WO2011043419A1 - リチウム二次電池用正極活物質材料、その製造方法、及びそれを用いたリチウム二次電池 - Google Patents

リチウム二次電池用正極活物質材料、その製造方法、及びそれを用いたリチウム二次電池 Download PDF

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WO2011043419A1
WO2011043419A1 PCT/JP2010/067647 JP2010067647W WO2011043419A1 WO 2011043419 A1 WO2011043419 A1 WO 2011043419A1 JP 2010067647 W JP2010067647 W JP 2010067647W WO 2011043419 A1 WO2011043419 A1 WO 2011043419A1
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lithium
positive electrode
active material
electrode active
secondary battery
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PCT/JP2010/067647
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English (en)
French (fr)
Japanese (ja)
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潤 金田
大 稲垣
有花 長嶺
順幸 諸石
真吾 池田
浩一郎 宮嶋
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東洋インキ製造株式会社
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Priority to CN201080045624.5A priority Critical patent/CN102576873B/zh
Priority to JP2011535452A priority patent/JP5640987B2/ja
Publication of WO2011043419A1 publication Critical patent/WO2011043419A1/ja

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • 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 composite oxide coated with conductive carbon suitable as a positive electrode active material for a lithium secondary battery, a method for producing the same, and a lithium secondary battery using the composite oxide.
  • lithium secondary batteries are being actively developed.
  • a positive electrode in which an electrode mixture composed of a positive electrode active material containing lithium ions, a conductive additive, an organic binder, and the like is fixed to the surface of a current collector of a metal foil, and a lithium ion
  • a negative electrode is used in which an electrode mixture composed of a removable negative electrode active material, a conductive additive, an organic binder, and the like is fixed to the surface of a current collector of a metal foil.
  • lithium transition metal composite oxides such as lithium cobaltate, lithium manganate, and lithium nickelate are used. These lithium transition metal composite oxides are thermally stable. There are problems such as performance degradation due to composition change at the time of charge and discharge, high price due to the use of rare metals, etc. As a countermeasure for these, lithium iron phosphorus composite oxide containing iron rich in resources and cheap Attention has been paid.
  • lithium iron phosphate having an olivine structure represented by LiFePO 4 is expected as a highly practical material because it has a potential of about 3.5 V with respect to metallic lithium. Yes.
  • a lithium transition metal phosphorus composite oxide having an olivine structure represented by LiFePO 4 is a crystal having a very poor electronic conductivity as compared with other positive electrode active materials, and the conduction of lithium ions in the crystal.
  • the high discharge capacity in the battery could not be expected.
  • the primary particles of the positive electrode active material are made into fine particles (Patent Documents 1, 2, 3, 4), and the surface of the positive electrode active material particles is coated with a conductive component (Patent Documents 5, 6, 7, 8, 9, 10), and countermeasures such as doping a different metal into the positive electrode active material crystal (Patent Document 11) have been reported.
  • Both methods improve the electronic conductivity of the positive electrode active material and / or improve the conductivity of lithium ions, and the battery has a good discharge capacity close to the theoretical value and good charge / discharge characteristics at high load. It is obtained.
  • many methods for coating the surface of the positive electrode active material particles with a conductive component have been proposed as methods for improving the electron conductivity of the positive electrode active material easily and effectively.
  • Patent Document 5 carbon black (Patent Document 5) which is a conductive fine particle, an organic compound (Patent Documents 6, 7, 8, 9) capable of forming a conductive carbon film by thermal decomposition, and Conductive metal oxides (Patent Document 10) have been reported.
  • Patent Documents 6, 7, 8, 9 organic compound capable of forming a conductive carbon film by thermal decomposition
  • Conductive metal oxides Patent Document 10.
  • a conductive carbon coating obtained by thermally decomposing saccharides as organic compounds is used as the conductive component. It has been reported.
  • Japanese Patent No. 4058680 Japanese Patent No. 4190912 JP 2002-015735 A JP 2008-159495 A Japanese Patent No. 4151210 Japanese Patent No. 4297406 Japanese Patent Laid-Open No. 2004-063386 JP 2007-250417 A JP 2008-034306 A Japanese Patent Laid-Open No. 2003-300734 International Publication WO20055041327
  • the problem is that a part or all of the particle surface of the lithium transition metal composite oxide is coated with conductive carbon, and the conductive carbon is composed of an unmodified or modified natural wax, natural resin, and vegetable oil.
  • a positive electrode active material for a lithium secondary battery which is a thermal decomposition product of a natural material selected from the group.
  • the present invention provides a positive electrode active material for a lithium secondary battery, wherein the conductive carbon content is 0.1 wt% or more and 30 wt% or less with respect to the entire positive electrode active material for a lithium secondary battery. Regarding materials.
  • the present invention also relates to a positive electrode active material for a lithium secondary battery, wherein the lithium transition metal composite oxide is a lithium transition metal phosphorus composite oxide having an olivine structure.
  • the present invention also includes a step of mixing a lithium-containing compound, a transition metal-containing compound, and an unmodified or modified natural material selected from the group consisting of natural wax, natural resin, and vegetable oil, and the mixture. And a method of producing a positive electrode active material for a lithium secondary battery, comprising a step of heating at 200 to 1100 ° C.
  • the present invention also includes a step of mixing a lithium-containing compound, a transition metal-containing compound, a phosphorus-containing compound, and a natural material selected from the group consisting of an unmodified or modified natural wax, natural resin, and vegetable oil. And a method for producing a positive electrode active material for a lithium secondary battery, comprising the step of heating the mixture at 200 to 1100 ° C.
  • the present invention also includes a step of mixing a lithium transition metal composite oxide with an unmodified or modified natural material selected from the group consisting of natural waxes, natural resins, and vegetable oils, and the mixture comprising 200-1100.
  • the manufacturing method of the positive electrode active material material for lithium secondary batteries including the process heated at degreeC.
  • the present invention also relates to a positive electrode active material for a lithium secondary battery produced using the production method.
  • the present invention also relates to an electrode containing the positive electrode active material for a lithium secondary battery.
  • the present invention also relates to a lithium secondary battery comprising the electrode as a positive electrode.
  • a natural material which is an inexpensively available material, is used as a conductive carbon source, and the particle surface of the lithium transition metal composite oxide is treated by heat treatment.
  • the surface of the particles of the lithium transition metal composite oxide can be coated with conductive carbon, and a positive electrode active material for a lithium secondary battery with improved conductivity can be produced at low cost.
  • the discharge capacity and charge / discharge characteristics of the lithium secondary battery can be improved by using the positive electrode active material for a lithium secondary battery according to a preferred embodiment of the present invention for the positive electrode of the lithium secondary battery. .
  • the positive electrode active material for a lithium secondary battery according to the present invention is formed by covering part or all of the particle surface of the lithium transition metal composite oxide with conductive carbon, and the conductive carbon is unmodified or modified.
  • the heat-decomposed product of a natural material selected from the group consisting of natural wax, natural resin, and vegetable oil is described below in detail.
  • the lithium transition metal composite oxide is not particularly limited, but is a metal oxide containing at least lithium and a transition metal.
  • the transition metal include Fe, Co, Ni, Mn, and the like, and one lithium transition metal composite oxide may contain two or more transition metals.
  • phosphorus (P) may be contained.
  • layered lithium nickel composite oxide, lithium cobalt composite oxide, lithium manganese composite oxide, lithium cobalt nickel composite oxide, lithium nickel manganese composite oxide, lithium cobalt nickel manganese composite examples thereof include oxides and lithium cobalt nickel aluminum based composite oxides.
  • the lithium manganese type complex oxide etc. of a spinel structure are mentioned.
  • lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate and the like, which are lithium transition metal phosphorus composite oxides having an olivine structure can be mentioned.
  • olivine-structured lithium iron phosphate is a preferable material from the viewpoint of cost and safety.
  • the lithium transition metal phosphorus composite oxide having an olivine structure has poor electronic conductivity as compared with other lithium transition metal composite oxides, so that it is difficult to obtain excellent battery performance.
  • the present inventors are such a complex oxide, the particle surface of which is a thermal decomposition product of a natural material selected from the group consisting of an unmodified or modified natural wax, natural resin, and vegetable oil. It has been found that by covering with conductive carbon, the electronic conductivity is improved, and the discharge capacity and charge / discharge characteristics of the lithium secondary battery are improved.
  • conductive carbon is produced by thermally decomposing a natural material.
  • a natural material selected from the group consisting of unmodified or modified natural wax, natural resin, and vegetable oil is preferable.
  • these natural materials can be used after being dissolved or dispersed in a medium such as a solvent or water.
  • Natural waxes include plant waxes and mineral waxes.
  • plant waxes include carnauba wax, rice wax, cadilla wax, and Japan wax, depending on the plant used as a raw material.
  • mineral waxes include montan wax produced by solvent extraction from brown coal, and are mainly used after being modified.
  • modified natural wax examples include oxidized or esterified modified products of montan wax.
  • Examples of commercially available plant-based natural waxes include natural waxes manufactured by Toyo Adri Co., Ltd. such as Carnauba No. 1, Carnauba No. 2, Carnauba No. 3, and Candelilla wax; Towa such as rice wax decolorized products, refined rice wax, Japan wax, etc. Natural wax produced by Kasei Co .; natural wax produced by Miki Chemical Industry Co., Ltd. such as bead wax;
  • Examples of commercially available mineral-modified natural waxes include modified natural waxes manufactured by Toyo Adre such as Montan Wax EP, Montan Wax OP, and Montan Wax NA; LUWAX-S, LUWAX-E, LUWAX-OP, LUWAX-LEG, and the like. Examples include, but are not limited to, modified natural waxes manufactured by BASF; modified natural waxes manufactured by Clariant, such as Recowax E, Recolve WE4, Recolve WE40, Recommont ET141, Recommont ET132, and the like.
  • Natural resins include non-volatile solid or semi-solid substances contained in the sap secreted from the bark and resinous substances secreted by the scale insects parasitic on the tree. Specific examples of natural resins include rosin, dammar, copal and shellac.
  • Examples of commercially available natural resins include natural resins manufactured by Harima Chemicals, Inc. such as tall rosin RX and tall rosin R-WW; natural resins manufactured by Arakawa Chemical Co., Ltd .; gum rosin; Chinese gum rosin X grade; Chinese gum rosin WW grade; Natural resin made by Azuchi Sangyo Co., Ltd.
  • natural resin is mentioned, it is not limited to these.
  • modified natural resins include modified resins such as rosin and terpene.
  • modified natural resins examples include, as modified rosins, polymerized rosin, high veil CH, superester L, superester A-18, superester A-75, superester A-100, superester A-115, Superester A-125, Superester T-125, Pencel A, Pencel AZ, Pencel C, Pencel D-125, Pencel D-135, Pencel 160, Pencel KK, Ester Gum AAG, Ester Gum AAL, Ester Gum A, Ester Gum AAV, Ester Gum 105, Ester Gum AT, Ester Gum H, Ester Gum HP, Ester Gum HD, Pine Crystal KR-85, Pine Crystal KR-612, Pine Crystal KR-614, Pine Crystal KE-100, In Crystal KE-311, Pine Crystal KE-359, Pine Crystal KE-604, Pine Crystal D-6011, Pine Crystal KE-615-3, Pine Crystal D-6250, Pine Crystal KM-1500, Pine Crystal KR-50M, Superester E-720
  • Vegetable oils include soybean oil, linseed oil, castor oil, coconut oil, tung oil, rice bran oil, palm oil, coconut oil, corn oil, olive oil, rapeseed oil, sunflower oil, tall oil, turpentine oil, and the like.
  • Examples of commercially available vegetable oils include vegetable oils manufactured by Marusho Co., Ltd. such as soybean oil KT; vegetable oils manufactured by Nissin Oilio Co., Ltd. such as soybean white squeezed oil and flaxseed oil; vegetable oils manufactured by Bosso fats such as rice salad oil; Vegetable oils; vegetable oils manufactured by Azuchi Sangyo Co., Ltd. such as limonene oil, eucalyptus oil, tung oil; vegetable oils manufactured by Harima Kasei Co., Ltd. such as Hartle SR-20, Hartle SR-30, Hartle R-30, etc .; Examples include, but are not limited to, turpentine made by Arakawa Chemical.
  • Modified vegetable oils include modified products such as soybean oil, linseed oil, castor oil, coconut oil, tung oil, sunflower oil, tall oil and the like.
  • modified vegetable oils examples include Arachid IA-120-60L, Arachid 1782-60, Araeze 3101X-60, Arachid 8042-80, Araeze 5301X-50, Arachid 8012, Araeze 5350, Arachid 1465-60, Arachid 3145- 80, Araeze 310, Arachid 5001, Arachid 251, Arachid 6300, Araeze S-5021, Arachid M-302, Araeze 7502X, Arachid 7506, Arachid 1232-60, Arachid 7100X-50, Arachid 7104, Arachid 7107, Arachid 7108, Arachid Modified vegetable oils manufactured by Arakawa Chemical Co., Ltd.
  • Haliftal 732-60 Haliftal COG40-5 T, Halfiftal SB-3600, Halfiftal SB-7150X, Halfiftal SB-7540, Halfiftal 3011, Halfiftal 3100, Halfiftal 3150, Halfiftal 3271, Halfiftal 3371, Halfiftal SC-3059TX, Halfiftal 764, Halfiftal SL816, Half Vital SL816 , Haliftal 3011PN, Haliftal 3254PN, Khalfartar 3256P, Khalfartar 3200PN, Khalfartar 3258P-N150, Halifartal 3530P, Khalfartal 3004, Halifaltal 3005, Haliftal 601, Haliftal 640, Halifartal 1284, Halifaltar SL-2184, F-8, Haripor F-16, Haridimer 200, Haridimer 250, Haridimer 270S, DIACID-1550, Hartle Q-1, Hartle Q-2, Hartle QFA-2, Hartle FE-
  • These natural materials are very inexpensive carbon-containing compounds, have a high carbon content in the compounds, and contain almost only carbon remaining in the elements by thermal decomposition in an inert gas atmosphere or a reducing gas atmosphere. In addition, it has the characteristic of easily producing carbon with electronic conductivity efficiently with a small addition amount. Further, by modifying with other compounds, physical properties such as melting point, softening point, decomposition temperature, etc. can be easily changed, so that it is improved to a more preferable compound as an organic compound that generates conductive carbon by thermal decomposition. You can also.
  • Saccharides which are the same natural materials, can be cited as materials that generate conductive carbon by thermal decomposition, but natural materials selected from the group consisting of unmodified or modified natural waxes, natural resins, and vegetable oils used in the present invention.
  • natural materials selected from the group consisting of unmodified or modified natural waxes, natural resins, and vegetable oils used in the present invention.
  • the effect of suppressing the crystal growth of lithium transition metal composite oxides during heating is poor, primary particle diameters vary greatly, and particles tend to sinter, and are uniformly coated with carbon at the primary particle level. It is difficult to obtain a positive electrode active material for a lithium secondary battery. Therefore, it is difficult to obtain better battery characteristics.
  • the amount of conductive carbon produced by thermal decomposition is significantly smaller when compared with the same addition amount and the same reaction conditions, and there are many materials that are not efficient in terms of productivity.
  • the content of the conductive carbon in the positive electrode active material for a lithium secondary battery is specifically 0.1 wt% or more and 30 wt% or less, preferably 0.5 wt% or more and 20 wt% or less, More preferably, it is desirable to use a material of 1 to 15% by weight, most preferably 1 to 10% by weight.
  • a positive electrode active material for a lithium secondary battery having a conductive carbon content of less than 0.1% by weight it may be difficult to obtain sufficient conductivity, and the internal resistance of the positive electrode is improved and high. Battery performance may be difficult to obtain.
  • a positive electrode active material for a lithium secondary battery having a conductive carbon content of more than 30% by weight is used, sufficient conductivity is obtained, but the content of the lithium transition metal composite oxide in the positive electrode decreases. At the same time, the lithium ion content also decreases, so the discharge capacity per volume of the battery may decrease, and it may be difficult to use as a highly practical battery.
  • the positive electrode active material for a lithium secondary battery in the present invention there is little sintering between particles of a lithium transition metal composite oxide (including a lithium transition metal phosphorus composite oxide having an olivine structure),
  • the primary particle size is as uniform as possible, and the particle surface of lithium transition metal composite oxide (including lithium transition metal phosphorus composite oxide having olivine structure) is uniformly treated with a small amount of conductive carbon. Is mentioned.
  • the lithium transition metal composite oxide is subjected to thermal decomposition of a natural material selected from the group consisting of unmodified or modified natural wax, natural resin, and vegetable oil.
  • the method for treating the conductive carbon produced by the process is not limited to one method.
  • a method for producing a positive electrode active material for a lithium secondary battery when synthesizing a lithium transition metal composite oxide whose surface is treated with conductive carbon, a lithium-containing compound, a transition metal-containing compound, A method comprising a step of preparing a mixture of a modified or modified natural material selected from the group consisting of natural wax, natural resin, and vegetable oil, and a step of heating and reacting the mixture.
  • a reaction for forming a lithium transition metal composite oxide upon heating and a reaction for generating conductive carbon by thermal decomposition of a natural material selected from the group consisting of unmodified or modified natural wax, natural resin, and vegetable oil The lithium transition metal composite oxide whose surface is treated with conductive carbon is finally obtained.
  • a lithium transition metal phosphorus composite oxide having an olivine structure a lithium-containing compound, a transition metal compound, phosphorus And a production method including a step of making a mixture of a contained compound and a natural material selected from the group consisting of unmodified or modified natural wax, natural resin, and vegetable oil, and a step of heating and reacting the mixture.
  • a lithium transition metal composite oxide (including a lithium transition metal phosphorus composite oxide having an olivine structure) is shown below.
  • ⁇ Mixing process, mixing device> The following dry processing machines and wet processing machines are used in the process of mixing the natural material selected from the group consisting of unmodified or natural wax, natural resin, and vegetable oil with other raw material components. Can be used.
  • dry processing machines include roll mills such as 2 rolls and 3 rolls, high-speed stirrers such as Henschel mixers and super mixers, fluid energy crushers such as micronizers and jet mills, attritors, and particle composites manufactured by Hosokawa Micron.
  • Examples of the apparatus include “Nanocure”, “Nobilta”, “Mechanofusion”, Nara Machinery Co., Ltd. powder surface modification device “Hybridization system”, “Mechanomicros”, “Miraro”, and the like.
  • natural materials selected from the group consisting of unmodified or modified natural waxes, natural resins, and vegetable oils, there are materials that are solid at room temperature but have a low melting point and softening point of less than 100 ° C. In some cases, it is possible to mix more uniformly by melting and mixing under heating than when mixing at normal temperature.
  • wet processing machines include mixers such as dispersers, homomixers, or planetary mixers; homogenizers such as “Clearmix” manufactured by M Technique, or “Fillmix” manufactured by PRIMIX; paint conditioner (Red Devil) ), Ball mill, sand mill (such as “Dynomill” manufactured by Shinmaru Enterprises), media type disperser such as attritor, pearl mill (such as “DCP mill” manufactured by Eirich), or coball mill; wet jet mill (Genus) "Genus PY” manufactured by Sugino Machine, “Starburst” manufactured by Sugino Machine, “Nanomizer” manufactured by Nanomizer, etc., "Claire SS-5" manufactured by M Technique, or “Micros” manufactured by Nara Machinery Co., Ltd. Disperser; or other Mill, but a kneader and the like, but is not limited thereto. Moreover, it is preferable to use what performed the metal mixing prevention process from an apparatus as a wet processing machine.
  • a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating is preferably used.
  • ceramic beads such as glass beads, zirconia beads, or alumina beads.
  • a roll mill it is preferable to use a ceramic roll. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.
  • a general pigment dispersant can be added together and dispersed and mixed.
  • Battery performance by selecting the best mixing or dispersing device for natural materials selected from the group consisting of unmodified or modified natural waxes, natural resins, and vegetable oils that produce conductive carbon by pyrolysis Excellent positive electrode active material for a lithium secondary battery can be obtained.
  • the heating temperature in the heating step varies depending on the target positive electrode active material for a lithium secondary battery, but is desirably 200 to 1100 ° C., preferably 400 to 1000 ° C.
  • the heating temperature in the heating step is lower than 200 ° C.
  • the heating temperature exceeds 1100 ° C. conductive carbon generated by pyrolysis of a natural material selected from the group consisting of unmodified or modified natural wax, natural resin, and vegetable oil tends to be lost by combustion.
  • impurities other than the target positive electrode active material for a lithium secondary battery may be easily generated.
  • the atmosphere in the heating process varies depending on the target positive electrode active material for the lithium secondary battery, but it is an air atmosphere, an inert gas atmosphere such as nitrogen or argon, or a reducing gas atmosphere containing hydrogen. Etc.
  • the positive electrode active material for a lithium secondary battery is a lithium transition metal phosphorus composite oxide having an olivine structure
  • the transition metal is easily oxidized by oxygen and a lithium transition metal phosphorus composite oxide having a different purpose is used. Since it may be produced, it is preferable to carry out in an inert gas atmosphere or a reducing gas atmosphere containing as little oxygen as possible.
  • Lithium-containing compound, transition metal-containing compound, phosphorus-containing compound For raw materials other than natural materials selected from the group consisting of unmodified or modified natural waxes, natural resins, and vegetable oils that produce conductive carbon by pyrolysis, the lithium transition metal composite oxide or olivine structure to be produced It varies depending on the composition of the lithium transition metal phosphorus-based composite oxide.
  • any compound containing lithium can be used.
  • organic acid salts such as oxides, hydroxides, chlorides, carbonates, phosphates, and acetates are preferable.
  • transition metal-containing compound any compound containing transition metals such as cobalt, nickel, manganese, iron and the like can be used.
  • organic acid salts such as oxides, hydroxides, chlorides, carbonates, phosphates, and acetates are preferable.
  • a phosphate is preferable from the viewpoint of storage stability and ease of handling.
  • ⁇ Method for producing lithium transition metal composite oxide> In the method for producing a positive electrode active material for a lithium secondary battery in the present invention, a specific example of a lithium transition metal composite oxide (including a lithium transition metal phosphorus-based composite oxide having an olivine structure) before treating conductive carbon Various production methods include a solid phase method, a hydrothermal method, a coprecipitation method, and the like.
  • lithium cobalt oxide and lithium manganate which are lithium transition metal composite oxides
  • Japanese Patent No. 3067165, Japanese Patent No. 3274016, Japanese Patent No. 3012229, and Japanese Patent No. 3030764 Etc. can be produced with reference to the above.
  • cobalt dioxide CoO 2
  • lithium carbonate Li 2 CO 3
  • lithium manganate manganese oxide (Mn 3 O 4 ) and lithium nitrate (LiNO 3 ) are mixed so that the element ratio of lithium and manganese is 1.025: 2, and then used in a dry pulverizer or the like.
  • firing, cooling and mixing are performed at 264 ° C. for 24 hours in an air atmosphere
  • firing, cooling and mixing are performed at 450 ° C. for 24 hours
  • firing and cooling are performed at 650 ° C. for 24 hours. It can be obtained by grinding the fired product.
  • lithium iron phosphate which is a lithium transition metal phosphorus composite oxide having an olivine structure is not particularly limited, it can be produced with reference to Japanese Patent Nos. 4187523 and 4187524.
  • ferrous phosphate octahydrate Fe 3 (PO 4 ) 2 ⁇ 8H 2 O
  • lithium phosphate Li 3 PO 4
  • the element ratio between lithium and iron is The mixture is mixed at 1: 1, pulverized and mixed by a dry pulverizer or the like, then fired at 600 ° C. for several hours in an inert gas atmosphere, and the obtained fired product is pulverized.
  • the electrode is obtained by coating an electrode mixture composed of at least a positive electrode active material for a lithium secondary battery and a binder on a current collector. Furthermore, in order to improve the electroconductivity of an electrode, a conductive support agent can also be added in an electrode mixture. Incidentally, it is preferable to use an aluminum foil for the positive electrode as the current collector.
  • composition ratio of each component in the electrode mixture constituting the electrode is as follows.
  • the composition ratio of the positive electrode active material for a lithium secondary battery is desirably 70% by weight or more and 99.0% by weight or less, preferably 80% by weight or more and 95% by weight or less in the electrode mixture.
  • the composition ratio of the positive electrode active material for a lithium secondary battery is less than 70% by weight, it may be difficult to obtain sufficient conductivity and discharge capacity.
  • the composition ratio exceeds 98.5% by weight, the ratio of the binder is increased. Therefore, the adhesion to the current collector may be reduced, and the positive electrode active material for the lithium secondary battery may be easily detached.
  • the composition ratio of the binder is desirably 1 to 10% by weight, preferably 2 to 8% by weight in the electrode mixture.
  • the composition ratio of the binder is less than 1% by weight, the binding property is lowered, so that the positive electrode active material for the lithium secondary battery and the conductive assistant may be easily detached from the current collector.
  • it exceeds since the ratio of the positive electrode active material material for lithium secondary batteries will fall, it may lead to the fall of battery performance.
  • the composition ratio of the conductive auxiliary agent is desirably 0.5 to 25% by weight, preferably 1.0 to 15% by weight in the electrode mixture. If the composition ratio of the conductive assistant is less than 0.5% by weight, it may be difficult to obtain sufficient conductivity. If the composition ratio exceeds 25% by weight, the positive electrode for a lithium secondary battery that greatly contributes to battery performance. Since the ratio of the active material decreases, problems such as a decrease in discharge capacity per volume of the battery may occur.
  • binder used in the electrode mixture examples include acrylic resin, polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, acrylic resin, formaldehyde resin, silicon resin, fluorine
  • binder resin such as carboxymethyl cellulose, synthetic rubber such as styrene-butadiene rubber and fluorine rubber, and conductive resin such as polyaniline and polyacetylene.
  • the modified body, mixture, or copolymer of these resin may be sufficient.
  • examples thereof include a copolymer contained as a structural unit.
  • a polymer compound having a fluorine atom in the molecule such as polyvinylidene fluoride, polyvinyl fluoride, and polytetrafluoroethylene.
  • the weight average molecular weight of these resins as binders is preferably 10,000 to 1,000,000. When the molecular weight is small, the resistance of the binder may decrease. When the molecular weight is increased, the resistance of the binder is improved, but the viscosity of the binder itself is increased, the workability is lowered, and it acts as an aggregating agent.
  • a carbon material is most preferable.
  • the carbon material is not particularly limited as long as it is a conductive carbon material, but graphite, carbon black, carbon nanotube, carbon nanofiber, carbon fiber, fullerene, etc. alone or in combination of two or more. Can be used. From the viewpoint of conductivity, availability, and cost, it is preferable to use carbon black.
  • Carbon black is a furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially ketjen black using ethylene heavy oil as a raw material.
  • Channel black rapidly cooled and precipitated, thermal black obtained by periodically repeating combustion and thermal decomposition using gas as a raw material, and various types such as acetylene black using acetylene gas as a raw material alone, Or two or more types can be used together.
  • Ordinarily oxidized carbon black, hollow carbon and the like can also be used.
  • the oxidation treatment of carbon is performed by treating carbon at a high temperature in the air or by secondary treatment with nitric acid, nitrogen dioxide, ozone, etc., for example, such as phenol group, quinone group, carboxyl group, carbonyl group.
  • This is a treatment for directly introducing (covalently bonding) an oxygen-containing polar functional group to the carbon surface, and is generally performed to improve the dispersibility of carbon.
  • it since it is common for the conductivity of carbon to fall, so that the introduction amount of a functional group increases, it is preferable to use the carbon which has not been oxidized.
  • the specific surface area (BET) determined from the adsorption amount of nitrogen is 20 m 2 / g or more and 1500 m 2 / g or less, preferably 50 m 2 / g or more and 1500 m 2 / g or less, more preferably 100 m 2. / G or more and 1500 m 2 / g or less are desirable.
  • BET specific surface area
  • the particle size of the carbon black used is preferably 0.005 to 1 ⁇ m, particularly preferably 0.01 to 0.2 ⁇ m in terms of primary particle size.
  • the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.
  • Examples of commercially available carbon black include furnace blacks manufactured by Tokai Carbon Co., Ltd. such as Toka Black # 4300, # 4400, # 4500, and # 5500; furnace blacks manufactured by Degussa such as Printex L; Raven7000, 5750, 5250, 5000ULTRAIII Furnace Black made by Colombian, such as 5000 ULTRA, Conductex SC ULTRA, 975 ULTRA, PUER BLACK 100, 115, and 205; # 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B, and # 5400B Furnace Black manufactured by Mitsubishi Chemical Corporation; MONARCH1400, 1300, 900, VulcanXC-72R, and Black Furnace black manufactured by Cabot, such as earls 2000; Furnace black manufactured by TIMCAL, such as Ensaco 250G, Ensaco 260G, Ensaco 350G, and SuperP-Li; Ke
  • the method for producing the electrode is not particularly limited.For example, after preparing a mixture paste by dispersing and mixing a positive electrode active material for a lithium secondary battery, a conductive additive, and a binder in a solvent, It is produced by applying to a current collector such as an aluminum foil and drying.
  • a disperser usually used for pigment dispersion or the like can be used.
  • mixers such as disperser, homomixer, or planetary mixer; homogenizers such as “Clearmix” manufactured by M Technique, or “Fillmix” manufactured by PRIMIX; paint conditioner (manufactured by Red Devil), ball mill, sand mill (Shinmaru Enterprises "Dynomill”, etc.), Attritor, Pearl Mill (Eirich “DCP Mill”, etc.), or Coball Mill, etc .; Media type dispersers; Wet Jet Mill (Genus, “Genus PY”, Sugino Media-less dispersers such as “Starburst” manufactured by Machine, “Nanomizer” manufactured by Nanomizer, etc., “Claire SS-5” manufactured by M Technique, or “Micros” manufactured by Nara Machinery Co., Ltd .; or other roll mills Etc. , But it is not limited thereto. Further, as the disperser, it is preferable to use a disperser that has been subjected to a metal mixing prevention treatment from the disperser
  • a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating is preferably used.
  • ceramic beads such as glass beads, zirconia beads, or alumina beads.
  • a roll mill it is preferable to use a ceramic roll. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.
  • solvent used in preparing the mixture paste examples include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, and carboxylic acids.
  • examples include esters, phosphate esters, ethers, nitriles, and water.
  • N-methyl-2-pyrrolidone an amide solvent obtained by dialkylating nitrogen such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, and N, N-diethylacetamide , Hexamethylphosphoric triamide, and dimethyl sulfoxide, but are not limited thereto. Two or more types can be used in combination.
  • Lithium secondary battery provided with an electrode using a positive electrode active material for a lithium secondary battery as a positive electrode will be described.
  • the lithium secondary battery includes a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium.
  • An electrode base layer may be formed between the positive electrode mixture layer and the current collector or between the negative electrode mixture layer and the current collector.
  • the material and shape of the current collector to be used are not particularly limited, and as the material, a metal or an alloy such as aluminum, copper, nickel, titanium, or stainless steel is used. Copper is preferred as the negative electrode material.
  • a flat plate foil is generally used, but a roughened surface, a perforated foil shape, and a mesh shape can also be used.
  • Examples of the method for forming the electrode base layer on the current collector include a method in which an electrode base paste in which carbon black as a conductive material and a binder component are dispersed in a solvent is applied to the electrode current collector and dried.
  • the film thickness of the electrode underlayer is not particularly limited as long as the conductivity and adhesion are maintained, but is generally 0.05 ⁇ m or more and 20 ⁇ m or less, preferably 0.1 ⁇ m or more and 10 ⁇ m or less. It is.
  • an electrode mixture layer on a current collector As a method of forming an electrode mixture layer on a current collector, a method of directly applying and drying the above-mentioned mixture paste on the current collector, and a mixture paste after forming an electrode base layer on the current collector The method of apply
  • coating and drying is mentioned.
  • the mixture paste When the electrode mixture layer is formed on the electrode underlayer, after applying the electrode undercoat paste on the current collector, the mixture paste may be applied in a wet state and dried. .
  • the thickness of the electrode mixture layer is generally 1 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 300 ⁇ m or less.
  • the coating method is not particularly limited, and a known method can be used. Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method. Moreover, you may perform the rolling process by a lithographic press, a calendar roll, etc. after application
  • an electrolyte containing lithium is dissolved in a non-aqueous solvent.
  • a non-aqueous solvent LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C , LiI, LiBr, LiCl, LiAlCl , LiHF 2, LiSCN, or LiBPh 4 etc. but are not limited to.
  • the non-aqueous solvent is not particularly limited.
  • carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate; ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ - Lactones such as octanoic lactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1,2 -Grimes such as dibutoxyethane; esters such as methyl formate, methyl acetate and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile. And the like.
  • These solvents may be used alone or in combination of two or more.
  • the above electrolyte solution can be held in a polymer matrix to form a gel polymer electrolyte.
  • the polymer matrix include, but are not limited to, an acrylate resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, and a polysiloxane having a polyalkylene oxide segment.
  • the structure of the lithium secondary battery is not particularly limited, but is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary, depending on the purpose of use, such as paper type, cylindrical type, button type, laminated type, etc. Various shapes can be used.
  • part means “part by weight”
  • % means “% by weight”.
  • the following measuring apparatus was used for the analysis of the positive electrode active material for a lithium secondary battery.
  • -XRD X-ray diffraction
  • X'Pert PRO MPD made by PANalytical SEM (scanning electron microscope): SEM S-4300 manufactured by Hitachi, Ltd.
  • -CHN elemental analysis Model 2400 CHN elemental analysis manufactured by PerkinElmer
  • Example 1 lithium cobalt composite oxide
  • Cobalt oxide (CoO 2 ), lithium carbonate (Li 2 CO 3 ), and natural wax Carnauba No. 2 manufactured by Toyo Adri Co., Ltd.
  • an element ratio of cobalt to lithium being 1: 1, natural in the raw material mixture
  • the fired product was pulverized in a mortar to obtain a positive electrode active material (1) for a lithium secondary battery, which was a lithium cobalt composite oxide.
  • the obtained lithium cobalt composite oxide was identified as LiCoO 2 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 3.0 to 5.0 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 0.2% from CHN elemental analysis.
  • Example 2 lithium manganese composite oxide
  • Manganese oxide (Mn 3 O 4 ), lithium nitrate (LiNO 3 ), and ester gum HD which is a modified natural resin, have an element ratio of manganese to lithium of 2: 1 in the raw material mixture Weighed so that the modified natural resin content is 2.0%, pulverized and mixed in a mortar, filled in an alumina crucible, fired in an electric furnace at 300 ° C. for 24 hours in an air atmosphere, and cooled. After performing, it mixes with a mortar, baked at 700 degreeC for 30 hours, The obtained baked material is grind
  • the obtained lithium manganese composite oxide was identified as LiMn 2 O 3 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 1.0 to 3.0 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 0.15% from CHN elemental analysis.
  • Example 3 Lithium iron phosphorus composite oxide
  • Example 3 of basic patent Distilling 13.44 parts of iron chloride tetrahydrate (FeCl 2 .4H 2 O), 2.87 parts of lithium chloride (LiCl), 6.63 parts of phosphoric acid (H 3 PO 4 ), and 12.30 parts of urea
  • a raw material aqueous solution was prepared by dissolving in 100 parts of water. After this raw material aqueous solution was charged in a pressure vessel, it was heated in an electric furnace at 300 ° C. for 5 hours, cooled to room temperature, and then a lithium iron phosphorus composite oxide was produced by filtration, washing with water and drying.
  • the obtained lithium iron phosphorus composite oxide and vegetable oil soybean oil KT (manufactured by Marusho Co., Ltd.) are mixed in a mortar so that the weight ratio of the lithium iron phosphorus composite oxide and vegetable oil is 1: 0.5. And calcination at 600 ° C. for 10 hours in a nitrogen atmosphere in an electric furnace.
  • the obtained fired product is pulverized in a mortar and is a lithium iron phosphorus composite oxide positive electrode active material for lithium secondary battery (3) Got.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.8 to 1.5 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 5.5% from CHN elemental analysis.
  • Example 4 lithium iron phosphorus composite oxide
  • FeCl 2 .4H 2 O Iron chloride tetrahydrate
  • LiCl lithium chloride
  • H 3 PO 4 phosphoric acid
  • 12.30 parts of urea A raw material aqueous solution was prepared by dissolving in 100 parts of water. After this raw material aqueous solution was charged in a pressure vessel, it was heated in an electric furnace at 300 ° C. for 5 hours, cooled to room temperature, and then a lithium iron phosphorus composite oxide was produced by filtration, washing with water and drying.
  • the obtained lithium iron phosphorus composite oxide and vegetable oil soybean oil KT (manufactured by Marusho) were mixed in a mortar so that the weight ratio of lithium iron phosphorus composite oxide and vegetable oil was 1: 0.15. And calcination at 600 ° C. for 10 hours in a nitrogen atmosphere in an electric furnace, and the fired product obtained is pulverized in a mortar and is a lithium iron phosphorus composite oxide positive electrode active material for a lithium secondary battery (4) Got.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.4 to 1.0 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 5.0% from CHN elemental analysis.
  • Example 5 Lithium iron phosphorus composite oxide
  • a raw material aqueous solution was prepared by dissolving in 100 parts of water. After this raw material aqueous solution was charged in a pressure vessel, it was heated in an electric furnace at 300 ° C. for 5 hours, cooled to room temperature, and then a lithium iron phosphorus composite oxide was produced by filtration, washing with water and drying.
  • the obtained lithium iron phosphorus composite oxide and natural resin GSN (manufactured by Gifu Shellac Manufacturing Co., Ltd.) are mortar so that the weight ratio of lithium iron phosphorus composite oxide and natural resin is 1: 0.2. , Baked at 700 ° C. for 10 hours in a nitrogen atmosphere in an electric furnace, and the fired product obtained was pulverized in a mortar to be a lithium iron phosphorus composite oxide positive electrode active material for a lithium secondary battery (5) was obtained.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.8 to 1.5 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 4.7% from CHN elemental analysis.
  • Example 6 Lithium iron phosphorus composite oxide
  • a raw material aqueous solution was prepared by dissolving in 100 parts of water. After this raw material aqueous solution was charged in a pressure vessel, it was heated in an electric furnace at 300 ° C. for 5 hours, cooled to room temperature, and then a lithium iron phosphorus composite oxide was produced by filtration, washing with water and drying.
  • the obtained lithium iron phosphorus composite oxide and the natural wax rice wax decolorized product (manufactured by Toa Kasei Co., Ltd.) are so prepared that the weight ratio of the lithium iron phosphorus composite oxide and the natural wax is 1: 0.15.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.8 to 1.5 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 3.0% from CHN elemental analysis.
  • Example 7 Lithium iron phosphorus composite oxide
  • Ferrous phosphate octahydrate (Fe 3 (PO 4 ) 2 ⁇ 8H 2 O), lithium phosphate (Li 3 PO 4 ), and modified natural wax LUWAX-S manufactured by BASF
  • the element ratio of iron and lithium is 1: 1, and the natural wax content in the raw material mixture is weighed to 10.0%, pulverized and mixed in a mortar, then filled into an alumina crucible, and placed in an electric furnace. After baking and cooling at 300 ° C. for 10 hours in a nitrogen atmosphere, mixing in a mortar, baking at 700 ° C. for 15 hours, pulverizing the obtained fired product in a mortar and lithium iron phosphorus composite oxidation As a result, a positive electrode active material (7) for a lithium secondary battery was obtained.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.07 to 0.2 ⁇ m (FIG. 1; 30000 times) from SEM (scanning electron microscope) observation, and the carbon content was 4.5% from CHN elemental analysis.
  • Example 8 Lithium iron phosphorus composite oxide
  • Ferrous phosphate octahydrate (Fe 3 (PO 4 ) 2 ⁇ 8H 2 O), lithium phosphate (Li 3 PO 4 ), and modified natural wax LUWAX-S manufactured by BASF
  • the element ratio of iron and lithium is 1: 1, and the content of the modified natural wax in the raw material mixture is weighed to be 5.0%, pulverized and mixed in a mortar, then filled into an alumina crucible, and an electric furnace After baking and cooling at 300 ° C. for 10 hours in a nitrogen atmosphere, mixing in a mortar, baking at 700 ° C. for 15 hours, and pulverizing the obtained fired product in a mortar and lithium iron phosphorus composite A positive electrode active material (8) for a lithium secondary battery, which was an oxide, was obtained.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.1 to 1.0 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 4.0% from CHN elemental analysis.
  • Example 9 Lithium iron phosphorus composite oxide
  • the element ratio of iron, phosphorus and lithium is 1: 1: 1, and the content of vegetable oil in the raw material mixture is 40.0%.
  • the alumina crucible Baked at 300 ° C. for 10 hours in an electric furnace in a nitrogen atmosphere, cooled, then mixed in a mortar, baked at 700 ° C. for 15 hours, and the resulting fired product in a mortar
  • the positive electrode active material (9) for lithium secondary batteries which is a pulverized lithium iron phosphorus composite oxide was obtained.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.2 to 0.5 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 6.4% from CHN elemental analysis.
  • Example 10 Lithium iron phosphorus composite oxide
  • the element ratio of iron, phosphorus and lithium is 1: 1: 1, and the content of vegetable oil in the raw material mixture is 20.0%.
  • the alumina crucible Baked at 300 ° C. for 10 hours in an electric furnace in a nitrogen atmosphere, cooled, then mixed in a mortar, baked at 700 ° C. for 15 hours, and the resulting fired product in a mortar
  • the positive electrode active material (10) for lithium secondary batteries which is a pulverized lithium iron phosphorus composite oxide was obtained.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.2 to 0.5 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 5.8% from CHN elemental analysis.
  • Example 11 Lithium iron phosphorus composite oxide
  • Iron phosphate dihydrate (FePO 4 .2H 2 O), lithium acetate (CH 3 COOLi), and natural resin tall rosin RX have an iron to lithium element ratio of 1: 1, the content of the natural resin in the raw material mixture was weighed so as to be 30.0%, pulverized and mixed in a mortar, filled in an alumina crucible, and 10% at 300 ° C. in a nitrogen atmosphere in an electric furnace. After time firing and cooling, mixing in a mortar, firing at 700 ° C. for 15 hours, and pulverizing the obtained fired product in a mortar to form a lithium iron phosphorus composite oxide positive electrode for a lithium secondary battery An active material (11) was obtained.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle size was 0.1 to 0.5 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 5.0% from CHN elemental analysis.
  • Example 12 Lithium iron phosphorus composite oxide
  • Iron phosphate dihydrate (FePO 4 .2H 2 O), lithium acetate (CH 3 COOLi), and natural resin tall rosin RX have an iron to lithium element ratio of 1: 1, the content of the natural resin in the raw material mixture was weighed so as to be 15.0%, pulverized and mixed in a mortar, filled in an alumina crucible, and 10% at 300 ° C. in a nitrogen atmosphere in an electric furnace. After time firing and cooling, mixing in a mortar, firing at 700 ° C. for 15 hours, and pulverizing the obtained fired product in a mortar to form a lithium iron phosphorus composite oxide positive electrode for a lithium secondary battery An active material (12) was obtained.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.1 to 0.6 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 4.3% from CHN elemental analysis.
  • Example 13 Lithium iron phosphorus composite oxide
  • ⁇ -FePO 4 iron phosphate anhydrate
  • Li 2 CO 3 lithium carbonate
  • Chinese rosin X manufactured by Arakawa Chemical Industries
  • the content of the natural resin in the raw material mixture would be 10.0%, pulverized and mixed in a mortar, filled in an alumina crucible, and then in an electric furnace under nitrogen atmosphere at 700 ° C. for 15 hours. Firing was performed, and the obtained fired product was pulverized in a mortar to obtain a positive electrode active material (13) for a lithium secondary battery, which is a lithium iron phosphorus composite oxide.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement. Further, the primary particle diameter is 0.05 to 0.2 ⁇ m (FIG. 2; 20000 times, FIG. 3; 50000 times) from SEM (scanning electron microscope) observation, and the carbon content is 4. It was 8%.
  • Example 14 Lithium iron phosphorus composite oxide
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.1 to 0.3 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 3.2% from CHN elemental analysis.
  • Example 15 Lithium iron phosphorus composite oxide
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement. Further, the primary particle diameter is 0.05 to 0.3 ⁇ m (FIG. 4; 20000 times, FIG. 5; 50000 times) from SEM (scanning electron microscope) observation, and the carbon content is 3. It was 5%.
  • Example 16 Lithium iron phosphorus composite oxide
  • the raw material mixture is weighed so that the content of the natural resin is 5.0%, pulverized and mixed in a mortar, then filled into an alumina crucible, and 300 ° C. in a nitrogen atmosphere in an electric furnace. After baking for 10 hours and cooling, mixing in a mortar, baking at 700 ° C. for 15 hours, pulverizing the obtained fired product in a mortar and lithium lithium phosphorus composite oxide lithium secondary battery A positive electrode active material (16) was obtained.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.05 to 0.4 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 2.0% from CHN elemental analysis.
  • Example 17 lithium iron phosphorus composite oxide
  • the ratio is 1: 1, the modified natural resin content in the raw material mixture is weighed to 7.0%, pulverized and mixed in a mortar, then filled into an alumina crucible, and in an electric furnace under a nitrogen atmosphere After baking and cooling at 300 ° C. for 10 hours, mixing in a mortar, baking at 700 ° C. for 15 hours, and pulverizing the obtained fired product in a mortar to obtain lithium iron phosphorus composite oxide lithium
  • a positive electrode active material (17) for secondary batteries was obtained.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.05 to 0.3 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 3.5% from CHN elemental analysis.
  • Example 18 Lithium manganese phosphorus composite oxide
  • the element ratio of lithium is 1: 1: 1, and the natural wax content in the raw material mixture is weighed so as to be 40.0%, pulverized and mixed in a mortar, then filled into an alumina crucible, and placed in an electric furnace. Then, after baking and cooling at 400 ° C. for 15 hours in a nitrogen atmosphere, mixing in a mortar, baking at 800 ° C. for 20 hours, and pulverizing the obtained fired product in a mortar and lithium manganese phosphorus composite oxidation As a result, a positive electrode active material (18) for a lithium secondary battery was obtained.
  • the obtained lithium manganese phosphorus composite oxide was identified as LiMnPO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.8 to 1.5 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 6.8% from CHN elemental analysis.
  • Example 19 lithium manganese phosphorus composite oxide
  • the element ratio of lithium is 1: 1: 1, and the natural wax content in the raw material mixture is weighed to 20.0%, pulverized and mixed in a mortar, then filled into an alumina crucible, and placed in an electric furnace. Then, after baking and cooling at 400 ° C. for 15 hours in a nitrogen atmosphere, mixing in a mortar, baking at 800 ° C. for 20 hours, and pulverizing the obtained fired product in a mortar and lithium manganese phosphorus composite oxidation As a result, a positive electrode active material (19) for a lithium secondary battery was obtained.
  • the obtained lithium manganese phosphorus composite oxide was identified as LiMnPO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 0.5 to 1.2 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 4.5% from CHN elemental analysis.
  • Example 20 Lithium manganese phosphorus composite oxide
  • Harimac T-80 manufactured by Harima Chemical Co., Ltd.
  • the element ratio of phosphorus and lithium is 1: 1: 1, and the natural resin content in the raw material mixture is weighed to be 40.0%, pulverized and mixed in a mortar, then filled into an alumina crucible, After firing and cooling at 400 ° C. for 15 hours in a nitrogen atmosphere in a furnace, mixing in a mortar, firing at 800 ° C. for 20 hours, and pulverizing the obtained fired product in a mortar to obtain lithium manganese phosphorus
  • the obtained lithium manganese phosphorus composite oxide was identified as LiMnPO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle size was 1.0 to 1.5 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 7.5% from CHN elemental analysis.
  • Example 21 lithium manganese phosphorus composite oxide
  • Harimac T-80 manufactured by Harima Chemical Co., Ltd.
  • the element ratio of phosphorus and lithium is 1: 1: 1, and weighed so that the content of the modified natural resin in the raw material mixture is 20.0%, pulverized and mixed in a mortar, and then filled into an alumina crucible, After firing and cooling at 400 ° C. for 15 hours in a nitrogen atmosphere in an electric furnace, mixing in a mortar, firing at 800 ° C. for 20 hours, and pulverizing the obtained fired product in a mortar, lithium manganese A positive electrode active material (21) for a lithium secondary battery, which was a phosphorus composite oxide, was obtained.
  • the obtained lithium manganese phosphorus composite oxide was identified as LiMnPO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 1.2 to 1.8 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 5.8% from CHN elemental analysis.
  • the obtained lithium cobalt composite oxide was identified as LiCoO 2 by XRD (X-ray diffraction) measurement.
  • the primary particle diameter was 1.0 to 8.0 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 0.3% from CHN elemental analysis.
  • the obtained lithium manganese composite oxide was identified as LiMn 2 O 3 by XRD (X-ray diffraction) measurement.
  • the primary particle size was 0.8 to 6.0 ⁇ m from SEM (scanning electron microscope) observation, and the carbon content was 0.25% from CHN elemental analysis.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement. Further, from SEM (scanning electron microscope) observation, the primary particle diameter was 0.05 to 1.0 ⁇ m (FIG. 6; 30000 times), and many large aggregated particles were confirmed by the fusion of the particles. Furthermore, the carbon content was 5.8% from CHN elemental analysis.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle size is 0.05 to 2.0 ⁇ m (FIG. 7; 20000 times, FIG. 8; 50000 times), and the particle size varies greatly. Many were confirmed.
  • the carbon content was as low as 1.8% by CHN elemental analysis.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle size was 0.1 to 0.4 ⁇ m and the variation in the particle size was small, but from CHN elemental analysis, the carbon content was 0.5%. Very few.
  • the obtained lithium iron phosphorus composite oxide was identified as LiFePO 4 by XRD (X-ray diffraction) measurement.
  • XRD X-ray diffraction
  • SEM scanning electron microscope
  • the obtained lithium manganese phosphorus composite oxide was identified as LiMnPO 4 by XRD (X-ray diffraction) measurement.
  • the primary particle size was 0.2-2.0 ⁇ m as observed by SEM (scanning electron microscope), and the particle size variation was large, and the carbon content was as low as 2.2% by CHN elemental analysis. .
  • NMP N-methyl-2-pyrrolidone
  • PVDF polyvinylidene fluoride (KF polymer W # 1100, manufactured by Kureha)
  • a separator made of a porous polypropylene film between the working electrode and the counter electrode (# 2400, manufactured by Celgard Co., Ltd.) with the positive electrode fabricated previously punched out to a diameter of 9 mm and used as a working electrode and a metal lithium foil (thickness 0.15 mm) as a counter electrode Are inserted and laminated, filled with an electrolyte (nonaqueous electrolyte in which LiPF 6 is dissolved at a concentration of 1 M in a mixed solvent of ethylene carbonate and diethyl carbonate in a ratio of 1: 1), and a bipolar metal cell (Hosen) (HS flat cell).
  • the cell was assembled in a glow box substituted with argon gas, and after the cell was assembled, predetermined battery characteristics were evaluated.
  • the particle diameter of the positive electrode active material is uniform in a narrow range, so that the packing density of the positive electrode active material in the electrode coating film is higher than in the comparative example, The conductivity in the electrode coating was improved, and the initial discharge capacity at 0.2C was improved. Also, in the high rate discharge capacity maintenance rate, the positive electrode active material of the example tended to be higher than the comparative example.

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PCT/JP2010/067647 2009-10-09 2010-10-07 リチウム二次電池用正極活物質材料、その製造方法、及びそれを用いたリチウム二次電池 WO2011043419A1 (ja)

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CN104167550A (zh) * 2014-07-28 2014-11-26 北京万源工业有限公司 一种纳米实心磷酸铁-碳源-石墨烯复合材料及制备方法
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KR101475922B1 (ko) * 2012-12-27 2014-12-23 전자부품연구원 망간 인산화물이 코팅된 리튬 이차전지용 양극 활물질 및 그의 제조 방법
US11302919B2 (en) 2016-07-20 2022-04-12 Samsung Sdi Co., Ltd. Nickel-based active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive electrode including the nickel-based active material
US11569503B2 (en) 2016-07-20 2023-01-31 Samsung Sdi Co., Ltd. Nickel-based active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive electrode including the nickel-based active material
CN108183233B (zh) * 2016-12-08 2021-09-03 三星Sdi株式会社 用于锂二次电池的基于镍的活性材料、其制备方法和包括含其的正极的锂二次电池
US11456458B2 (en) 2016-12-08 2022-09-27 Samsung Sdi Co., Ltd. Nickel-based active material precursor for lithium secondary battery, preparing method thereof, nickel-based active material for lithium secondary battery formed thereof, and lithium secondary battery comprising positive electrode including the nickel-based active material
CN106784735A (zh) * 2017-02-06 2017-05-31 安徽鹰龙工业设计有限公司 一种锂电池用复合正极材料及其制备方法
TW202036966A (zh) * 2019-03-22 2020-10-01 宏總科技股份有限公司 二次電池正極材料製備方法
CN115172718A (zh) * 2022-08-01 2022-10-11 湖北万润新能源科技股份有限公司 一种固相包覆法制备磷酸锰铁锂的方法

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