  • Example 2 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
  • Example 1 Mol ratio to Fe Example 1 1 1.0 1.0 5.8
  • Example 2 1 1.0 1.0 2.7
  • Example 3 1 1.0 1.0 0
  • Example 4 1 1.0 1.0 5.7 Comparative Example 1 1 1.0 1.0 5.3 Comparative Example 2 1 1.0 1.0 5.7
  • Example 1 131 138 Example 2 138 134 Example 3 117 110 Example 4 132 126 Comparative Example 1 87 66 Comparative Example 2 113 87 Example 5
  • a 60 L reaction vessel was charged with 40 L of an aqueous solution containing 52.8 mo 1 of NaOH, purged with nitrogen gas, and kept at 80 ° C.
  • 20 L of an aqueous solution containing 6 mol of Fe S0 4 and 6 mol of Fe 2 (S 0 4 ) 3 was added with nitrogen aeration and stirring, and mixed at 80 ° C. for 3 hours.
  • the obtained suspension was filtered, washed and dried to obtain fine-particle magnetite (Fe 3 0 4 ).
  • the specific surface area of the sample was measured by the BET method.
  • the BET value of the obtained sample was 74.2 m 2 / g.
  • Figure 17 shows a TEM photograph of the sample obtained. The particle size was calculated from an average value of 200 particles randomly measured from a TEM photograph. The obtained sample had an average particle size of 11 nm and a coefficient of variation of 0.34.
  • the olivine-type iron phosphate was synthesized from the iron oxide (Fe 3 4 ) obtained in (1) above. Put the iron oxide obtained in (1) 0.05 mol, Li 2 C0 3 0.0 0.0 mol, (NH 4 ) 2 HP0 4 0.15 mo 1 and 4 g glucose into an 80 mL planetary pole mill container, Further, 2 OmL of pure water was added and mixed at 25 Or.pm for 12 hours. After drying at 120 ° C., the mixture was pulverized in an agate mortar and fired at 650 ° C. for 6 hours in an N 2 atmosphere to obtain a positive electrode active material L 1 Fe P0 4 . The obtained sample had a BET value of 12.501 2 and a carbon content of 3.3% by weight.
  • Figure 18 shows a SEM photograph of the obtained sample. The particle size was calculated as an average value by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 80 nm and a coefficient of variation of 0.32.
  • FIG. 19 shows the X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
  • a coin cell was assembled and a charge / discharge test was performed. The initial charge / discharge capacity was a charge capacity of 14 OmAh / g and a discharge capacity of 138 mAh / g.
  • non-aqueous electrolyte battery using the positive electrode active material of the present invention examples include lithium secondary batteries such as a metal lithium battery, a lithium ion battery, and a lithium polymer battery.

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Abstract

L'invention porte sur un composé ayant une structure d'olivine, qui forme une matière active d'électrodes positive à faible coût ayant une haute sécurité et d'excellentes caractéristiques de batterie telles que la densité d'énergie. L'invention porte également sur un procédé de fabrication d'un tel composé et sur une batterie d'électrolyte non aqueux ayant une électrode positive contenant un tel composé. De façon spécifique, l'invention porte sur un procédé de fabrication d'un composé ayant une structure d'olivine, qui est caractérisé par le fait qu'une source de fer contenant des particules d'oxyde de fer, une source de lithium et une source de phosphore sont mélangées et calcinées.
PCT/JP2008/050650 2007-01-29 2008-01-11 Composé ayant une structure d'olivine, son procédé de fabrication, matière active d'électrode positive utilisant un composé ayant une structure d'olivine et batterie a électrolyte non aqueux WO2008093551A1 (fr)

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JP2012056827A (ja) * 2010-09-13 2012-03-22 Mitsui Mining & Smelting Co Ltd 酸化鉄粒子
JP2012530672A (ja) * 2009-06-24 2012-12-06 ビーエーエスエフ ソシエタス・ヨーロピア ＬｉＦｅＰＯ４−炭素合成物を製造するための方法
JP2013143298A (ja) * 2012-01-11 2013-07-22 Idemitsu Kosan Co Ltd 電極材料、電極及びそれを用いた電池
JP2016056093A (ja) * 2010-06-30 2016-04-21 株式会社半導体エネルギー研究所 正極活物質の作製方法、正極活物質、及び二次電池
CN106058307A (zh) * 2016-08-17 2016-10-26 刘新保 一种利用磷酸铁锂废料制备锂离子电池正极材料磷酸铁锂的方法
WO2023206226A1 (fr) * 2022-04-28 2023-11-02 Dic Corporation Particules de forstérite et procédé de production de particules de forstérite

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JP2011210376A (ja) * 2010-03-28 2011-10-20 Niigata Univ Ｌｉイオン電池用正極活物質およびその製造方法
JP2016056093A (ja) * 2010-06-30 2016-04-21 株式会社半導体エネルギー研究所 正極活物質の作製方法、正極活物質、及び二次電池
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JP2013143298A (ja) * 2012-01-11 2013-07-22 Idemitsu Kosan Co Ltd 電極材料、電極及びそれを用いた電池
CN106058307A (zh) * 2016-08-17 2016-10-26 刘新保 一种利用磷酸铁锂废料制备锂离子电池正极材料磷酸铁锂的方法
CN106058307B (zh) * 2016-08-17 2018-11-27 刘新保 一种利用磷酸铁锂废料制备锂离子电池正极材料磷酸铁锂的方法
WO2023206226A1 (fr) * 2022-04-28 2023-11-02 Dic Corporation Particules de forstérite et procédé de production de particules de forstérite

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