CN105633369B - A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material - Google Patents

A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material Download PDF

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CN105633369B
CN105633369B CN201610001218.8A CN201610001218A CN105633369B CN 105633369 B CN105633369 B CN 105633369B CN 201610001218 A CN201610001218 A CN 201610001218A CN 105633369 B CN105633369 B CN 105633369B
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carbon
lifepo4
lifepo
lithium ion
ion batteries
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CN105633369A (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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    • 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
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    • H01M4/625—Carbon or graphite
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    • Y02E60/10—Energy storage using batteries

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Abstract

A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material, surface modification is carried out to pure phase LiFePO4 first, again in one layer of ion liquid polymer of LiFePO4 Surface coating, then the ion liquid polymer on Pintsch process LiFePO4 surface, obtains the LiFePO 4 material of carbon coating；Using ion liquid polymer as carbon source, porous, nitrogenous, boracic can be formed on lithium iron phosphate particles surface or the carbon coating layer of the element such as phosphorous.It is this it is porous, be more beneficial for transfer of the electric charge on LiFePO4 surface containing heteroatomic carbon coating layer, therefore the carbon-coated LiFePO 4 for lithium ion batteries prepared has good cycle performance and high rate performance as lithium ion anode material.

Description

A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material
Technical field
The present invention relates to a kind of using ion liquid polymer as the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries of carbon source, belong to one Plant the preparation method of anode material for lithium-ion batteries.
Background technology
Lithium ion battery anode material lithium iron phosphate (LiFePO4) theoretical capacity be 170mAh/g, reversible discharge and recharge specific volume Amount is higher, while have again, raw material sources are extensive, pollute the advantages such as low, security is good, have extended cycle life, and are ideal at present Power type and accumulation energy type anode material for lithium-ion batteries.But, the ionic conductance and electron conductivity of LiFePO4 compared with It is low, it is only suitable under low current density carrying out discharge and recharge, specific capacity is reduced during high power charging-discharging, which has limited answering for the material With.Carry out substantial amounts of study on the modification to LiFePO4 to improve the electric conductivity of LiFePO4 both at home and abroad, it is main to include preparing Nanoscale LiFePO4, prepare porous LiFePO4, carbon coating, the research master of the mode, wherein coated modified carbon such as metal ion mixing Concentrate on the carbon coating that different shape is realized using different carbon source and coating technology.
Chinese patent CN103346315A provides a kind of carbon-coated LiFePO 4 for lithium ion batteries material using mesoporous carbon CMK-3 as carbon source Preparation method, carbon-coated LiFePO 4 for lithium ion batteries is to be mixed to form mixing by a certain percentage by ferric nitrate, ammonium dihydrogen phosphate, citric acid Thing, under stirring, lithium acetate solution is slowly added dropwise into mixture, forms mixed material, at a certain temperature will be mesoporous Carbon CMK-3 is impregnated into solution, and stirring, ultrasound obtain slimy solution, gained muddy material freeze-day with constant temperature, is ground, is forged Carbon-coated LiFePO 4 for lithium ion batteries powder body material is obtained after burning processing.The particle diameter of the carbon-coated LiFePO 4 for lithium ion batteries of preparation is 200-400nm, particle 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 lithium from Sub- cell positive material.
Chinese patent CN101777636A discloses a kind of preparation method of pyrolytic carbon-coated lithium iron phosphate composite.Adopt It is raw material with one kind in LiFePO4 one or more in pure phase LiFePO4, carbon dope and metal ion, with glucose, poly- second The organic matters such as glycol, polyvinyl alcohol mix above raw material with being dissolved with the solution or organic precursor of organic carbon source as carbon source Close, be placed in pyrolysis stirred autoclave, 0.5~24h is reacted in 100~1000 DEG C, the powder for reacting acquisition is placed in indifferent gas 1~10h is sintered in 200~1000 DEG C in atmosphere reacting furnace, carbon-coated LiFePO 4 for lithium ion batteries is obtained.LiFePO4 prepared by this method is combined Material carbon coating layer is homogeneous, and cladding process causes raw particles to constitute offspring, improves the packing density and electrification of material Learn performance.
Chinese patent CN103346323A discloses a kind of using polystyrene microsphere and polyethylene glycol as the carbon coating of carbon source The preparation method of LiFePO 4 material.Synthetic polystyrene microballoon, molten by the polystyrene microsphere of synthesis and polyethylene glycol first In deionized water, lithium acetate, ferric nitrate, ammonium dihydrogen phosphate are then mixed to form mixture by a certain percentage, in a constant temperature The lower stirring of degree obtains carbon coating ferric phosphate after obtaining gelinite, freeze-day with constant temperature, the grinding in an oven of gained gelinite, calcination processing Powder for lithium material.The particle diameter of the carbon-coated LiFePO 4 for lithium ion batteries of preparation is 200-400nm, and particle is tiny, uniform, purity is high, enhances Electronic conductivity and ion diffusivity.
Chinese patent CN103456924A discloses one kind using high molecular polymer as the secondary carbon-coated LiFePO 4 for lithium ion batteries of carbon source The preparation method of compound, high molecular polymer is that carbon source carbon-coated LiFePO 4 for lithium ion batteries compound is by lithium source, source of iron, phosphorus source and Portugal Grape sugar is placed in solvent to be mixed in molar ratio, and LiFePO4 forerunner's slurry is formed by grinding, and LiFePO4 forerunner slurry passes through Dry, pre-add is heat-treated to form ferric lithium phosphate precursor；By ferric lithium phosphate precursor, high molecular polymer carbon source and compatilizer are pressed According to well mixed in ratio input high speed mixer；Said mixture is added to extruding pelletization after being melted in plastic extruder； The compound is used into carbothermic method again, constant temperature calcining is cooled to room temperature after 5~15 hours under hypoxic atmosphere, obtains high score Sub- polymer is the lithium iron phosphate compound of the secondary carbon coating of carbon source.
The content of the invention
The purpose of the present invention is that instead of organic matters such as glucose, as carbon source, there is provided a kind of carbon bag using ion liquid polymer Cover the preparation method of LiFePO 4 material.
The present invention is a kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material, using ion liquid polymer as carbon source, and it is walked Suddenly it is：
（1）LiFePO4 surface is modified：By LiFePO4 and coupling agent with mass ratio 1:1~1:20 mixing, and by quality Compare LiFePO4:Ethanol=1:20~1:50 add ethanol, then ammoniacal liquor by volume:Ethanol=1:100~1:200 add dense ammonia Then water, 30 DEG C of 20~40h of reflow treatment filter, wash, obtain the LiFePO 4 powder of surface modification；
（2）LiFePO4 Surface coating ion liquid polymer：In step（1）The LiFePO 4 powder that gained surface is modified In LiFePO4 in mass ratio:Solvent=1:20~1:50 add solvent, 20~60min of ultrasonic disperse；Ferric phosphate is compared with quality Lithium:Orqanics Monomer=10:1~1:10 add Orqanics Monomer, compare LiFePO4 with quality:Ionic liquid=10:1~1:10 add Enter ionic liquid monomer；Using initiator and monomer gross mass ratio as 0.01:1~0.1:1 adds initiator；With crosslinking agent and monomer Total mass ratio is 0.01:1~0.1:1 adds crosslinking agent；Under inert gas shielding, at normal temperature~90 DEG C back flow reaction 4~ 40h, obtains the LiFePO 4 powder of ion liquid polymer cladding；
（3）LiFePO4 coated with carbon：By step（2）The LiFePO 4 powder of gained ion liquid polymer cladding exists 400~1000 DEG C of 10~300min of insulation are heated under inert atmosphere protection, carbon-coated LiFePO 4 for lithium ion batteries material is obtained.
The beneficial effects of the invention are as follows：Surface is carried out using silane coupler or titanate coupling agent to LiFePO4 to change Property, then in one layer of ion liquid polymer of LiFePO4 Surface coating, then Pintsch process obtains carbon-coated LiFePO 4 for lithium ion batteries.Using Ion liquid polymer can obtain nitrogen or boron or phosphorus doping as carbon source in metal oxide surface, and structure and morphology is controllable Compound carbon-coating.Ti in the silane coupler or titanate coupling agent of use4+Or Si4+Ion enters during Pintsch process Enter LiFePO4 lattice as Doped ions, Ti4+Or Si4+Ion doping is conducive to improving the chemical property of LiFePO4.This Carbon-coated LiFePO 4 for lithium ion batteries prepared by invention has good cycle performance and high rate performance as anode material for lithium-ion batteries.Adopt Technological operation is simple, easily controllable.
Brief description of the drawings
Fig. 1 is the process chart of the present invention, and Fig. 2 is the XRD for the carbon-coated LiFePO 4 for lithium ion batteries that the present invention is synthesized, and Fig. 3 is The specific discharge capacity cyclic curve for the carbon-coated LiFePO 4 for lithium ion batteries that the present invention is synthesized.
Embodiment
The present invention is a kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material, using ion liquid polymer as carbon source, and it is walked Suddenly it is：
（1）LiFePO4 surface is modified：By LiFePO4 and coupling agent with mass ratio 1:1~1:20 mixing, and by quality Compare LiFePO4:Ethanol=1:20~1:50 add ethanol, then ammoniacal liquor by volume:Ethanol=1:100~1:200 add dense ammonia Then water, 30 DEG C of 20~40h of reflow treatment filter, wash, obtain the LiFePO 4 powder of surface modification；
（2）LiFePO4 Surface coating ion liquid polymer：In step（1）The LiFePO 4 powder that gained surface is modified In LiFePO4 in mass ratio:Solvent=1:20~1:50 add solvent, 20~60min of ultrasonic disperse；Ferric phosphate is compared with quality Lithium:Orqanics Monomer=10:1~1:10 add Orqanics Monomer, compare LiFePO4 with quality:Ionic liquid=10:1~1:10 add Enter ionic liquid monomer；Using initiator and monomer gross mass ratio as 0.01:1~0.1:1 adds initiator；With crosslinking agent and monomer Total mass ratio is 0.01:1~0.1:1 adds crosslinking agent；Under inert gas shielding, at normal temperature~90 DEG C back flow reaction 4~ 40h, obtains the LiFePO 4 powder of ion liquid polymer cladding；
（3）LiFePO4 coated with carbon：By step（2）The LiFePO 4 powder of gained ion liquid polymer cladding exists 400~1000 DEG C of 10~300min of insulation are heated under inert atmosphere protection, carbon-coated LiFePO 4 for lithium ion batteries material is obtained.
Above-described preparation method, described coupling agent is silane resin acceptor kh-550, or silane coupler KH- 560, either Silane coupling reagent KH-570 or long-acting silane coupler CX-550, either titanate coupling agent XY-01 or Titanate coupling agent XY-11, either titanate coupling agent XY-21 or titanate coupling agent XY-31, or titanate esters coupling Agent XY-41.
Above-described preparation method, described solvent is deionized water, either methanol or ethanol, or acetone, or Person's dichloromethane, either cyclohexane or toluene.
Above-described preparation method, described Orqanics Monomer is acrylonitrile, either styrene or aniline, or The combination of methyl methacrylate, either butyl methacrylate or vinylacetate, or above-mentioned organic monomer.
Above-described preparation method, described ionic liquid is 1- vinyl -3- methyl imidazolium tetrafluoroborates [VMIm]BF4, either 1- vinyl -3- methylimidazole dintrile amine salt [VMI] DCA or 1- vinyl -3- ethyl imidazol(e) hexafluoros Phosphate, either 1- vinyl -3- methylimidazoles bromide [VMIm] Br or 1- vinyl -3- butyl imidazole tetrafluoroborates [VBIm]BF4, or 1- vinyl -3- butyl imidazole trifluoromethanesulfonimide salt [VBIm] NTF2, or 1- pi-allyls -3- Methyl imidazolium tetrafluoroborate [AMIm] BF4, or 1- pi-allyls -3- methylimidazoles hexafluorophosphate [AMIm] PF6, or 1- Pi-allyl -3- vinyl imidazoles tetrafluoroborate [AVIm] BF4, or 1- pi-allyl -3- hexyl imidazoliums pair（Fluoroform sulphur Acyl）Inferior amine salt [AHIm] NTF2, or above-mentioned ionic liquid combination.
Above-described preparation method, described initiator is azodiisobutyronitrile, either potassium peroxydisulfate or persulfuric acid The combination of ammonium, either dibenzoyl peroxide or above-mentioned initiator.
Above-described preparation method, described crosslinking agent is polyethyleneglycol diacrylate, or divinylbenzene, or Person's diisocyanate, or N, N- methylene-bisacrylamide, either cumyl peroxide or above-mentioned crosslinking agent group Close.
The present invention is described further with specific embodiment below in conjunction with the accompanying drawings, but the present invention is not limited to following reality Apply example.
Embodiment 1：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 9.0g acrylonitrile, 1.0g1- pi-allyl -3- methyl imidazolium tetrafluoroborates, 0.04g Azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, flow back at 70 DEG C 6h is reacted, the LiFePO4 of ion liquid polymer cladding is obtained.The LiFePO4 of ion liquid polymer cladding is in indifferent gas 650 DEG C of insulation 150min are heated in the tube furnace of atmosphere protection, the Si of carbon coating is obtained4+Doped iron lithium phosphate powder, such as Fig. 2 institutes Show.
The battery performance test of gained lithium iron phosphate positive material uses CR2025 button cells, full of inert atmosphere Glove box in assembled.Negative pole uses metal lithium sheet, and electrolyte uses 1mol.L-LiPF6/EC:DMC(1:1), wherein EC For ethylene carbonate, DMC is dimethyl carbonate.Positive plate preparation technology is as follows：By the positive electrode prepared and conductive agent second Acetylene black, binding agent PVDF（Polyvinylidene fluoride）By 85:8:7 are well mixed, and add appropriate NMP（1-METHYLPYRROLIDONE）In agate Grind uniform in Nao mortars, form sticky colloidal mixture, be then uniformly coated on the thick aluminium foils of 0.02mm, be placed in 120 DEG C vacuum drying 20h, the battery assembled carries out charge-discharge performance test with blue electricity battery test system.Charge-discharge magnification is Under the conditions of 0.2C, material initial discharge specific capacity be 144.6mAh/g, 50 circulation volume conservation rates 91.0%, as shown in Figure 3.
Embodiment 2：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 1.0g acrylonitrile, 9.0g1- pi-allyl -3- methyl imidazolium tetrafluoroborates, 0.04g Azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, flow back at 70 DEG C 6h is reacted, the LiFePO4 of ion liquid polymer cladding is obtained.The LiFePO4 of ion liquid polymer cladding is in indifferent gas 650 DEG C of insulation 150min are heated in the tube furnace of atmosphere protection, the Si of carbon coating is obtained4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 142.1mAh/g, through 50 circulation volume conservation rates 89.7%.
Embodiment 3：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent XY-11 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 9.0g acrylonitrile, 1.0g1- pi-allyl -3- methyl imidazolium tetrafluoroborates, 0.04g Azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, flow back at 70 DEG C 6h is reacted, the LiFePO4 of ion liquid polymer cladding is obtained.The LiFePO4 of ion liquid polymer cladding is in indifferent gas 650 DEG C of insulation 150min are heated in the tube furnace of atmosphere protection, the Ti of carbon coating is obtained4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 149.2mAh/g, through 50 circulation volume conservation rates 87.4%.
Embodiment 4：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 9.0g acrylonitrile, 1.0g1- vinyl -3- methyl imidazolium tetrafluoroborates, 0.04g Azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, flow back at 70 DEG C 6h is reacted, the LiFePO4 of ion liquid polymer cladding is obtained.The LiFePO4 of ion liquid polymer cladding is in indifferent gas 650 DEG C of insulation 150min are heated in the tube furnace of atmosphere protection, the Si of carbon coating is obtained4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 141.3mAh/g, through 50 circulation volume conservation rates 89.6%.
Embodiment 5：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 9.0g acrylonitrile, 1.0g1- vinyl -3- ethyl imidazol(e)s hexafluorophosphate, 0.04g Azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, flow back at 70 DEG C 6h is reacted, the LiFePO4 of ion liquid polymer cladding is obtained.The LiFePO4 of ion liquid polymer cladding is in indifferent gas 650 DEG C of insulation 150min are heated in the tube furnace of atmosphere protection, the Si of carbon coating is obtained4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 138.5mAh/g, through 50 circulation volume conservation rates 85.4%.
Embodiment 6：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 5.0g acrylonitrile, 3.0g1- vinyl -3- methyl imidazolium tetrafluoroborates, 2.0g1- Vinyl -3- butyl imidazole trifluoromethanesulfonimides salt, 0.04g azodiisobutyronitriles and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, the back flow reaction 6h at 70 DEG C obtains the phosphoric acid of ion liquid polymer cladding Iron lithium.The LiFePO4 of ion liquid polymer cladding is heated to 650 DEG C of insulations in the tube furnace of inert atmosphere protection 150min, obtains the Si of carbon coating4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 142.5mAh/g, through 50 circulation volume conservation rates 86.3%.
Embodiment 7：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 3.0g acrylonitrile, 3.0g styrene, 4.0g1- vinyl -3- methylimidazole tetrafluoro boron Hydrochlorate, 0.04g azodiisobutyronitriles and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, Back flow reaction 6h at 70 DEG C, obtains the LiFePO4 of ion liquid polymer cladding.The ferric phosphate of ion liquid polymer cladding Lithium is heated to 750 DEG C of insulation 150min in the tube furnace of inert atmosphere protection, obtains the Si of carbon coating4+Doped iron lithium phosphate powder Body.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 141.3mAh/g, through 50 circulation volume conservation rates 89.6%.
Embodiment 8：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 9.0g styrene, 1.0g1- pi-allyl -3- methyl imidazolium tetrafluoroborates, 0.04g Azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, flow back at 70 DEG C 24h is reacted, the LiFePO4 of ion liquid polymer cladding is obtained.The LiFePO4 of ion liquid polymer cladding is in indifferent gas 750 DEG C of insulation 150min are heated in the tube furnace of atmosphere protection, the Si of carbon coating is obtained4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 147.8mAh/g, through 50 circulation volume conservation rates 82.4%.
Embodiment 9：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 9.0g acrylonitrile, 1.0g1- pi-allyl -3- methyl imidazolium tetrafluoroborates, 0.03g Ammonium persulfate and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, the back flow reaction at 70 DEG C 10h, obtains the LiFePO4 of ion liquid polymer cladding.The LiFePO4 of ion liquid polymer cladding is protected in inert atmosphere 650 DEG C of insulation 150min are heated in the tube furnace of shield, the Si of carbon coating is obtained4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 132mAh/g, through 50 circulation volume conservation rates 82.4%.
Embodiment 10：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 9.0g acrylonitrile, 1.0g1- pi-allyl -3- methyl imidazolium tetrafluoroborates, 0.04g Azodiisobutyronitrile and 0.2gN, N- methylene-bisacrylamide, under inert gas shielding, back flow reaction 6h, is obtained at 70 DEG C The LiFePO4 coated to ion liquid polymer.Pipe of the LiFePO4 of ion liquid polymer cladding in inert atmosphere protection 650 DEG C of insulation 150min are heated in formula stove, the Si of carbon coating is obtained4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 139.7mAh/g, through 50 circulation volume conservation rates 90.4%.
Embodiment 11：5.0g LiFePO4s are added in 200mL ethanol, 50.0g coupling agent KH570 and 1.5mL ammonia is added Water, 30 DEG C of reflow treatment 24h, filtering, washing obtain the LiFePO 4 powder of surface modification；200mL second is added in the powder Alcohol and ultrasonic disperse 30min, then add 9.0g acrylonitrile, 1.0g1- pi-allyl -3- methyl imidazolium tetrafluoroborates, 0.04g Azodiisobutyronitrile and 0.2g polyethyleneglycol diacrylates (PEGDA-200), under inert gas shielding, flow back at 70 DEG C 6h is reacted, the LiFePO4 of ion liquid polymer cladding is obtained.The LiFePO4 of ion liquid polymer cladding is in indifferent gas 800W heating 30min, obtains the Si of carbon coating in the microwave of atmosphere protection4+Doped iron lithium phosphate powder.
According to the method assembled battery of embodiment 1, tested, charge-discharge magnification is under the conditions of 0.2C, material is initially put Capacitance reaches 140.5mAh/g, through 50 circulation volume conservation rates 90.1%.

Claims (7)

1. a kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material, using ion liquid polymer as carbon source, it is characterised in that it is walked Suddenly it is：
（1）LiFePO4 surface is modified：By LiFePO4 and coupling agent with mass ratio 1:1~1:20 mixing, and phosphorus in mass ratio Sour iron lithium:Ethanol=1:20~1:50 add ethanol, then ammoniacal liquor by volume:Ethanol=1:100~1:200 add concentrated ammonia liquor, 30 DEG C 20~40h of reflow treatment, then filters, washs, obtain the LiFePO 4 powder of surface modification；
（2）LiFePO4 Surface coating ion liquid polymer：In step（1）Pressed in the LiFePO 4 powder that gained surface is modified Quality compares LiFePO4:Solvent=1:20~1:50 add solvent, 20~60min of ultrasonic disperse；LiFePO4 is compared with quality:Have Machine thing monomer=10:1~1:10 add Orqanics Monomer, compare LiFePO4 with quality:Ionic liquid=10:1~1:10 add from Sub- liquid monomer；Using initiator and monomer gross mass ratio as 0.01:1~0.1:1 adds initiator；With crosslinking agent and the total matter of monomer Amount is than being 0.01:1~0.1:1 adds crosslinking agent；Under inert gas shielding, 4~40h of back flow reaction at normal temperature~90 DEG C, Obtain the LiFePO 4 powder of ion liquid polymer cladding；
（3）LiFePO4 coated with carbon：By step（2）The LiFePO 4 powder of gained ion liquid polymer cladding is in inertia 400~1000 DEG C of 10~300min of insulation are heated under atmosphere protection, carbon-coated LiFePO 4 for lithium ion batteries material is obtained.
2. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterised in that described coupling agent is Silane resin acceptor kh-550, either silane coupler KH-560 or Silane coupling reagent KH-570, or long-acting silane coupler CX-550, either titanate coupling agent XY-01 or titanate coupling agent XY-11, either 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 to go Ionized water, either methanol or ethanol, either acetone or dichloromethane, either cyclohexane or toluene.
4. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterised in that described organic matter list Body is acrylonitrile, either styrene or aniline, either methyl methacrylate or butyl methacrylate, or acetic acid Vinyl acetate, or above-mentioned organic monomer combination.
5. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterised in that described ionic liquid For 1- vinyl -3- methyl imidazolium tetrafluoroborates [VMIm] BF4, or 1- vinyl -3- methylimidazole dintrile amine salt [VMI] DCA, either 1- vinyl -3- ethyl imidazol(e)s hexafluorophosphate or 1- vinyl -3- methylimidazoles bromide [VMIm] Br, or Person 1- vinyl -3- butyl imidazoles tetrafluoroborate [VBIm] BF4, or 1- vinyl -3- butyl imidazole fluoroform sulphonyl Inferior amine salt [VBIm] NTF2, or 1- pi-allyl -3- methyl imidazolium tetrafluoroborates [AMIm] BF4, or 1- pi-allyl -3- first Base limidazolium hexafluorophosphate [AMIm] PF6, or 1- pi-allyls -3- vinyl imidazoles tetrafluoroborate [AVIm] BF4, or 1- Pi-allyl -3- hexyl imidazoliums are double（Fluoroform sulphonyl）Inferior amine salt [AHIm] NTF2, or above-mentioned ionic liquid combination.
6. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterised in that described initiator is The group of azodiisobutyronitrile, either potassium peroxydisulfate or ammonium persulfate, either dibenzoyl peroxide or above-mentioned initiator Close.
7. carbon-coated LiFePO 4 for lithium ion batteries material preparation method according to claim 1, it is characterised in that described crosslinking agent is Polyethyleneglycol diacrylate, either divinylbenzene or diisocyanate, or N, N- methylene-bisacrylamide, or Person's cumyl peroxide, or above-mentioned crosslinking agent combination.
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