CN105633369A - Preparation method of carbon-coated lithium iron phosphate material - Google Patents

Preparation method of carbon-coated lithium iron phosphate material Download PDF

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CN105633369A
CN105633369A CN201610001218.8A CN201610001218A CN105633369A CN 105633369 A CN105633369 A CN 105633369A CN 201610001218 A CN201610001218 A CN 201610001218A CN 105633369 A CN105633369 A CN 105633369A
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carbon
lifepo4
lifepo
coated
ion batteries
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CN105633369B (en
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蒙延双
蒙延佩
王功瑞
朱福良
张定军
王磊
夏军
白恒富
薛等斌
黄丹
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Lanzhou University of Technology
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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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 provides a preparation method of a carbon-coated lithium iron phosphate material. The method comprises the following steps: carrying out surface modification on pure-phase lithium iron phosphate; coating the lithium iron phosphate surface with a layer of ionic liquid-polymer; and carrying out high-temperature pyrolysis on the ionic liquid-polymer on the lithium iron phosphate surface to obtain the carbon-coated lithium iron phosphate material. With the ionic liquid-polymer as a carbon source, a porous carbon coating layer containing the elements of nitrogen, boron or phosphorus and the like can be formed on the lithium iron phosphate particle surface. The porous carbon coating layer containing heteroatoms is relatively beneficial to charge transferring on the lithium iron phosphate surface, so that the prepared carbon-coated lithium iron phosphate has good cycle performance and rate capability as a lithium-ion cathode material.

Description

A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material
Technical field
The preparation method that the present invention relates to a kind of carbon-coated LiFePO 4 for lithium ion batteries being carbon source with ion liquid polymer, the preparation method belonging to a kind of anode material for lithium-ion batteries.
Background technology
Lithium ion battery anode material lithium iron phosphate (LiFePO4) theoretical capacity is 170mAh/g, reversible charging and discharging capacity is higher, have again simultaneously raw material sources extensively, pollute the advantages such as low, safety good, has extended cycle life, be power type ideal at present and accumulation energy type anode material for lithium-ion batteries. But, the ionic conductance of LiFePO4 and electron conductivity are all relatively low, are only suitable for carrying out discharge and recharge under low current density, and during high power charging-discharging, specific capacity reduces, and which has limited the application of this material. Both at home and abroad LiFePO4 is carried out substantial amounts of study on the modification to improve the electric conductivity of LiFePO4, mainly included preparing nanoscale LiFePO4, preparation porous LiFePO4, carbon cladding, the mode such as metal ion mixing, wherein the research of coated modified carbon is concentrated mainly on the carbon cladding adopting different carbon source and coating technology to realize different shape.
The preparation method that Chinese patent CN103346315A provides a kind of carbon-coated LiFePO 4 for lithium ion batteries material being carbon source with mesoporous carbon CMK-3, carbon-coated LiFePO 4 for lithium ion batteries is to be mixed to form mixture by a certain percentage by ferric nitrate, ammonium dihydrogen phosphate, citric acid, under stirring, lithium acetate solution it is slowly added dropwise in mixture, form mixed material, at a certain temperature mesoporous carbon CMK-3 is impregnated in solution, stirring, ultrasonic obtain slimy solution, after gained muddy material freeze-day with constant temperature, grinding, calcination processing, obtain carbon-coated LiFePO 4 for lithium ion batteries powder body material. The particle diameter of the carbon-coated LiFePO 4 for lithium ion batteries of preparation is 200-400nm, and granule is tiny, uniform, purity is high, enhances electronic conductivity and ion diffusivity. The carbon-coated LiFePO 4 for lithium ion batteries of preparation can be used as anode material for lithium-ion batteries.
The preparation method that Chinese patent CN101777636A discloses a kind of pyrolytic carbon-coated lithium iron phosphate composite. In employing pure phase LiFePO4, carbon dope and metal ion, in one or more LiFePO4, one is raw material, using Organic substances such as glucose, Polyethylene Glycol, polyvinyl alcohol as carbon source, above raw material is mixed with the solution being dissolved with organic carbon source or organic precursor, it is placed in pyrolysis stirred autoclave, 0.5��24h is reacted in 100��1000 DEG C, it is placed in inert atmosphere reacting furnace by the powder body that reaction obtains to sinter 1��10h in 200��1000 DEG C, obtain carbon-coated LiFePO 4 for lithium ion batteries. Composite ferric lithium phosphate material carbon coating layer prepared by the method is homogeneous, and cladding process makes raw particles constitute offspring, improves packing density and the chemical property of material.
The preparation method that Chinese patent CN103346323A discloses a kind of carbon-coated LiFePO 4 for lithium ion batteries material being carbon source with polystyrene microsphere and Polyethylene Glycol. First synthetic polystyrene microsphere, the polystyrene microsphere of synthesis and Polyethylene Glycol are dissolved in deionized water, then lithium acetate, ferric nitrate, ammonium dihydrogen phosphate are mixed to form mixture by a certain percentage, stirring at a certain temperature obtains gelinite, gained gelinite freeze-day with constant temperature in an oven, grinding, obtain carbon-coated LiFePO 4 for lithium ion batteries powder body material after calcination processing. The particle diameter of the carbon-coated LiFePO 4 for lithium ion batteries of preparation is 200-400nm, and granule is tiny, uniform, purity is high, enhances electronic conductivity and ion diffusivity.
Chinese patent CN103456924A discloses a kind of preparation method with high molecular polymer for carbon source secondary carbon-coated LiFePO 4 for lithium ion batteries complex, high molecular polymer is carbon source and carbon coated LiFePO 4 for lithium ion batteries complex is be placed in solvent by lithium source, source of iron, phosphorus source and glucose to mix in molar ratio, forming LiFePO4 forerunner's slurry through grinding, LiFePO4 forerunner's slurry forms ferric lithium phosphate precursor through drying, preheat process; By ferric lithium phosphate precursor, high molecular polymer carbon source and compatilizer proportionally put into mix homogeneously in high speed mixer; Said mixture is added to melted rear extruding pelletization in plastic extruder; Again this complex being adopted carbothermic method, under hypoxic atmosphere, constant temperature calcining was cooled to room temperature after 5��15 hours, obtained the lithium iron phosphate compound that high molecular polymer is carbon source secondary carbon cladding.
Summary of the invention
It is an object of the invention to replace the Organic substance such as glucose as carbon source using ion liquid polymer, it is provided that the preparation method of a kind of carbon-coated LiFePO 4 for lithium ion batteries material.
The present invention is the preparation method of a kind of carbon-coated LiFePO 4 for lithium ion batteries material, with ion liquid polymer for carbon source, the steps include:
(1) LiFePO4 surface modification: LiFePO4 is mixed with mass ratio 1:1��1:20 with coupling agent, and LiFePO4 in mass ratio: ethanol=1:20��1:50 adds ethanol, ammonia by volume again: ethanol=1:100��1:200 adds strong aqua ammonia, 30 DEG C of reflow treatment 20��40h, then filter, wash, obtain the LiFePO 4 powder of surface modification;
(2) LiFePO4 Surface coating ion liquid polymer: LiFePO4 in mass ratio in the LiFePO 4 powder of step (1) gained surface modification: solvent=1:20��1:50 adds solvent, ultrasonic disperse 20��60min; With quality than LiFePO4: Orqanics Monomer=10:1��1:10 adds Orqanics Monomer, with quality than LiFePO4: ionic liquid=10:1��1:10 adds ionic liquid monomer; Initiator is added with monomer total mass ratio for 0.01:1��0.1:1 with initiator; Cross-linking agent is added with monomer total mass ratio for 0.01:1��0.1:1 with cross-linking agent; Under inert gas shielding, back flow reaction 4��40h at room temperature��90 DEG C, obtain the LiFePO 4 powder of ion liquid polymer cladding;
(3) LiFePO4 coated with carbon: the LiFePO 4 powder that step (2) gained ion liquid polymer is coated with is heated under inert atmosphere protection to 400��1000 DEG C of insulation 10��300min, obtain carbon-coated LiFePO 4 for lithium ion batteries material.
The invention has the beneficial effects as follows: adopting silane coupler or titanate coupling agent that LiFePO4 is carried out surface modification, then at one layer of ion liquid polymer of LiFePO4 Surface coating, then Pintsch process obtains carbon-coated LiFePO 4 for lithium ion batteries. Adopt ion liquid polymer can obtain nitrogen or boron or phosphorus doping and the compound carbon-coating that structure and morphology is controlled at metal oxide surface as carbon source. Ti in the silane coupler adopted or titanate coupling agent4+Or Si4+Ion enters LiFePO4 lattice in Pintsch process process becomes dopant ion, Ti4+Or Si4+Ion doping is conducive to improving the chemical property of LiFePO4. Carbon-coated LiFePO 4 for lithium ion batteries prepared by the present invention has good cycle performance and high rate performance as anode material for lithium-ion batteries. The technological operation adopted is simple, easily controllable.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention, and Fig. 2 is the XRD figure of the carbon-coated LiFePO 4 for lithium ion batteries that the present invention synthesizes, and Fig. 3 is the specific discharge capacity cyclic curve of the carbon-coated LiFePO 4 for lithium ion batteries that the present invention synthesizes.
Detailed description of the invention
The present invention is the preparation method of a kind of carbon-coated LiFePO 4 for lithium ion batteries material, with ion liquid polymer for carbon source, the steps include:
(1) LiFePO4 surface modification: LiFePO4 is mixed with mass ratio 1:1��1:20 with coupling agent, and LiFePO4 in mass ratio: ethanol=1:20��1:50 adds ethanol, ammonia by volume again: ethanol=1:100��1:200 adds strong aqua ammonia, 30 DEG C of reflow treatment 20��40h, then filter, wash, obtain the LiFePO 4 powder of surface modification;
(2) LiFePO4 Surface coating ion liquid polymer: LiFePO4 in mass ratio in the LiFePO 4 powder of step (1) gained surface modification: solvent=1:20��1:50 adds solvent, ultrasonic disperse 20��60min; With quality than LiFePO4: Orqanics Monomer=10:1��1:10 adds Orqanics Monomer, with quality than LiFePO4: ionic liquid=10:1��1:10 adds ionic liquid monomer; Initiator is added with monomer total mass ratio for 0.01:1��0.1:1 with initiator; Cross-linking agent is added with monomer total mass ratio for 0.01:1��0.1:1 with cross-linking agent; Under inert gas shielding, back flow reaction 4��40h at room temperature��90 DEG C, obtain the LiFePO 4 powder of ion liquid polymer cladding;
(3) LiFePO4 coated with carbon: the LiFePO 4 powder that step (2) gained ion liquid polymer is coated with is heated under inert atmosphere protection to 400��1000 DEG C of insulation 10��300min, obtain carbon-coated LiFePO 4 for lithium ion batteries material.
Above-described preparation method, described coupling agent is silane resin acceptor kh-550, or silane coupler KH-560, or Silane coupling reagent KH-570, or long-acting silane coupler CX-550, or titanate coupling agent XY-01, or titanate coupling agent XY-11, or titanate coupling agent XY-21, or titanate coupling agent XY-31, or titanate coupling agent XY-41.
Above-described preparation method, described solvent is deionized water, or methanol, or ethanol, or acetone, or dichloromethane, or cyclohexane, or toluene.
Above-described preparation method, described Orqanics Monomer is acrylonitrile, or styrene, or aniline, or methyl methacrylate, or butyl methacrylate, or vinylacetate, or the combination of above-mentioned organic monomer.
Above-described preparation method, described ionic liquid is 1-vinyl-3-methyl imidazolium tetrafluoroborate [VMIm] BF4Or 1-vinyl-3-Methylimidazole. dintrile amine salt [VMI] DCA, or 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, or 1-vinyl-3-Methylimidazole. bromine salt [VMIm] Br, or 1-vinyl-3-1-Butyl-1H-imidazole tetrafluoroborate [VBIm] BF4, or 1-vinyl-3-1-Butyl-1H-imidazole trifluoromethanesulfonimide salt [VBIm] NTF2, or 1-pi-allyl-3-methyl imidazolium tetrafluoroborate [AMIm] BF4, or 1-pi-allyl-3-Methylimidazole. hexafluorophosphate [AMIm] PF6, or 1-pi-allyl-3-vinyl imidazole tetrafluoroborate [AVIm] BF4, or double; two (fluoroform sulphonyl) inferior amine salt [AHIm] NTF of 1-pi-allyl-3-hexyl imidazolium2, or the combination of above-mentioned ionic liquid.
Above-described preparation method, described initiator is azodiisobutyronitrile, or potassium peroxydisulfate, or Ammonium persulfate., or dibenzoyl peroxide, or the combination of above-mentioned initiator.
Above-described preparation method, described cross-linking agent is polyethyleneglycol diacrylate, or divinylbenzene, or diisocyanate, or N,N methylene bis acrylamide, or cumyl peroxide, or the combination of above-mentioned cross-linking agent.
Below in conjunction with the drawings and specific embodiments, the present invention is described further, but the present invention is not limited to following example.
Embodiment 1: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 9.0g acrylonitrile, 1.0g1-pi-allyl-3-methyl imidazolium tetrafluoroborate, 0.04g azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 650 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder, as shown in Figure 2.
The battery performance test of gained lithium iron phosphate positive material all adopts CR2025 button cell, assembles in the glove box of full inert atmosphere. Negative pole adopts metal lithium sheet, and electrolyte adopts 1mol.L-LiPF6/EC:DMC (1:1), wherein EC is ethylene carbonate, and DMC is dimethyl carbonate. Positive plate preparation technology is as follows: by the positive electrode prepared and conductive agent acetylene black, binding agent PVDF(polyvinylidene fluoride) mix homogeneously by 85:8:7, add appropriate NMP(N-methyl pyrrolidone) grind uniformly in agate mortar, form the colloidal mixture of thickness, then it is uniformly coated on the thick aluminium foil of 0.02mm, being placed in 120 DEG C of vacuum drying 20h, the battery assembled blue electricity battery test system carries out charge-discharge performance test. When charge-discharge magnification is 0.2C, material initial discharge specific capacity is 144.6mAh/g, 50 circulation volume conservation rates 91.0%, as shown in Figure 3.
Embodiment 2: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 1.0g acrylonitrile, 9.0g1-pi-allyl-3-methyl imidazolium tetrafluoroborate, 0.04g azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 650 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 142.1mAh/g, through 50 circulation volume conservation rates 89.7%.
Embodiment 3: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent XY-11 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 9.0g acrylonitrile, 1.0g1-pi-allyl-3-methyl imidazolium tetrafluoroborate, 0.04g azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 650 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Ti of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 149.2mAh/g, through 50 circulation volume conservation rates 87.4%.
Embodiment 4: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 9.0g acrylonitrile, 1.0g1-vinyl-3-methyl imidazolium tetrafluoroborate, 0.04g azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 650 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 141.3mAh/g, through 50 circulation volume conservation rates 89.6%.
Embodiment 5: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 9.0g acrylonitrile, 1.0g1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, 0.04g azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 650 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 138.5mAh/g, through 50 circulation volume conservation rates 85.4%.
Embodiment 6: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 5.0g acrylonitrile, 3.0g1-vinyl-3-methyl imidazolium tetrafluoroborate, 2.0g1-vinyl-3-1-Butyl-1H-imidazole trifluoromethanesulfonimide salt, 0.04g azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 650 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 142.5mAh/g, through 50 circulation volume conservation rates 86.3%.
Embodiment 7: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 3.0g acrylonitrile, 3.0g styrene, 4.0g1-vinyl-3-methyl imidazolium tetrafluoroborate, 0.04g azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 750 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 141.3mAh/g, through 50 circulation volume conservation rates 89.6%.
Embodiment 8: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 9.0g styrene, 1.0g1-pi-allyl-3-methyl imidazolium tetrafluoroborate, 0.04g azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 24h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 750 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 147.8mAh/g, through 50 circulation volume conservation rates 82.4%.
Embodiment 9: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 9.0g acrylonitrile, 1.0g1-pi-allyl-3-methyl imidazolium tetrafluoroborate, 0.03g Ammonium persulfate. and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 10h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 650 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 132mAh/g, through 50 circulation volume conservation rates 82.4%.
Embodiment 10: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 9.0g acrylonitrile, 1.0g1-pi-allyl-3-methyl imidazolium tetrafluoroborate, 0.04g azodiisobutyronitrile and 0.2gN; N-methylene-bisacrylamide; under inert gas shielding; back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding heats to 650 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 139.7mAh/g, through 50 circulation volume conservation rates 90.4%.
Embodiment 11: added by 5.0g LiFePO4 in 200mL ethanol, adds 50.0g coupling agent KH570 and 1.5mL ammonia, 30 DEG C of reflow treatment 24h, filters, washs the LiFePO 4 powder obtaining surface modification; This powder body adds 200mL ethanol ultrasonic disperse 30min; it is subsequently adding 9.0g acrylonitrile, 1.0g1-pi-allyl-3-methyl imidazolium tetrafluoroborate, 0.04g azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylate (PEGDA-200); under inert gas shielding; back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding. The LiFePO4 of ion liquid polymer cladding 800W in the microwave of inert atmosphere protection heats 30min, obtains the Si of carbon cladding4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, testing, when charge-discharge magnification is 0.2C, material initial discharge capacity reaches 140.5mAh/g, through 50 circulation volume conservation rates 90.1%.

Claims (7)

1. a preparation method for carbon-coated LiFePO 4 for lithium ion batteries material, with ion liquid polymer for carbon source, it is characterised in that the steps include:
(1) LiFePO4 surface modification: LiFePO4 is mixed with mass ratio 1:1��1:20 with coupling agent, and LiFePO4 in mass ratio: ethanol=1:20��1:50 adds ethanol, ammonia by volume again: ethanol=1:100��1:200 adds strong aqua ammonia, 30 DEG C of reflow treatment 20��40h, then filter, wash, obtain the LiFePO 4 powder of surface modification;
(2) LiFePO4 Surface coating ion liquid polymer: LiFePO4 in mass ratio in the LiFePO 4 powder of step (1) gained surface modification: solvent=1:20��1:50 adds solvent, ultrasonic disperse 20��60min; With quality than LiFePO4: Orqanics Monomer=10:1��1:10 adds Orqanics Monomer, with quality than LiFePO4: ionic liquid=10:1��1:10 adds ionic liquid monomer; Initiator is added with monomer total mass ratio for 0.01:1��0.1:1 with initiator; Cross-linking agent is added with monomer total mass ratio for 0.01:1��0.1:1 with cross-linking agent; Under inert gas shielding, back flow reaction 4��40h at room temperature��90 DEG C, obtain the LiFePO 4 powder of ion liquid polymer cladding;
(3) LiFePO4 coated with carbon: the LiFePO 4 powder that step (2) gained ion liquid polymer is coated with is heated under inert atmosphere protection to 400��1000 DEG C of insulation 10��300min, obtain carbon-coated LiFePO 4 for lithium ion batteries material.
2. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterized in that described coupling agent is silane resin acceptor kh-550, or silane coupler KH-560, or Silane coupling reagent KH-570, or long-acting silane coupler CX-550, or titanate coupling agent XY-01, or titanate coupling agent XY-11, or titanate coupling agent XY-21, or titanate coupling agent XY-31, or titanate coupling agent XY-41.
3. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterised in that described solvent is deionized water, or methanol, or ethanol, or acetone, or dichloromethane, or cyclohexane, or toluene.
4. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterized in that described Orqanics Monomer is acrylonitrile, or styrene, or aniline, or methyl methacrylate, or butyl methacrylate, or vinylacetate, or the combination of above-mentioned organic monomer.
5. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterised in that described ionic liquid is 1-vinyl-3-methyl imidazolium tetrafluoroborate [VMIm] BF4Or 1-vinyl-3-Methylimidazole. dintrile amine salt [VMI] DCA, or 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, or 1-vinyl-3-Methylimidazole. bromine salt [VMIm] Br, or 1-vinyl-3-1-Butyl-1H-imidazole tetrafluoroborate [VBIm] BF4, or 1-vinyl-3-1-Butyl-1H-imidazole trifluoromethanesulfonimide salt [VBIm] NTF2, or 1-pi-allyl-3-methyl imidazolium tetrafluoroborate [AMIm] BF4, or 1-pi-allyl-3-Methylimidazole. hexafluorophosphate [AMIm] PF6, or 1-pi-allyl-3-vinyl imidazole tetrafluoroborate [AVIm] BF4, or double; two (fluoroform sulphonyl) inferior amine salt [AHIm] NTF of 1-pi-allyl-3-hexyl imidazolium2, or the combination of above-mentioned ionic liquid.
6. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterised in that described initiator is azodiisobutyronitrile, or potassium peroxydisulfate, or Ammonium persulfate., or dibenzoyl peroxide, or the combination of above-mentioned initiator.
7. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterized in that described cross-linking agent is polyethyleneglycol diacrylate, or divinylbenzene, or diisocyanate, or N, N-methylene-bisacrylamide, or cumyl peroxide, or the combination of above-mentioned cross-linking agent.
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