CN103531792A - Manufacturing method of high-property lithium salt composite-phase lithium iron phosphate material - Google Patents

Manufacturing method of high-property lithium salt composite-phase lithium iron phosphate material Download PDF

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CN103531792A
CN103531792A CN201210090208.8A CN201210090208A CN103531792A CN 103531792 A CN103531792 A CN 103531792A CN 201210090208 A CN201210090208 A CN 201210090208A CN 103531792 A CN103531792 A CN 103531792A
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lithium
iron phosphate
lifepo
phosphate
lithium iron
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喻维杰
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

Abstract

The invention relates to a manufacturing method of a high-property lithium salt composite-phase lithium iron phosphate material, and belongs to a manufacturing method of a positive electrode material of a lithium ion battery in the field of new energy materials. The manufacturing method is characterized by comprising the following steps of: preburning to obtain an LiFePO4 precursor; then adding an additive, carrying out ball milling, and sintering to form a LiFePO4/Li(1-x)MgyV2-zNzO5 (N=Ti, Mn or La) composite-phase material. According to the invention, the lithium salt Li(1-x)MgyV2-zNzO5 with excellent lithium ion-electron composite conductor characteristics and lithium iron phosphate sub-micron crystal particles of about 200 nanometers are cocrystallized to form secondary particles with d50 at about 2 micrometers, so that the tap density and pole piece processing property of a powdery material are greatly enhanced; a lithium salt solid solution positioned on a crystal boundary position can not only provide excellent lithium ions and electron conduction property, but also effectively inhibits the lithium iron phosphate particles from growing in sintering, so that the high-current charge and discharge property of a battery is very excellent.

Description

A kind of manufacture method of high-performance lithium salts composite phase lithium iron phosphate material
Technical field
The invention belongs to the manufacture method of a kind of positive electrode of lithium ion battery in new energy materials field.
Background technology
LiFePO4 (the LiFePO of olivine-type structure 4) material, it has the reversible de-embedding/embedded performance of lithium ion, can be used as the positive electrode of lithium ion battery.LiFePO 4olivine-type structure there is the LiMO of ratio 2the layer structure of (M=Co, Ni, Mn) and LiMn 2o 4spinel structure is stable structure feature more, and it changes very little in battery charging and discharging state lower volume, and battery can charge and discharge cycles more than 3000 times.LiFePO 4theoretical specific capacity be 170mAh/g, with respect to the stable discharging voltage platform of lithium anode, be 3.45V.Current LiFePO 4be acknowledged as the best positive electrode of manufacturing large capacity, high safety, low cost, long-life lithium ion battery, started to be applied to the driving electrical source of power of electric automobile.
But LiFePO 4material also has serious defect.In its crystal structure, FeO 6octahedra on bc face with common summit but not altogether limit form be connected. adjacent FeO 6octahedra by PO 4tetrahedron is kept apart and cannot be formed continuous FeO 6network configuration, so electronics is difficult to conduction, its material is insulator feature, electronic conductivity only has 10 -9s/cm.In the crystal of this material, oxygen atom, by arranging close to the closelypacked mode of six sides, can only provide limited passage for lithium ion in addition, and under room temperature, lithium ion migration rate is therein very little.LiFePO 4as positive electrode lithium ion in the charge and discharge process of battery, need to pass FePO 4/ LiFePO 4the interface of several nano thickness.Due to the passage and the FePO that lack lithium ion in structure and move freely 4/ LiFePO 4interface potential barrier restriction, LiFePO 4lithium ion migration rate in material is very little, and lithium ion diffusion coefficient is 1.8 * 10 -14cm 2/ 8.
People attempt by Li +case dopes high volence metal ion (as Mg 2+) form the conduction velocity that its lithium ion is improved in lithium ion room, at Fe 2+case dopes high volence metal ion (as Ti 4+, Nb 5+) change its band structure to improve its electrical conductivity speed.But in actual battery industrialization manufacture process, electrical conductivity and the lithium ion conduction performance of the resulting LiFePO 4 material of these metal ion adulterating methods are still very poor, and battery polarization is serious.So people have to need to be to lithium iron phosphate particles coated with conductive carbon.After but carbon is coated, LiFePO 4the tap density of/C material reduces (1.1g/cm greatly 3left and right), drawing abillity is very poor, low (the < 2.3g/cm of compacted density of positive plate 3), the volume capacity of battery is less.People attempt again to add nano-silver powder or copper powder to improve the electric conductivity between material granule and the tap density that do not reduce material.But the metal nanoparticle adding and lithium iron phosphate particles are difficult to tight bonding, also the conduction velocity of lithium ion show no sign of and can improve, nano metal powder is expensive, this has all limited the method and has moved towards real industrialization.
Due to LiFePO 4the lithium ion conduction of material and electrical conductivity performance are very poor, so need to be by LiFePO 4tinyization of particle.Work as LiFePO 4the particle diameter of particle is when 200nm left and right, and its gram volume, high rate performance, high rate during charging-discharging are very outstanding.But primary particle particle diameter is at the LiFePO of 200nm 4, its specific area is up to 60m 2/ g, such positive electrode is cannot be bonding well in the painting process of industrialization battery production, pole piece dry linting is very serious, cannot make battery.
Summary of the invention
The object of the invention is to the lithium salts solid solution Li with a kind of good lithium ion-electron recombination conductor 1-xmg yv 2-zn zo 5(N=Ti, Mn and La) be that crystal boundary material and LiFePO4 sub-micron grain (250nm left and right) form compound phase material, lithium salts solid solution at grain boundaries can either provide good lithium ion and electrical conductivity performance, it can play pinning effect again simultaneously, can effectively suppress growing up of lithium iron phosphate particles, the composite phase lithium iron phosphate granular size homogeneous, the LiFePO that produce 4primary particle particle diameter is at the particle diameter d of 200nm left and right, compound phase agglomerated particle 50in 2um left and right, the tap density of material is high, powder is especially easily bonding, and the high rate during charging-discharging of pole piece processing characteristics and battery is very outstanding.LiFePO 4/ Li 1-xmg yv 2-zn zo 5compound phase material, wherein M is one or more in Ti, Mn and La.First the pre-burning of preparing burden generates LiFePO 4submicron particles, then according to the lithium salts solid solution Li that forms 0.1-5%wt 1-xmg yv 2-zn zo 5(wherein in lithium salts solid solution, each metallic element molar ratio is Li: Mg: V: N=0.2-1: 0.1-0.5: 1.5-2: 0-0.5) stoichiometry adds LiOHH 2o or Li 2cO 3, Mg (OH) 2or MgO, V 2o 5or NH 4vO 3and TiO 2or H 2tiO 3, MnO 2or Mn 3o 4, La 2o 3in one or more.Through ball milling, sintering, pulverizing, obtain LiFePO 4/ Li 1-xmg yv 2-zn zo 5compound phase material material.
Concrete steps of the present invention are: by Fe source compound, P source compound, Li source compound according to LiFePO 4stoichiometry batching, adds organic dispersing agent, ball milling 2 hours, vacuumize.Vacuum or pass into nitrogen or argon gas at 500--650 ℃ of pre-burning 2-10 hour, after material is cooling, according to the lithium salts solid solution Li that forms 0.1-5%wt 1-xmg yv 2-zn zo 5(wherein in lithium salts solid solution, each constitutive molar ratio example is Li: Mg: V: N=0.2-1: 0.1-0.5: 1.5-2: stoichiometry 0-0.5) adds LiOHH 2o or Li 2cO 3, Mg (OH) 2or MgO, V 2o 5or NH 4vO 3and TiO 2or H 2tiO 3, MnO 2or Mn 2o 3, La 2o 3in one or more, through ball milling 2 hours, pass into nitrogen or argon gas at 600--750 ℃ of sintering 2-10 hour, the cooling rear mechanical crushing of material and air-flow crushing, obtain high performance LiFePO 4/ Li 1-xmg yv 2-zn zo 5compound phase material.
Above-described Li source compound is lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate; Source of iron raw material is ferrous oxalate, di-iron trioxide or ferric phosphate; P source compound is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, lithium dihydrogen phosphate or lithium phosphate.
Above-described organic dispersing agent can be acetone, butanone or absolute ethyl alcohol.
Synthesized of the present invention goes out LiFePO 4/ Li 1-xmg yv 2-zn zo 5compound phase material, with current carbon-coated LiFePO 4 for lithium ion batteries material compared, has following outstanding advantage:
1.LiFePO 4/ Li 1-xmg yv 2-zn zo 5the tap density of compound phase material can reach 1.4g/cm3, is far longer than the tap density (1.1g/cm3) of carbon-coated LiFePO 4 for lithium ion batteries material.
2. when manufacturing lithium ion battery, the LiFePO of synthesized of the present invention 4/ Li 1-xmg yv 2-zn zo 5compound phase material shows as good processing characteristics, and powder is easily bonding, not dry linting; And carbon-coated LiFePO 4 for lithium ion batteries materials processing performance is bad.
3. than the volume and capacity ratio of the lithium ion battery of current carbon-coated LiFePO 4 for lithium ion batteries material manufacture, to improve 15-25%.
4. 0.1-5%wt lithium salts solid solution can stop growing up of lithium iron phosphate particles effectively, and the composite phase lithium iron phosphate material primary particle particle that obtains is more tiny, homogeneous.
5. good lithium ion conduction and the electrical conductivity performance of lithium salts solid solution, makes composite phase lithium iron phosphate material have outstanding high rate during charging-discharging, and multiplying power is fine, and cycle performance is outstanding, and the internal resistance of cell is low.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of composite phase lithium iron phosphate material in embodiment 1.
Fig. 2 is the electron scanning micrograph of composite phase lithium iron phosphate material in embodiment 1.
Fig. 3 is the battery discharge curve that in embodiment 1, composite phase lithium iron phosphate is positive electrode.
Fig. 4 is the circulating battery curve that in embodiment 1, composite phase lithium iron phosphate is positive electrode.
Fig. 5 be in embodiment 2 composite phase lithium iron phosphate material X-ray diffraction spectrogram.
Fig. 6 is the electron scanning micrograph of composite phase lithium iron phosphate material in embodiment 2.
Fig. 7 is the battery discharge curve that in embodiment 2, composite phase lithium iron phosphate is positive electrode.
Fig. 8 is the circulating battery curve that in embodiment 2, composite phase lithium iron phosphate is positive electrode.
Embodiment
Embodiment 1:
With FeC 2o 4.2H 2o, LiH 2pO 4for primary raw material, according to LiFePO 4stoichiometry batching, adding absolute ethyl alcohol is dispersant, stirring ball-milling 2 hours, the slurry obtaining becomes the powder of homogeneous components through vacuumize, pack magazine into, passes into high pure nitrogen (99.999%) 550 ℃ of pre-burnings 5 hours.After material is cooling, wherein according to 3%wt lithium salts solid solution Li 0.4mg 0.2v 1.9ti 0.1o 5stoichiometry adds Li 2cO 3, Mg (OH) 2, NH 4vO 3and TiO 2, ball milling 2 hours, packs magazine into, passes into high pure nitrogen (99.999%) 620 ℃ of sintering 10 hours.After powder is cooling, through mechanical crushing and air-flow crushing, obtained composite phase lithium iron phosphate material.Fig. 1 is LiFePO 4/ Li 0.4mg 0.2v 1.9ti 0.1o 5the X-ray diffraction spectrogram of compound phase material.Due to lithium salts solid solution Li 0.4mg 0.2v 1.9ti 0.1o 5content seldom only has 3%wt, at 16.55 ° and 27.62 °, locates LiV 2o 5faint the presenting of significant diffraction maximum of phase.Fig. 2 is LiFePO 4/ Li 0.4mg 0.2v 1.9ti 0.1o 5the electron scanning micrograph of compound phase material.The primary particle particle diameter of lithium iron phosphate particles is at 200nm left and right, tiny homogeneous.The particle of 200nm left and right connects into larger second particle by crystal boundary.Between particle, there is very large porosity.This lithium iron phosphate positive material high porosity structure is particularly conducive to the embedding of lithium ion and deviates from.Fig. 3 be take the discharge-rate curve of the 5Ah flexible-packed battery that composite phase lithium iron phosphate material that this example manufactures makes as positive pole.Battery 1C electric discharge gram volume is 135mAh/g, and voltage platform is high, and discharge capacity ratio 5C/1C=95.4%, shows as outstanding heavy-current discharge performance.Fig. 4 be take the 1C charging of the 5Ah flexible-packed battery that composite phase lithium iron phosphate material that this example manufactures makes as positive pole, the cyclic curve of 5C electric discharge, and cycle performance is outstanding, and the capability retention after 190 times that circulates is 96.7%.
Embodiment 2:
With Fe 2o 3, LiH 2pO 4for primary raw material, add organic polymerization inhibitor, take absolute ethyl alcohol as dispersant, stirring ball-milling 2 hours, vacuumize, passes into high pure nitrogen (99.999%) 500 ℃ of low temperature presinterings 3 hours.After cooling, wherein according to 2%wt lithium salts solid solution Li 0.2mg 0.3v 1.95mn 0.05o 5stoichiometry adds LiOHH 2o, MgO, V 2o 5and Mn 3o 4ball milling 2 hours, passes into high pure nitrogen (99.999%) 660 ℃ of sintering 4 hours.Cooling rear pulverizing, classification, obtain LiFePO 4/ Li 0.2mg 0.3v 1.95mn 0.05o 5composite phase lithium iron phosphate material.Fig. 5 is LiFePO 4/ Li 0.2mg 0.3v 1.95mn 0.05o 5the X-ray diffraction spectrogram of composite phase lithium iron phosphate material.Due to lithium salts solid solution Li 0.2mg 0.3v 1.95mn 0.05o 5content seldom only has 2%wt, at 16.55 ° and 27.62 °, locates LiV 2o 5faint the presenting of significant diffraction maximum of phase.Fig. 6 is the LiFePO that this example is manufactured 4/ Li 0.2mg 0.3v 1.95mn 0.05o 5the electron scanning micrograph of composite phase lithium iron phosphate material.The primary particle particle diameter of lithium iron phosphate particles is at 200nm left and right, tiny homogeneous.The particle of 200nm left and right connects into larger second particle by crystal boundary.Between particle, there is very large porosity.The high porosity structure of this lithium iron phosphate positive material is particularly conducive to the embedding of lithium ion and deviates from.Fig. 7 be take the discharge-rate curve of the 5Ah flexible-packed battery that composite phase lithium iron phosphate material that this example manufactures makes as positive pole.Battery 1C electric discharge gram volume is 132mAh/g, and voltage platform is high, and discharge capacity ratio 5C/1C=94.2%, shows as outstanding heavy-current discharge performance.Fig. 8 be take the 1C charging of the 5Ah flexible-packed battery that composite phase lithium iron phosphate material that this example manufactures makes as positive pole, the cyclic curve of 5C electric discharge, and cycle performance is very outstanding, and capability retention 99% circulates 290 times.

Claims (5)

1. a manufacture method for lithium salts composite phase lithium iron phosphate material, is characterized in that: in pre-burned, obtain LiFePO 4after presoma, add sintering after additive to form LiFePO 4/ Li 1-xmg yv 2-zn zo 5(N=Ti, Mn and La) compound phase material, has the lithium salts Li of good lithium ion-electron recombination conductor characteristics 1-xmg yv 2-zn zo 5form d with LiFePO4 200nm left and right sub-micron grain eutectic 50second particle in 2um left and right.
2. the manufacture method of a kind of lithium salts composite phase lithium iron phosphate material according to claim 1, is characterized in that: by Fe source compound, P source compound and Li source compound according to LiFePO 4stoichiometry batching, adds organic dispersing agent, ball milling 2 hours, vacuumize, vacuum or pass into nitrogen (99.999%) or argon gas (99.999%) at 500--650 ℃ of pre-burning 2-10 hour, after material is cooling, according to the lithium salts solid solution Li that forms 0.1-5%wt 1-xmg yv 2-zn zo 5the stoichiometry of (N=Ti, Mn and La) adds LiOHH 2o or Li 2cO 3, Mg (OH) 2or MgO, V 2o 5or NH 4vO 3, add TiO 2or H 2tiO 3, MnO 2or Mn 2o 3, La 2o 3in one or more, through ball milling 2 hours, pass into nitrogen (99.999%) or argon gas (99.999%) at 600--750 ℃ of sintering 2-10 hour, the cooling rear mechanical crushing of material and air-flow crushing, obtain high performance LiFePO 4/ Li 1-xmg yv 2-zn zo 5compound phase material.
3. the manufacture method of a kind of lithium salts composite phase lithium iron phosphate material according to claim 1, is characterized in that: lithium salts solid solution Li 1-xmg yv 2-zn zo 5in (N=Ti, Mn and La), each metallic element molar ratio is Li: Mg: V: N=0.2-1: 0.1-0.5: 1.5-2: 0-0.5.
4. the manufacture method of a kind of lithium salts composite phase lithium iron phosphate material according to claim 1, is characterized in that: pre-burning forms LiFePO 4li source compound be lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate, source of iron raw material is ferrous oxalate, di-iron trioxide or ferric phosphate, P source compound is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, lithium dihydrogen phosphate or lithium phosphate.
5. the manufacture method of a kind of lithium salts composite phase lithium iron phosphate material according to claim 1, is characterized in that: organic dispersing agent is acetone, butanone or absolute ethyl alcohol.
CN201210090208.8A 2012-07-02 2012-07-02 Manufacturing method of high-property lithium salt composite-phase lithium iron phosphate material Pending CN103531792A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1925194A (en) * 2005-09-01 2007-03-07 中南大学 Method for preparing anode material gamma-LiV2O5 of lithium ion battery
CN101164870A (en) * 2006-10-19 2008-04-23 喻维杰 Method for manufacturing high performance composite phase lithium iron phosphate material
CN101262058A (en) * 2008-04-15 2008-09-10 中南大学 An anode material for compound lithium ion battery
CN102024947A (en) * 2010-11-09 2011-04-20 罗绍华 LiFePO4/Li-Al-O composite positive electrode material and preparation method thereof
CN102427134A (en) * 2011-12-02 2012-04-25 湘潭大学 Mixed conductor composite material LiFePO4-MXy and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1925194A (en) * 2005-09-01 2007-03-07 中南大学 Method for preparing anode material gamma-LiV2O5 of lithium ion battery
CN101164870A (en) * 2006-10-19 2008-04-23 喻维杰 Method for manufacturing high performance composite phase lithium iron phosphate material
CN101262058A (en) * 2008-04-15 2008-09-10 中南大学 An anode material for compound lithium ion battery
CN102024947A (en) * 2010-11-09 2011-04-20 罗绍华 LiFePO4/Li-Al-O composite positive electrode material and preparation method thereof
CN102427134A (en) * 2011-12-02 2012-04-25 湘潭大学 Mixed conductor composite material LiFePO4-MXy and preparation method thereof

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