CN101481106A - 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法 - Google Patents

含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法 Download PDF

Info

Publication number
CN101481106A
CN101481106A CNA2009100954019A CN200910095401A CN101481106A CN 101481106 A CN101481106 A CN 101481106A CN A2009100954019 A CNA2009100954019 A CN A2009100954019A CN 200910095401 A CN200910095401 A CN 200910095401A CN 101481106 A CN101481106 A CN 101481106A
Authority
CN
China
Prior art keywords
oxygen
phosphate
sintering method
solid phase
phase sintering
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2009100954019A
Other languages
English (en)
Inventor
金江剑
王国光
徐君
包大新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hengdian Group DMEGC Magnetics Co Ltd
Original Assignee
Hengdian Group DMEGC Magnetics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hengdian Group DMEGC Magnetics Co Ltd filed Critical Hengdian Group DMEGC Magnetics Co Ltd
Priority to CNA2009100954019A priority Critical patent/CN101481106A/zh
Publication of CN101481106A publication Critical patent/CN101481106A/zh
Priority to US12/622,397 priority patent/US8241521B2/en
Priority to EP10150049A priority patent/EP2207229B1/en
Priority to ES10150049T priority patent/ES2371050T3/es
Priority to CN2010103000236A priority patent/CN101764226B/zh
Priority to AT10150049T priority patent/ATE529907T1/de
Pending legal-status Critical Current

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/26Phosphates
    • C01B25/45Phosphates containing plural metal, or metal and ammonium
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • C04B35/6261Milling
    • C04B35/6262Milling of calcined, sintered clinker or ceramics
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • C04B35/62645Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/636Polysaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201Alkali metal oxides or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203Lithium oxide or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206Magnesium oxides or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3289Noble metal oxides
    • C04B2235/3291Silver oxides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422Carbon
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444Halide containing anions, e.g. bromide, iodate, chlorite
    • C04B2235/445Fluoride containing anions, e.g. fluosilicate
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5463Particle size distributions
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602Making the green bodies or pre-forms by moulding
    • C04B2235/6021Extrusion moulding
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562Heating rate
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567Treatment time
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658Atmosphere during thermal treatment
    • C04B2235/6582Hydrogen containing atmosphere
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658Atmosphere during thermal treatment
    • C04B2235/6586Processes characterised by the flow of gas
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/667Sintering using wave energy, e.g. microwave sintering
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明涉及一种含氧空位和Fe位掺杂型锂离子正极材料磷酸铁锂及其快速微波烧结制备方法。本发明提供一种生产效率高、能耗低、所制备的产物具有优良的极片加工性能、导电性能和电化学性能的一种含氧空位和Fe位掺杂型磷酸铁锂的快速固相微波烧结方法。本发明产物分子式为LiFe1-x-aMeaMxPO4-yNz,其中Me为Mg、Mn或者Nd中的一种或一种以上,M为Li、Na、K、Ag、Cu中的一种或一种以上;0≤x≤0.1,0≤a≤0.1,0<y≤0.5,0≤z≤0.5,其中x、y、z不能同时为0。

Description

含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法
技术领域
本发明涉及一种锂离子电池材料及制备方法,尤其涉及一种含氧空位和Fe位掺杂型锂离子正极材料磷酸铁锂及其快速微波烧结制备方法。
背景技术
近年来,锂离子电池发展十分迅速,各种便携式电子产品和通讯工具对锂离子电池的需求量不断增加,大型动力锂离子电源也在发展热潮中。正极材料是锂离子电池的重要组成部分,新型正极材料的研制已成为决定锂离子电池发展的关键。目前大规模商品化的LiCoO2,毒性较大,价格昂贵,存在一定的安全问题。LiNiO2成本较低,容量较高,但制备困难,热稳定性差,存在较大的安全隐患。尖晶石LiMn2O4成本低,安全性好,但容量低,高温循环性能差。因此需要开发新型价格低廉性能优良的正极材料以满足日益增长的市场需求。而作为新型锂离子电池正极材料的正交晶系橄榄石型LiFePO4具有容量高,充放电电压平稳特别是其价格低廉,安全性好,热稳定性好,对环境无污染等更使它成为最有潜力的正极材料之一。
LiFePO4在自然界中以磷铁锂矿的形式存在,具有有序的橄榄石结构,属于正交晶系(D162h,Pmnb)。在每个晶胞中有4个LiFePO4单元其晶胞参数为a=6.0089
Figure A200910095401D0004132618QIETU
,b=10.334
Figure A200910095401D0004132618QIETU
和c=4.693
Figure A200910095401D0004132618QIETU
[3]。在LiFePO4中,氧原子近似呈六方紧密堆积,磷原子在四面体的空隙,铁原子、锂原子分别在八面体的空隙。在晶体b-c平面上FeO6八面体共点连结。一个FeO6八面体与两个LiO6八面体共边,而一个PO4四面体则与一个FeO6八面体和两个LiO6八面体共边。且Li+具有二维可移动性,在充放电过程中可以脱出和嵌入。强的P—O共价键形成离域的三维立体化学键,使LiFePO4具有很强的热力学和动力学稳定性。纯LiFePO4存在的主要问题是离子扩散系数和电子传导率均较低。针对这种情况,本发明通过进入Fe位掺杂和引入氧空位来提高磷酸铁锂的电导率和离子扩散系数。
影响磷酸铁锂商品化的两个重要因素是价格和批量稳定性问题,这两个问题目前并没有引起人们的足够重视。当前合成磷酸铁锂的主要方法有高温固相反应法,液相共沉积法,水热法,液相氧化还原法,固相微波烧结法和机械球磨法等。目前广泛采用的高温固相反应法是采用亚铁盐作为铁源,再与锂源及磷源混合,然后在惰性气氛中烧结合成磷酸铁锂。二价铁源价格较贵,而且由于需要防止二价铁源氧化,制备工艺复杂,产物纯度不易控制,从而使成本增加,并且一般烧结时间都在6小时以上。本发明提出使用三价铁源为原料,在烧结过程中采用快速微波固相烧结法,可以大大缩短材料的制备时间,并且生产的产品综合性能高,特别是振实密度较高。
发明内容
本发明针对现有技术在所存在的能耗高、烧结时间长、作为电极时性能低等问题,提供一种生产效率高、能耗低、所制备的产物具有优良的极片加工性能、导电性能和电化学性能的一种含氧空位和Fe位掺杂型磷酸铁锂的快速固相微波烧结方法。
本发明的目的是通过以下技术方案得以实施的:
本发明含氧空位和Fe位掺杂型磷酸铁锂,其分子式为LiFe1-x-aMeaMxPO4-yNz,其中Me为Mg、Mn或者Nd中的一种或一种以上,M为Li、Na、K、Ag、Cu中的一种或一种以上;0≤x≤0.1,0≤a≤0.1,0<y≤0.5,0≤z≤0.5,其中x、y、z不能同时为0。
磷酸铁锂快速微波固相烧结方法步骤如下:
1、配料:将锂化合物,Fe3+化合物,磷酸盐,掺杂物和导电用碳源按比例混合,其中Li:Fe:Me:M:P摩尔比为1:(1-x):a:x:1。碳源的加入量为混合物总质量的5~20%,优选为10%~15%,碳源的加入可以在高温下与混合物实现分子级的混合,最终以非晶态碳的形态均匀的包覆在磷酸铁锂颗粒周围,增加材料的导电性能,以使材料发挥良好的容量并可提高材料的高倍率放电性能和循环性能。碳源添加量太少可能导致材料导电性能不好,碳源过多可能会使材料振实密度减小且涂覆性能降低,优选10%~15%碳源时,可以获得良好的综合性能。
2、混料。设备采用搅拌机或砂磨机,溶剂可使用去离子水、自来水或酒精、煤油等有机溶剂,混合时间为1~10小时,其中优选时间为1~3小时,混合后的浆料用烘箱烘干或者用喷雾造粒设备烘干,烘干温度采用烘箱时为40~120℃,优选90~110℃,采用喷雾造粒设备时为120~260℃,优选170~220℃。
3、混料烘干后进行压块,压块是使用压力机或者挤压机将上述混合物压制成块状或蜂窝煤状或条状,或者不压块,将上述混合物放入微波反应炉,在流速为0.01~50升/分钟的高纯Ar气和/或H2气混合气保护下加热处理,其中H2气体体积占总气体体积的6~10%。升温速率为40~80℃/分钟,升温至700~800℃,热处理时间为20~60分钟,然后降温到室温。选用的加热处理设备为工业用功率为1.5~5KW的微波烧结炉。
4、粉碎处理,采用二次球磨或气流磨等方法,得到颗粒分布均匀的磷酸铁锂。其中含碳量为1~8wt%。
作为优选,所述锂化合物为碳酸锂,草酸锂,醋酸锂,单水氢氧化锂,磷酸二氢锂中的一种或者一种以上。
作为优选,所述Fe3+化合物为铁红、磷酸铁中的一种或一种以上;铁红主成分为三氧化二铁。
作为优选,所述磷酸盐为磷酸、磷酸氢二铵、磷酸二氢铵、磷酸三铵、磷酸二氢锂中的一种或一种以上。
作为优选,所述碳源为碳黑、乙炔黑、蔗糖、淀粉、葡萄糖、活性炭、聚乙烯醇中的一种或一种以上。
作为优选,所述的混合时加入的溶剂为去离子水或自来水或酒精或煤油。
在半导体中引入氧空位,将导致材料中电子电导的增强,呈现n型电导。在磷酸铁锂中,锂离子的扩散是在磷酸根四面体组成的通道中扩散的,受到0的相互作用的影响。当存在氧空位时,锂离子受到的库仑力减少,从而提高锂离子的扩散系数。由于本发明的正极材料中含氧空位,材料的电子电导率和离子电导率可以显著提高,在电池中作为正极材料应用时,相比现有的体系,其高倍率性能更加优越。在Fe位中掺杂引入金属离子后,可以在不改变材料的橄榄石结构,保持了稳定的循环性能的前提下,大大提高了磷酸铁锂的电导率,改善了材料的高倍率性能。而且本发明使用价格低廉的三价铁源并且采用一步快速微波固相烧结法制备导电性能优异的磷酸铁锂
本发明材料与现有技术相比具有以下优点:
(1)避开了其它合成方法中繁琐的亚铁盐合成步骤,解决了亚铁盐容易氧化导致产物不纯的问题。
(2)使用添加剂将三价铁还原为二价,刚生成的二价铁活性好,与锂源及磷源的反应速度快,结合稳定,生成磷酸铁锂的纯度高,所制备的产物具有优良的极片加工性能、导电性能和电化学性能。
(3)采用微波固相烧结法,将反应所需时间从传统的6~30小时降低到20~60分钟,可以大大提高材料的生产效率,节药能耗。
本发明涉及的正极材料具有广泛的用途,采用该正极材料制备的锂离子电池安全性能好,成本低,可用于电动自行车、电动摩托车、电动汽车、矿灯、滑板车、笔记本电脑、电动工具以及一些非常规的可移动电源等领域。
附图说明
图1是按实施例1所制备的模拟钮扣电池在不同充放电倍率下放电曲线,电压范围为2.0~4.2V,充放电倍率分别为0.1C,0.5C,3C,5C,8C,测试温度为30℃±1℃。
图2是按实施例2所制备的17500圆柱型锂离子电池的循环性能图,电压范围为2.5~4.2V,充放电倍率为0.5C,温度温度为30℃±1℃。
具体实施方式
以下为本发明的具体实施方式,对本发明的技术特征做进一步的说明,但是本发明并不限于这些实施例。
实施例1:制备本发明的磷酸铁锂正极材料LiFe0.8Mg0.1Na0.1PO3.95
首先,按照摩尔比1:0.8:0.1:0.1:1称取单水氢氧化锂,氧化铁,氢氧化镁,氟化钠和磷酸二氢铵,并加入混合料质量比12%的葡萄糖,放入砂磨机中,球料水比例为2:1:1,混合3.5小时。将混合后的浆料用烘箱烘干,然后使用连续式挤压机制成块状,并放入微波反应炉,在10升/分钟的高纯Ar气和氢气混合气,保护下,其中氢气体积比为8%,以50℃/分的速率升温到750℃,保温45分钟,然后降温至室温。将烧结后的材料用破碎机破碎后,在气流磨上分级处理,得到颗粒均匀的磷酸铁锂。
测得材料中含碳量为5.6%。
测得材料的振实密度为1.4g/cm3。测得活性材料的粒度及分布如图1所示。制备材料在激光粒度分布仪上测试,测得的磷酸铁锂颗粒均匀细小,平均粒径1.12微米,D10为0.43微米,D90为2.92微米,粒度分布呈正态。
以82:8:10的质量比分别称取实施例1所得的正极材料:乙炔黑:PVDF,研磨均匀后制成电极,负极选用金属锂片,电解液为溶解在碳酸乙酯和碳酸二乙醋混合溶剂中的1.0mol/l的LiPF6,碳酸乙酯和碳酸二乙醋体积比1:1,隔膜为聚丙烯微孔薄膜,组装成电池。
图1为不同充放电倍率下的放电曲线,在0.1C放电时,材料可逆克容量可达160mAh/g,0.5C放电时可逆克容量为153mAh/g,3C放电时可逆克容量为134mAh/g,5C放电时可逆克容量为120mAh/g,8C放电时克容量为110mAh/g。材料克容量高,放电平台稳定,性能优越。
实施例2、制备本发明的含氧空位的磷酸铁锂材料LiFePO3.94N0.04
含氧空位的磷酸铁锂材料LiFePO3.94N0.04可以通过以下步骤制备。首先,分别称取30.0千克磷酸锂,62.2千克三氧化二铁,68.7千克磷酸氢二铵,803克Li3N和24.0千克蔗糖及12.0千克葡萄糖混合,放入混料机中,加酒精50升,加入玛瑙球200公斤,混合2小时。然后再用超细磨混合1小时,将混合后的浆料用喷雾造粒机烘干,温度控制在120-180℃左右。然后将粉料装入坩锅中,并放入功率为4KW的连续式工业用微波反应炉,在10升/分钟的氮气气氛下,以40℃/分的速率升温到750℃,保温30分钟,然后降温至室温。将烧结后的材料用破碎机破碎后,在气流磨上分级处理,得到颗粒均匀的磷酸铁锂。
将所得材料送锂离子电池厂制备成电极片并组装成17500圆柱电池,在0.5C的充放电倍率下,测得材料的循环性能如图2所示。
实施例3:
制备本发明的含氧空位的磷酸铁锂材料LiFe0.98Mn0.02PO3.97N0.02首先,按照摩尔比0.94:0.49:0.013:1:0.02称取单水氢氧化锂,氧化铁,四氧化三锰,磷酸二氢铵和氮化锂,并加入混合料质量比10%的葡萄糖,放入砂磨机中,球料水比例为2:1:1,混合3小时。将混合后的浆料用喷雾干燥塔喷雾干燥,放入微波反应炉,在10升/分钟的高纯Ar气和氢气混合气,保护下,其中氢气体积比为6%,以50℃/分的速率升温到750℃,保温45分钟,然后降温至室温。将烧结后的材料用破碎机破碎后,在气流磨上分级处理,得到颗粒均匀的磷酸铁锂。
测得材料中含碳量为4.2%。
以85:5:10的质量比分别称取实施例1所得的正极材料:乙炔黑:PVDF,研磨均匀后制成电极,负极选用金属锂片,电解液为溶解在碳酸乙酯和碳酸二乙醋混合溶剂中的1.0mol/l的LiPF6,碳酸乙酯和碳酸二乙醋体积比1∶1,隔膜为聚丙烯微孔薄膜,组装成电池。
在0.2C放电时,材料可逆克容量可达155mAh/g,1C放电时可逆克容量为144mAh/g。材料克容量高,放电平台良好,稳定,性能优越。
本发明中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。
尽管对本发明已作出了详细的说明并引证了一些具体实例,但是对本领域熟练技术人员来说,只要不离开本发明的精神和范围可作各种变化或修正是显然的。

Claims (10)

1.一种含氧空位和Fe位掺杂型磷酸铁锂,其特征在于:其分子式为LiFe1-x-aMeaMxPO4-yNz,其中Me为Mg、Mn或者Nd中的一种或一种以上,M为Li、Na、K、Ag、Cu中的一种或一种以上;0≤x≤0.1,0≤a≤0.1,0<y≤0.5,0≤z≤0.5,其中x、y、z不能同时为0。
2.一种含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法,磷酸铁锂的分子式为LiFe1-x-aMeaMxPO4-yNz,其中Me为Mg、Mn或者Nd中的一种或一种以上,M为Li、Na、K、Ag、Cu中的一种或一种以上;0≤x≤0.1,0≤a≤0.1,0<y≤0.5,0≤z≤0.5,其中x、y、z不能同时为0,烧结方法的步骤为:
(1)按上述化学式组成的摩尔比称取锂化合物、Fe3+化合物、Me和M掺杂物和磷酸盐,混合后加入导电用碳源,碳源的加入量为混合物总质量的5~20wt%;
(2)将上述混合物搅拌或者砂磨混合,混合的同时加溶剂,混合1~10小时,然后烘干浆料;
(3)烧结:将烘干后的浆料压块或者直接放入微波烧结炉,在流速为0.01~50升/分钟的Ar气和H2气混合气体保护下加热处理,升温速率为40~80℃/分钟,升温至700~800℃,热处理时间为20~60分钟,然后降温到室温;
(4)制粉:采用二次球磨或气流磨方法粉磨,得到磷酸铁锂。
3.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法,其特征在于所述Fe3+化合物选自三氧化二铁或磷酸铁或其混合物。
4.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法,其特征在于,所述的锂化合物为碳酸锂、草酸锂、醋酸锂、单水氢氧化锂、磷酸二氢锂中的至少一种。
5.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法,其特征在于,所述的磷酸盐为磷酸、磷酸氢二铵、磷酸二氢铵、磷酸三铵、磷酸二氢锂中至少一种。
6.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法,其特征在于,所述的碳源的加入量为混合物总质量的10wt%~15wt%。
7.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法,其特征在于,所述的碳源为碳黑、乙炔黑、蔗糖、淀粉、葡萄糖、活性炭、聚乙烯醇中的一种或一种以上。
8.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法,其特征在于,所述的Ar气和H2气混合气体中,H2的气体积比为总体积的6~10%。
9.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法,其特征在于,所述的混合时加入的溶剂为去离子水或自来水或酒精或煤油,混合时间为1~3小时。
10.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法,其特征在于,所述的烘干为用烘箱烘干或者用喷雾造粒设备烘干,烘干温度采用烘箱时为40~120℃,采用喷雾造粒设备时为120~260℃。
CNA2009100954019A 2009-01-08 2009-01-08 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法 Pending CN101481106A (zh)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CNA2009100954019A CN101481106A (zh) 2009-01-08 2009-01-08 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法
US12/622,397 US8241521B2 (en) 2009-01-08 2009-11-19 Lithium iron phosphate having oxygen vacancy and doped in the position of Fe and method of quick solid phase sintering for the same
EP10150049A EP2207229B1 (en) 2009-01-08 2010-01-04 Lithium iron phosphate having an oxygen vacancy and doped in the position of Fe and method of quick solid phase sintering for the same
ES10150049T ES2371050T3 (es) 2009-01-08 2010-01-04 FOSFATO DE LITIO-HIERRO QUE TIENE UNA VACANTE DE OXÍGENO Y ESTÁ DOPADO EN LA POSICIÓN DEL Fe Y PROCEDIMIENTO DE SINTERIZACIÓN RÁPIDA EN FASE SÓLIDA PARA EL MISMO.
CN2010103000236A CN101764226B (zh) 2009-01-08 2010-01-04 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法
AT10150049T ATE529907T1 (de) 2009-01-08 2010-01-04 Lithiumeisenphosphat, das eine sauerstoffleerstelle aufweist und in der fe- stellung dotiert ist, und verfahren zum schnellen festphasensintern für das lithiumeisenphosphat

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2009100954019A CN101481106A (zh) 2009-01-08 2009-01-08 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法

Publications (1)

Publication Number Publication Date
CN101481106A true CN101481106A (zh) 2009-07-15

Family

ID=40878426

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2009100954019A Pending CN101481106A (zh) 2009-01-08 2009-01-08 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法

Country Status (5)

Country Link
US (1) US8241521B2 (zh)
EP (1) EP2207229B1 (zh)
CN (1) CN101481106A (zh)
AT (1) ATE529907T1 (zh)
ES (1) ES2371050T3 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120214064A1 (en) * 2009-11-18 2012-08-23 Sony Corporation Solid-state electrolyte battery and cathode activating substance
CN102779997A (zh) * 2011-05-13 2012-11-14 信越化学工业株式会社 制备用于锂离子电池的粒状正电极材料的方法
CN107863528A (zh) * 2017-10-26 2018-03-30 合肥国轩高科动力能源有限公司 一种LiFePO4正极材料O位修饰的改性方法

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101481106A (zh) 2009-01-08 2009-07-15 横店集团东磁股份有限公司 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法
KR101748406B1 (ko) * 2009-08-07 2017-06-16 가부시키가이샤 한도오따이 에네루기 켄큐쇼 양극 활물질의 제작 방법
SG187660A1 (en) * 2010-08-20 2013-03-28 Univ Singapore Mesoporous metal phosphate materials for energy storage application
US8932481B2 (en) * 2010-08-31 2015-01-13 Samsung Sdi Co., Ltd. Cathode active material, method of preparing the same, and cathode and lithium battery including the cathode active material
US20120231341A1 (en) * 2011-03-09 2012-09-13 Jun-Sik Kim Positive active material, and electrode and lithium battery containing the positive active material
CN102361077A (zh) * 2011-10-26 2012-02-22 吴润秀 银、钡活化磷酸铁锂正极材料制备方法
TW201342697A (zh) * 2012-03-30 2013-10-16 Sumitomo Osaka Cement Co Ltd 電極材料
CN107834059A (zh) * 2017-07-08 2018-03-23 郑春燕 一种新型复合电极材料的制备工艺
CN107834066A (zh) * 2017-07-09 2018-03-23 郑春燕 一种掺杂锰的高导电率复合电极材料及工艺
EP4217329A1 (en) * 2020-09-22 2023-08-02 Tesla, Inc. Sintered cathode active material elements and methods thereof
CN113991071A (zh) * 2021-09-14 2022-01-28 陕西创普斯新能源科技有限公司 一种氟代磷酸铁锂复合材料及其制备方法和应用
CN115286046B (zh) * 2022-06-27 2023-07-07 广东邦普循环科技有限公司 掺杂铜的钴酸锂前驱体、正极材料及其制备方法和应用
CN115180608A (zh) * 2022-07-26 2022-10-14 江西赣锋锂电科技股份有限公司 一种高振实密度球形磷酸锰铁锂的制备方法
CN118239460B (zh) * 2024-05-28 2024-08-13 宜宾天原锂电新材有限公司 一种高压实密度磷酸铁锂正极材料及其制备方法和电池

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10117904B4 (de) * 2001-04-10 2012-11-15 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung Binäre, ternäre und quaternäre Lithiumeisenphosphate, Verfahren zu ihrer Herstellung und ihre Verwendung
US7008726B2 (en) * 2004-01-22 2006-03-07 Valence Technology, Inc. Secondary battery electrode active materials and methods for making the same
CN1328808C (zh) 2004-04-23 2007-07-25 中国科学院物理研究所 一种用于二次锂电池的氮磷酸盐的正极材料及其用途
CN100377392C (zh) 2004-12-21 2008-03-26 中国科学院物理研究所 用于二次锂电池的含氧空位的磷酸铁锂正极材料及其用途
CN100564250C (zh) 2007-05-30 2009-12-02 横店集团东磁股份有限公司 锂离子电池正极材料磷酸铁锂的微波快速固相烧结方法
CN101481106A (zh) 2009-01-08 2009-07-15 横店集团东磁股份有限公司 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120214064A1 (en) * 2009-11-18 2012-08-23 Sony Corporation Solid-state electrolyte battery and cathode activating substance
US9123960B2 (en) * 2009-11-18 2015-09-01 Sony Corporation Solid-state electrolyte battery and cathode activating substance
CN102779997A (zh) * 2011-05-13 2012-11-14 信越化学工业株式会社 制备用于锂离子电池的粒状正电极材料的方法
CN107863528A (zh) * 2017-10-26 2018-03-30 合肥国轩高科动力能源有限公司 一种LiFePO4正极材料O位修饰的改性方法
CN107863528B (zh) * 2017-10-26 2020-09-04 合肥国轩高科动力能源有限公司 一种LiFePO4正极材料O位修饰的改性方法

Also Published As

Publication number Publication date
ES2371050T3 (es) 2011-12-26
EP2207229A1 (en) 2010-07-14
EP2207229B1 (en) 2011-10-19
US8241521B2 (en) 2012-08-14
ATE529907T1 (de) 2011-11-15
US20100171071A1 (en) 2010-07-08

Similar Documents

Publication Publication Date Title
CN101481106A (zh) 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法
CN100491239C (zh) 锂离子电池正极材料磷酸铁锂的制备方法及其产品
CN101630739B (zh) 掺杂改性的磷酸铁锂的制备方法
CN101764226B (zh) 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法
CN101330141B (zh) 一种锂离子电池正极材料球形LiFePO4/C的制备方法
CN100448071C (zh) 锂电池正极材料及其制备方法
CN100564250C (zh) 锂离子电池正极材料磷酸铁锂的微波快速固相烧结方法
CN104752718B (zh) 一种LiMnxFe1‑xPO4正极活性材料及其制备方法
CN102275887A (zh) 一种高容量高压实密度磷酸铁锂材料的制备方法及其产品
CN101591012B (zh) 一种用于锂离子电池正极材料磷酸铁锂的制备方法
CN101420034A (zh) 碳包覆粒度可控球形磷酸铁锂复合正极材料及其制备方法
CN101339992B (zh) 锂离子电池正极材料硅酸钒锂的制备方法
CN102104143A (zh) 一种高性能动力电池用复合材料的水热合成法
CN101973539B (zh) 一种合成磷酸铁锂正极材料的方法
CN102311109A (zh) 连续反应制备LiFePO4/C复合正极材料的方法
CN102522551A (zh) 一种动力电池正极材料LiFePO4超细粉的制备方法
CN101475155A (zh) 锂离子电池正极材料磷酸铁锂的制备方法
CN114426265A (zh) 多元结晶型磷酸铁锂正极材料及其制备方法、锂离子电池和涉电设备
CN102280673A (zh) 一种锂离子电池正极材料磷酸铁锂废料的再生方法
CN101894942B (zh) LiFePO4/ N复合电极材料及其制备方法
CN104752719B (zh) 一种LiMnxFe1‑xPO4正极活性材料及其制备方法
CN110311132A (zh) 一种石墨烯电池导电剂及制备方法和应用、一种电极材料
CN102544493B (zh) 一种石墨烯复合的锂离子电池复合正极材料的制备方法
CN101656311A (zh) 一种LiFePO4/C复合材料的制备方法
CN102244243B (zh) 一种以氧化铁为原料制备磷酸亚铁锂复合材料的方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20090715