CN101145611B - Lithium ion cell anode material lithium vanadium phosphate preparation method - Google Patents
Lithium ion cell anode material lithium vanadium phosphate preparation method Download PDFInfo
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Abstract
The invention discloses a lithium vanadium phosphate anode material used in a lithium battery and a preparation method thereof, and solves the technical problem that can improve the electrical conductivity and high-rate discharge property of the anode material. The inventive anode material comprises a matrix coated outside with a conductive nano-composite material with a particle size of 5-50 Mu mand a specific surface area of 5-25m<2>/g. The inventive anode material is prepared by the following steps: wet-method superfine ball mill, liquid-phase mixture reaction, spray drying, pretreatment,calcinations treatment, coating with conductive composite material, and fusion. Compared with the prior art, the invention can synthesize lithium vanadium phosphate anode material by the secondary molding liquid phase method of nanoparticles, and the product purity is high, the particle agglomeration is efficiently prevented. The synthetic lithium vanadium phosphate anode material has a dischargevoltage about 4V, three discharge voltage platform zones, higher charge/discharge capacity, excellent rate discharge capability and loop stability, and low cost; and is suitable for the industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, particularly a kind of phosphoric acid vanadium lithium material and preparation method thereof with high conductivity, high high rate performance.
Background technology
Lithium rechargeable battery has the energy density height, have extended cycle life and advantage that self-discharge rate is little, since nineteen ninety Sony company successfully realizes commercially producing of lithium rechargeable battery, lithium ion battery is widely used on various portable type electronic products and the Move tool, and it is also having great application prospect aspect electric automobile (EV) and hybrid-electric car (HEV) power supply.At present, it is several that anode material for lithium-ion batteries mainly contains lithium and cobalt oxides, lithium manganese oxide and LiFePO 4 etc., lithium and cobalt oxides is to use as anode material for lithium-ion batteries the earliest, technology maturation, but cobalt is as strategic resource, shortage of resources, cost height, toxicity are higher, and lithium and cobalt oxides is because reasons in structure own exists poor heat stability, oxygen easily to overflow and burn, fail safe is relatively poor, and its discharge voltage is lower, and (average discharge volt is 3.6～3.7V), capacity is lower than 150mAh/g.Lithium manganese oxide anode material aboundresources, cost are low, but its electrochemistry capacitance is lower, and its application is restricted.Lithium iron phosphate cathode material has lower, the better stable and good advantage of security performance of cost, but its discharge voltage plateau is lower, and about 3.4V, theoretical capacity (170mAh/g) is also lower.Among all kinds of anode material for lithium-ion batteries of being studied, phosphoric acid vanadium lithium has the following advantages: higher discharge voltage plateau, average discharge volt are about 4.0V; Higher charge/discharge capacity, theoretical capacity is 197mAh/g, reversible capacity is more than 170mAh/g; Excellent cyclical stability; Good fail safe and lower cost, thereby be expected to become anode material for lithium-ion batteries of new generation.
At present, the research of cathode material lithium vanadium phosphate of lithium ion battery is also just begun, the research report is few, and known phosphoric acid vanadium lithium synthetic method mainly contains three kinds of high temperature solid-state method, sol-gal process and microwave sintering methods.The raw material that high temperature solid-state method adopts is lithium salts, vanadic salts and phosphate nearly all, through pre-burning, adds carbon reduction or hydrogen reducing roasting again, operates more loaded down with trivial detailsly, has the problem that purity is low and production cost is high of sintetics.The control of sol-gal process synthesis condition is harsh, is unsuitable for suitability for industrialized production.The microwave method generated time is short, and energy consumption is low, but because heating-up temperature and time are wayward, has influenced properties of product, and product purity also can not get guaranteeing.And the conductivity of the phosphoric acid vanadium lithium positive electrode that above-mentioned three kinds of methods are synthetic and big multiplying power discharging property can not satisfy with the high rate performance requirement of high-power electric appliance to lithium ion battery.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cathode material lithium vanadium phosphate of lithium ion battery, the technical problem that solve improve the conductivity and the big multiplying power discharging property of positive electrode, improve high rate performance, the security performance of lithium ion battery.
The present invention is by the following technical solutions: a kind of preparation method of cathode material lithium vanadium phosphate of lithium ion battery may further comprise the steps: one, the preparation of nano particle: respectively with Li source compound, vanadium source compound, P source compound and complexing agent through the wet method super-fine ball-milling treatment to nano-scale particle; Two, liquid-phase mixing reaction: by the ratio Li of amount of substance: V: P: complexing agent=3.0～3.3: 2: 3: 1.5～2.2 take by weighing Li source compound, vanadium source compound, P source compound and complexing agent is dissolved in 40～90 ℃ of deionized waters, stirs and obtains composite material in 1～3 hour; Three, the preparation of precursor: with composite material ball milling 0.5～24 hour under the rotating speed of 200～500r/min, spray drying obtains anode material precursor under 100～360 ℃ of conditions then, precursor be shaped as almost spherical that sphere, major axis and minor axis are 5～50 μ m, rhombus, taper, sheet, stratiform or/and block post forming particle; Four, preliminary treatment: the post forming particle under inert atmosphere protection, 200～450 ℃ of preliminary treatment 2～12 hours, is obtained the preliminary treatment powder behind the natural cooling; Five, calcination process: in corundum or graphite saggar, calcination process is 5～24 hours under inert atmosphere protection, in 600～950 ℃ with the preliminary treatment powder packing, is cooled to room temperature then naturally, obtains Li
3V
2(PO
4)
3Matrix; Six, with Li
3V
2(PO
4)
3Matrix surface clad nano composite conducting material was handled under 500～1200 ℃ temperature 1～12 hour then; Described nano combined electric conducting material is nano combined conductive agent, nano metal or nano-metal-oxide conductive agent, and covering amount is 0.1～3wt.% of matrix; Described nano combined conductive agent is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile; butadiene-styrene rubber (SBR); cellulose; the pyrolytic carbon that coal tar pitch or petroleum asphalt organic substance form; conductive acetylene carbon black; carbon nano-fiber; carbon nano-tube or nano-sized carbon microballoon conduction raw material of wood-charcoal material; nano metal is Al; Mg; Cr; Co; Mn; Zn; Cu; Au; Ni; Ag or Nb metallic element simple substance, and nano-metal-oxide is Al; Mg; Cr; Co; Mn; Zn; Cu; Au; Ni; the metal oxide of Ag or Nb; Seven, above-mentioned material is carried out mechanical fusion treatment 0.5～4 hour under the rotating speed of 200～1100r/min, obtain spherical compound phosphoric acid vanadium lithium anode material.
The Li source compound of the inventive method is lithium hydroxide LiOH, lithium carbonate Li
2CO
3, lithium acetate LiCH
3COO, lithium chloride, lithium sulfate, lithium nitrate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 or lithium oxalate; Described vanadium source compound is vanadic oxide V
2O
5, vanadium trioxide V
2O
3, vanadium dioxide VO
2, ammonium metavanadate NH
4VO
3, sodium metavanadate or carbonic acid vanadium; Described P source compound is phosphoric acid H
3PO
4, ammonium phosphate (NH
4)
3PO
4, diammonium hydrogen phosphate (NH
4)
2HPO
4, ammonium dihydrogen phosphate NH
4H
2PO
4, phosphorus pentoxide P
2O
5, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate or dipotassium hydrogen phosphate; Described complexing agent is sucrose, glucose, tartaric acid, citric acid, urea, acrylic acid, fructose, ascorbic acid, polyethylene glycol or glycerol.
Method of the present invention is by the ratio Li of amount of substance: V: P: complexing agent=3.0～3.3: 2: 3: 1.5～2.2 take by weighing Li source compound, vanadium source compound, P source compound and complexing agent, earlier Li source compound, vanadium source compound and P source compound solids are mixed, complexing agent is dissolved in 40～90 ℃ of deionized waters, the solids that mixes is dissolved in the enveloping agent solution, 40～90 ℃ were stirred 1～3 hour down again; Or P source compound is dissolved in 40～90 ℃ of deionized waters, again complexing agent, Li source compound, vanadium source compound solids are added in the P source compound solution successively, 40～90 ℃ were stirred 1～3 hour down; Or be dissolved in 40～90 ℃ of deionized waters respectively Li source compound, vanadium source compound, P source compound and complexing agent and stirring, contain Li source compound, vanadium source compound and the enveloping agent solution that will prepare then add in the P source compound solution, and 40～90 ℃ were stirred 1～3 hour down.
The composite material of the inventive method ball milling under the rotating speed of 200～500r/min adopts stirring ball mill, circulating agitating ball mill, sand mill, colloid mill, planetary ball mill or impact type micro mist balling machine, and ball grinder and abrading-ball material are stainless steel, corundum, zirconia or agate.
Method of the present invention is spray drying under 100～360 ℃ of conditions, carries out in centrifugal spray granulating and drying machine.
Before preliminary treatment under the inert atmosphere protection, fusion treatment is 0.5～2 hour under the rotating speed of 200～1100r/min with the post forming particle for method of the present invention.
Method of the present invention is before calcination process, and on the fusion machine, fusion treatment is 0.5～4 hour under the rotating speed of 200～1100r/min with the preliminary treatment powder; The phosphoric acid vanadium lithium that obtains after the calcination process is with fusion machine fusion treatment 0.5～4 hour under the rotating speed of 200～1100r/min.
Pulverize after roasting of the inventive method and the fusion treatment with classification and handle.
The clad nano composite conducting material of the inventive method adopts matrix and nano combined electric conducting material to mix on fusion machine, blade paddle mixer, conical agitator, twin-shaft mixer or planetary stirring machine mixing mixing plant and coated 0.5～6 hour, afterwards compound is handled under 500～1200 ℃ temperature 1～12 hour.
The present invention compared with prior art, utilize nano particle post forming liquid phase method to synthesize anode material vanadium lithium phosphate, little and the even dispersion of the particle of synthetic material, the purity height of product, carbon and nano combined conductive agent or nano metal, the metal conductive oxide agent is full and uniform to the coating of active material, stoped particle agglomeration effectively, synthetic phosphoric acid vanadium lithium positive electrode has discharge voltage and 3 the discharge voltage plateau zones about 4V, higher charge/discharge capacity, excellent multiplying power discharging property and cyclical stability, and this material is compared with lithium cobalt oxide as positive electrode material and is also had the low and safe advantage of cost, the synthetic phosphoric acid vanadium lithium of liquid phase method has guaranteed that reactant can carry out hybrid reaction on the molecule rank, sufficient reacting, need not the pH value of strict control solution, simplified operation sequence, reduced production cost, help the purity of processing procedure control and raising synthetic material, more be applicable to suitability for industrialized production.Phosphoric acid vanadium lithium positive electrode of the present invention, be assembled into simulated battery with metal lithium sheet, with the 0.25C rate charge-discharge, when charging/discharging voltage is 3.0-4.3V, 3.0-4.9V, maximum discharge capacity reaches respectively greater than 125mAh/g and 170mAh/g, coulombic efficiency is greater than 95% first, and the capability retention after 30 weeks of circulating is greater than 96%.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of the phosphoric acid vanadium lithium of embodiment 1 preparation.
Fig. 2 is the stereoscan photograph of the phosphoric acid vanadium lithium presoma of embodiment 1 preparation.
Fig. 3-the 1st, the stereoscan photograph of phosphoric acid vanadium lithium under 500 times of embodiment 1 preparation.
Fig. 3-the 2nd, the stereoscan photograph of phosphoric acid vanadium lithium under 2000 times of embodiment 1 preparation.
Fig. 4 is the photo of ESEM of the phosphoric acid vanadium lithium primary particle of embodiment 1 preparation.
Fig. 5 is the charging and discharging curve of phosphoric acid vanadium lithium in 3.0-4.3V, 3.0-4.9V charging/discharging voltage scope of embodiment 1 preparation.
Fig. 6 be the phosphoric acid vanadium lithium of embodiment 1 preparation in 3.0-4.3V, 3.0-4.9V charging/discharging voltage scope, the capacity cyclic curve under the 0.25C multiplying power.
Fig. 7 be the phosphoric acid vanadium lithium of embodiment 1 preparation in 3.0-4.9V charging/discharging voltage scope, the charging and discharging curve under 0.25C, 1C, 5C and the 10C multiplying power.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.Cathode material lithium vanadium phosphate of lithium ion battery of the present invention has phosphoric acid vanadium lithium Li
3V
2(PO
4)
3Matrix, matrix is coated with nano combined conductive agent, nano metal or nano-metal-oxide conductive agent, positive electrode has almost spherical that sphere, major and minor axis are 5～50 μ m, rhombus, taper, sheet, stratiform or/and block microscopic feature, its granularity is 5～50 μ m, and specific area is 5～25m
2/ g.
Nano combined electric conducting material of the present invention is nano combined conductive agent, nano metal or nano-metal-oxide conductive agent, and covering amount is 0.1～3wt.% of matrix.Described nano combined conductive agent is the pyrolytic carbon that furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, butadiene-styrene rubber (SBR), cellulose (CMC), coke, coal tar pitch or petroleum asphalt organic substance form, conductive acetylene carbon black (Super-P), carbon nano-fiber, carbon nano-tube or nano-sized carbon microballoon conduction raw material of wood-charcoal material; Described nano metal is Al, Mg, Cr, Co, Mn, Zn, Cu, Au, Ni, Ag or Nb metallic element simple substance and nano-metal-oxide thereof.
The preparation method of cathode material lithium vanadium phosphate of lithium ion battery of the present invention, adopt following steps:
One, the preparation of nano particle: respectively water-insoluble Li source compound, vanadium source compound, P source compound and complexing agent are passed through the wet method super-fine ball-milling treatment to nano-scale particle; Adopt ball milling or disintegrating apparatus, ball milling or disintegrating apparatus are stirring ball mill, sand mill, colloidal mill, airslide disintegrating mill, impact type micro ball-mill, air-flow spiral pulverizing mill, impact grinder or bar type mechanical crusher.
Two, liquid-phase mixing reaction: by the ratio Li of amount of substance: V: P: L (complexing agent)=(3.0～3.3): 2: 3: (1.5～2.2) take by weighing Li source compound, vanadium source compound, P source compound and complexing agent and are dissolved in 40～90 ℃ of deionized waters, stir and obtain composite material in 1～3 hour; Or earlier Li source compound, vanadium source compound and P source compound solids are mixed, complexing agent is dissolved in 40～90 ℃ of deionized waters, the solids that mixes is dissolved in the enveloping agent solution again, and 40～90 ℃ were stirred 1～3 hour down; Or P source compound is dissolved in 40～90 ℃ of deionized waters, again complexing agent, Li source compound, vanadium source compound solids are added in the P source compound solution successively, 40～90 ℃ were stirred 1～3 hour down; Or Li source compound, vanadium source compound, P source compound and complexing agent divided or be dissolved in 40～90 ℃ of deionized waters respectively and stir, contain Li source compound, vanadium source compound and the enveloping agent solution that will prepare then add in the P source compound solution, and 40～90 ℃ were stirred 1～3 hour down.
Three, the preparation of precursor: adopt stirring ball mill, circulating agitating ball mill, sand mill, colloid mill, planetary ball mill or impact type micro mist balling machine, ball grinder and abrading-ball material are stainless steel, corundum, zirconia or agate, with composite material ball milling 0.5～24 hour under the rotating speed of 200～500r/min, then under 100～360 ℃ of conditions, in centrifugal spray granulating and drying machine, carry out drying and obtain anode material precursor, precursor be shaped as sphere, major and minor axis is the almost spherical of 5～50 μ m, rhombus, taper, sheet, stratiform is or/and block post forming particle.
Four, preliminary treatment: with the post forming particle in fusion treatment under the rotating speed of 200～1100r/min after 0.5～4 hour, in inert gas helium He, argon Ar or nitrogen N
2Under the protection, 200～450 ℃ of preliminary treatment 2～12 hours, obtain the preliminary treatment powder behind the natural cooling; Preliminary treatment is carried out in enclosed vacuum drying oven, vacuum drier, box type furnace, tube furnace, vacuum furnace, bell jar stove, steel band stove, rotary furnace or tunnel cave.
Five, fusion treatment: on the fusion machine, fusion treatment is 0.5～4 hour under the rotating speed of 200～1100r/min with the preliminary treatment powder, improves the uniformity of material.
Six, calcination process: in corundum or graphite saggar, calcination process is 5～24 hours under inert atmosphere protection, in 600～950 ℃ with the preliminary treatment powder packing, is cooled to room temperature then naturally, obtains Li
3V
2(PO
4)
3Matrix.
Seven, the Li that obtains after the calcination process
3V
2(PO
4)
3Matrix is with fusion machine fusion treatment 0.5～4 hour under the rotating speed of 200～1100r/min.
Eight, pulverize after the fusion treatment and classification is handled, pulverize to adopt earlier and pulverize at a high speed, the method that back low speed is pulverized is pulverized employing airslide disintegrating mill, high pressure flour mill or bar type mechanical crusher at a high speed; Low speed is pulverized and is adopted low velocity impact formula nodularization pulverizer, air-flow vortex formula pulverizer, micronizer, ultra micro ball mill, internal classification impact type micro mist pulverizer or pendulum type ring roll pulverizer; Classification adopts gas flow sizing machine, jet classifying machine, sub-micron grader or ultra micro rice gas flow sizing machine to handle.
Nine, with Li
3V
2(PO
4)
3Matrix surface clad nano composite conducting material, nano combined electric conducting material is nano combined conductive agent, nano metal or nano-metal-oxide conductive agent, matrix mixes coating 0.5～6 hour with nano combined electric conducting material on fusion machine, blade paddle mixer, conical agitator, twin-shaft mixer or planetary stirring machine mixing mixing plant, afterwards compound was handled under 500～1200 ℃ temperature 1～12 hour.
Ten, above-mentioned material is carried out mechanical fusion treatment 0.5～4 hour under the rotating speed of 200～1100r/min, obtain spherical compound phosphoric acid vanadium lithium anode material after pulverizing and the classification.
Described nano combined conductive agent is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile; butadiene-styrene rubber (SBR); cellulose (CMC); coke; the pyrolytic carbon that coal tar pitch or petroleum asphalt organic substance form; conductive acetylene carbon black (Super-P); carbon nano-fiber; carbon nano-tube or nano-sized carbon microballoon conduction raw material of wood-charcoal material; nano metal is nanoscale Al; Mg; Cr; Co; Mn; Zn; Cu; Au; Ni; metallic element simple substance and oxides thereof such as Ag or Nb, covering amount are 0.1～3wt.% of matrix.
Li source compound is lithium hydroxide LiOH, lithium carbonate Li
2CO
3, lithium acetate LiCH
3COO, lithium chloride, lithium sulfate, lithium nitrate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 or lithium oxalate; Described vanadium source compound is vanadic oxide V
2O
5, vanadium trioxide V
2O
3, vanadium dioxide VO
2, ammonium metavanadate NH
4VO
3, sodium metavanadate or carbonic acid vanadium; Described P source compound is phosphoric acid H
3PO
4, ammonium phosphate (NH
4)
3PO
4, diammonium hydrogen phosphate (NH
4)
2HPO
4, ammonium dihydrogen phosphate NH
4H
2PO
4, phosphorus pentoxide P
2O
5, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate or dipotassium hydrogen phosphate; Described complexing agent is sucrose, glucose, tartaric acid, citric acid, urea, acrylic acid, fructose, ascorbic acid, polyethylene glycol or glycerol.
Embodiment 1
It is nanometer scale that raw material lithium carbonate, ammonium metavanadate, glucose are crushed to granularity through circulating agitating ball mill respectively, accurately takes by weighing lithium carbonate (Li
2CO
3) 108.8 the gram, ammonium metavanadate (NH
4VO
3) 229.6 the gram, phosphoric acid (H
3PO
4) 339.4 grams and glucose 353.2 gram be dissolved in 400 milliliters of 60 ℃ of deionized waters constant temperature stirring 3 hours respectively; Glucose solution is added in the phosphoric acid solution earlier, lithium carbonate and ammonium metavanadate solution are added successively again, 60 ℃ of constant temperature stirs and reacted completely to mixed solution in 2 hours, does not have bubble to produce.
With above-mentioned sample ball milling (QM-1SP4 planetary ball mill) 1 hour under the rotating speed of 300r/min; spray-drying process in centrifugal spray granulating and drying machine, under 100 ℃ of conditions; then product is placed under the argon shield and handled 4 hours down at 300 ℃, obtain the pretreatment sample powder behind the natural cooling at tube furnace.
Gained pretreatment sample powder is adopting fusion machine (the star technological development IQM-50 of Co., Ltd is opened in Luoyang) fusion treatment after 1 hour under the rotating speed of 200r/min; place under the argon shield and handled 9 hours down for 750 ℃ at tube furnace; naturally cool to room temperature, obtain the cathode material lithium vanadium phosphate of lithium ion battery matrix through pulverizing, shaping, classification after 1.5 hours through the 1000r/min fusion treatment.With above-mentioned phosphoric acid vanadium lithium matrix and 2wt%SBR, 1%Ag mix to coat 0.5 hour, and 1000 ℃ of following carbonization treatment 5 hours, above-mentioned material was carried out mechanical fusion treatment 3 hours under the rotating speed of 500r/min.The modified phosphate vanadium lithium material for preparing.Synthetic phosphoric acid vanadium lithium positive electrode for the almost spherical spherical, that major and minor axis is 5～50 μ m, rhombus, taper, sheet, stratiform or/and bulk, particle mean size d
50=20.14 μ m, specific area is 10.286m
2/ g.Ground and did X-ray diffraction X ' the Pert PRO diffractometer of company (Dutch PANalytical) behind 200 mesh sieves, ESEM (the KYKY-2800B type ESEM of Beijing KYKY Technology Development Co., Ltd.) is analyzed and electrochemical property test.The electrochemical property test of simulated battery carries out on the new Weir battery testing system in Shenzhen; the positive pole of button simulated battery that is used for electric performance test is by synthetic sample, conductive agent acetylene black, the binding agent PVdF ratio according to 90: 5: 5; making solvent with NMP is applied on the Al paper tinsel after evenly; 120 ℃ of dryings are after 12 hours; spreading and to be die-cut into diameter be the 8.4mm disk; simulated battery is assembled in the MBRAUN glove box of argon shield and carries out H
2O and O
2Content be lower than 2ppm, negative pole is a metal lithium sheet, barrier film is Celgard2400, electrolyte is 1molL
-1LiPF
6/ DMC+DEC+EC (volume ratio is 1: 1: 1), with the 0.25C rate charge-discharge, when charging/discharging voltage is 3.0-4.3V, 3.0-4.9V, maximum discharge capacity reaches 128.34mAh/g and 175.62mAh/g respectively, coulombic efficiency is respectively 98.9% and 97.5% first, and the capability retention after 30 weeks of circulating is respectively 98.3% and 89.0%.The X-ray diffracting spectrum of the phosphoric acid vanadium lithium that the present invention synthesizes is seen Fig. 1; The SEM of synthetic sample presoma sees Fig. 2; Sample is seen Fig. 3-1 and Fig. 3-2 at 500 times and 2000 times of following stereoscan photographs; The stereoscan photograph of synthetic sample primary particle is seen Fig. 4; Charging and discharging curve in 3.0-4.3V, 3.0-4.9V charging/discharging voltage scope is seen Fig. 5; In 3.0-4.3V, 3.0-4.9V charging/discharging voltage scope, the capacity cyclic curve under the 0.25C rate charge-discharge is seen Fig. 6; In 3.0-4.9V charging/discharging voltage scope, the reversible capacity in 0.25C, 1C, 5C and 10C multiplying power following time is respectively 175.62,156.34,130.14,105.21mAh/g, and discharge curve is seen Fig. 7, and material has excellent multiplying power discharging property.
Feed hydrogen lithia, vanadic oxide, ammonium dihydrogen phosphate and the ball mill grinding of citric acid process to nanoscale, are accurately taken by weighing lithium hydroxide (LiOHH
2O) 87.52 grams, vanadic oxide (V
2O
5) 138.10 the gram, ammonium dihydrogen phosphate (NH
4H
2PO
4) 256.52 grams and citric acid 309.32 grams.Citric acid is dissolved in 1700 milliliters of 80 ℃ of deionized waters, and constant temperature stirred 3 hours; Lithium hydroxide, vanadic oxide and ammonium dihydrogen phosphate are mixed back ball milling 0.5 hour under the rotating speed of 300r/min, then mixture is added in the citric acid solution, stirred 3 hours at 80 ℃ of following constant temperature, until reacting completely.
With above-mentioned sample ball milling 1 hour under the rotating speed of 400r/min, spray-drying process under 300 ℃ of conditions places product then under the argon shield and handled 4 hours down at 350 ℃ at tube furnace, obtains the presoma of phosphoric acid vanadium lithium behind the natural cooling.
The presoma of gained phosphoric acid vanadium lithium is adopting fusion machine fusion treatment after 1 hour under the rotating speed of 300r/min; place under the argon shield and handled 8 hours down for 800 ℃ at tube furnace; naturally cool to room temperature, through the 900r/min fusion treatment after 1.5 hours through obtaining the cathode material lithium vanadium phosphate of lithium ion battery matrix after pulverizing, shaping, the classification.Above-mentioned phosphoric acid vanadium lithium matrix mixed coating with 1wt% coal tar pitch, 1wt.% nano-sized carbon microballoon, 1wt.%CuO 4 hours, and, above-mentioned material was carried out mechanical fusion treatment 4 hours under the rotating speed of 200r/min 500 ℃ of following carbonization treatment 12 hours.The modified phosphate vanadium lithium material for preparing.Synthetic phosphoric acid vanadium lithium positive electrode particle mean size d
50=18.54 μ m, specific area is 8.631m
2/ g.Ground electrochemical property test behind 200 mesh sieves, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery (method and embodiment 1 are together), with the 0.25C rate charge-discharge, when charging/discharging voltage is 3.0-4.3V, 3.0-4.9V, maximum discharge capacity reaches 126.54mAh/g and 175.24mAh/g respectively, coulombic efficiency is respectively 96.5% and 94.3% first, and the capability retention after 30 weeks of circulating is respectively 98.4% and 88.7%.
Embodiment 3
Lithium hydroxide, ammonium metavanadate, ammonium dihydrogen phosphate, citric acid raw material are milled to nano particle with sand mill respectively, accurately take by weighing lithium hydroxide (LiOHH
2O) 13.00 grams, ammonium metavanadate (NH
4VO
3) 23.18 the gram, ammonium dihydrogen phosphate (NH
4H
2PO
4) 34.22 grams and citric acid 30.94 grams.Lithium hydroxide, ammonium metavanadate and ammonium dihydrogen phosphate are dissolved in respectively in 120 milliliters of 70 ℃ of deionized waters, after the dissolving three kinds of solution are mixed, add citric acid then, constant temperature stirred 1.5 hours; Mixed liquor stirred 1 hour at 80 ℃ of following constant temperature, to reacting completely.
With above-mentioned solution ball milling 1 hour under the rotating speed of 300r/min, spray-drying process under 130 ℃ of conditions places product then under the nitrogen protection and handled 5 hours down at 350 ℃ at tube furnace, obtains the pretreatment sample powder behind the natural cooling.
Gained pretreatment sample powder is adopting fusion machine fusion treatment after 1.5 hours under the rotating speed of 300r/min; place under the nitrogen protection and handled 10 hours down for 800 ℃ at tube furnace; naturally cool to room temperature, the 1000r/min fusion treatment obtained the cathode material lithium vanadium phosphate of lithium ion battery matrix through pulverizing, shaping, classification after 1 hour.Above-mentioned phosphoric acid vanadium lithium matrix mixed coating with 2wt% coal tar pitch, 0.5wt.% nanometer Au powder 6 hours, and, above-mentioned material was carried out mechanical fusion treatment 0.5 hour under the rotating speed of 1100r/min 1200 times carbonization treatment 1 hour.The phosphoric acid vanadium lithium material for preparing.Synthetic phosphoric acid vanadium lithium positive electrode particle mean size d
50=17.78 μ m, specific area is 9.563m
2/ g.Did physical property test and electrochemical property test after grinding 200 mesh sieves, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery (method and embodiment 1 are together), with the 0.25C rate charge-discharge, when charging/discharging voltage is 3.0-4.3V, 3.0-4.9V, maximum discharge capacity reaches 127.83mAh/g and 175.53mAh/g respectively, coulombic efficiency is respectively 96.1% and 93.6% first, and the capability retention after 30 weeks of circulating is respectively 97.4% and 87.8%.
Embodiment 4
Lithium acetate, vanadic oxide and tartaric acid raw material are milled to nanometer scale with impact type micro mist balling machine.Accurately take by weighing lithium acetate (LiCH
3COO2H
2O) 752.2 grams, vanadic oxide (V
2O
5) 451.1 the gram, phosphoric acid (H
3PO
4) 850.3 grams and tartaric acid 736.4 grams.Phosphoric acid is dissolved in 250 milliliters of 70 ℃ of deionized waters, and constant temperature stirred 2.5 hours; The tartaric acid that takes by weighing is added while stirring; Subsequently lithium acetate and vanadic oxide are stirred in the above-mentioned solution of adding successively, stirred 1.5 hours at 70 ℃ of following constant temperature, until reacting completely; Mixed solution is placed 100 ℃ dry 24 hours of baking oven, and this moment, solution parched fully.
The above-mentioned dry sample of crossing was adopted fusion machine fusion treatment 1 hour under the rotating speed of 800r/min; spray-drying process under 260 ℃ of conditions; then product is placed under the nitrogen protection and handled 3 hours down at 350 ℃, obtain the pretreatment sample powder behind the natural cooling at box type furnace.
Gained pretreatment sample powder is at ball milling under the rotating speed of 300r/min after 1 hour; place under the nitrogen protection and handled 10 hours down for 800 ℃ at box type furnace; naturally cool to room temperature, through the 900r/min fusion treatment after 1.5 hours through obtaining the cathode material lithium vanadium phosphate of lithium ion battery matrix after pulverizing, shaping, the classification.With above-mentioned phosphoric acid vanadium lithium matrix and 2wt% coal tar pitch, the 1wt% carbon nano-fiber mix to coat 4 hours, and 700 ℃ of following carbonization treatment 9 hours, above-mentioned material was carried out mechanical fusion treatment 2.5 hours under the rotating speed of 800r/min.The phosphoric acid vanadium lithium material for preparing.Synthetic phosphoric acid vanadium lithium positive electrode particle mean size d
50=14.63 μ m, specific area is 13.425m
2/ g.Ground electrochemical property test behind 200 mesh sieves, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery (method and embodiment 1 are together), with the 0.25C rate charge-discharge, when charging/discharging voltage is 3.0-4.3V, 3.0-4.9V, maximum discharge capacity reaches 127.35mAh/g and 174.25mAh/g respectively, coulombic efficiency is respectively 97.2% and 95.9% first, and the capability retention after 30 weeks of circulating is respectively 97.9% and 87.9%.
Embodiment 5
Lithium oxalate, vanadium trioxide and urea raw material are milled to nanoscale with stirring ball mill.Accurately take by weighing lithium oxalate 816.0 grams, vanadium trioxide 735.4 grams, phosphorus pentoxide 1044.8 grams and urea 294.6 grams.Phosphorus pentoxide is dissolved in 1 liter of 60 ℃ of warm water, stirred 1.5 hours; Again lithium oxalate, vanadium trioxide are stirred successively and add in the above-mentioned solution; Add urea at last; Constant temperature stirred 3 hours, reacted completely to mixed solution, did not have bubble to produce.
With above-mentioned solution spray-drying process under 280 ℃ of conditions, then product is placed under the nitrogen protection and handled 6 hours down at 300 ℃ at box type furnace, obtain the pretreatment sample powder behind the natural cooling.
Gained pretreatment sample powder is adopting fusion machine fusion treatment after 1 hour under the rotating speed of 600r/min; place under the argon shield and handled 12 hours down for 800 ℃ at tube furnace; naturally cool to room temperature, through the 1000r/min fusion treatment after 1.5 hours pulverizing again, shaping, classification obtain the cathode material lithium vanadium phosphate of lithium ion battery matrix.With above-mentioned phosphoric acid vanadium lithium matrix and 2wt%SBR, 0.5wt.% nanometer Al powder mix to coat 2 hours, and 1000 ℃ of following carbonization treatment 4 hours, above-mentioned material was carried out mechanical fusion treatment 2 hours under the rotating speed of 500r/min.Synthetic phosphoric acid vanadium lithium positive electrode particle mean size d
50=14.46 μ m, specific area is 7.638m
2/ g.After grinding 200 mesh sieves, the phosphoric acid vanadium lithium material for preparing did electrochemical property test, do negative pole and electrode is assembled into simulated battery (method and embodiment 1 are together) with metal lithium sheet, with the 0.25C rate charge-discharge, when charging/discharging voltage is 3.0-4.3V, 3.0-4.9V, maximum discharge capacity reaches 128.77mAh/g and 174.98mAh/g respectively, coulombic efficiency is respectively 95.8% and 96.6% first, and the capability retention after 30 weeks of circulating is respectively 96.3% and 89.7%.
Embodiment 6
It is nanometer scale that raw material lithium carbonate, vanadic oxide and glucose are crushed to granularity through circulating agitating ball mill respectively, accurately takes by weighing lithium carbonate (Li
2CO
3) 163.2 the gram, vanadic oxide (V
2O
5) 270.9 the gram, phosphoric acid (H
3PO
4) 509.3 grams and glucose 532.9 restrains and be dissolved in respectively in 500 milliliters of 40 ℃ of deionized waters; Glucose solution is added in the phosphoric acid solution earlier, lithium carbonate and vanadic oxide solution are added successively again, 40 ℃ of constant temperature stirs and reacted completely to mixed solution in 3 hours, does not have bubble to produce.
With above-mentioned sample ball milling 12 hours under the rotating speed of 200r/min, spray-drying process under 180 ℃ of conditions places product then under the argon shield and handled 2 hours down at 450 ℃ at tube furnace, obtains the pretreatment sample powder behind the natural cooling.
Gained pretreatment sample powder is adopting fusion machine fusion treatment after 0.5 hour under the rotating speed of 1100r/min; place under the argon shield and handled 8 hours down for 600 ℃ at tube furnace; naturally cool to room temperature, obtain the cathode material lithium vanadium phosphate of lithium ion battery matrix through pulverizing, shaping, classification after 4 hours through the 200r/min fusion treatment.With above-mentioned phosphoric acid vanadium lithium matrix and 2wt% polyacrylonitrile, 1% carbon nano-tube is mixed coating 3.5 hours, 1200 ℃ of following carbonization treatment 1 hour, above-mentioned material was carried out mechanical fusion treatment 4 hours under the rotating speed of 3r/min, the modified phosphate vanadium lithium material for preparing.Synthetic phosphoric acid vanadium lithium positive electrode particle mean size d
50=18.43 μ m, specific area is 10.213m
2/ g.Did rerum natura and electrochemical property test after grinding 200 mesh sieves.Do negative pole and electrode is assembled into simulated battery (method and embodiment 1 are together) with metal lithium sheet, with the 0.25C rate charge-discharge, when charging/discharging voltage is 3.0-4.3V, 3.0-4.9V, maximum discharge capacity reaches 126.46mAh/g and 176.53mAh/g respectively, coulombic efficiency is respectively 98.6% and 96.8% first, and the capability retention after 30 weeks of circulating is respectively 97.3% and 89.5%.
Embodiment 7
Raw material lithium oxalate, vanadic oxide, ammonium dihydrogen phosphate and the ball mill grinding of citric acid process to nanoscale, are accurately taken by weighing lithium oxalate 150 grams, vanadic oxide 180.4 grams, ammonium dihydrogen phosphate 339.5 grams and citric acid 412.3 grams.Citric acid is dissolved in 1.5 liters of 90 ℃ of deionized waters, and constant temperature stirred 1 hour; Lithium oxalate, vanadic oxide and ammonium dihydrogen phosphate are mixed back ball milling 0.5 hour under the rotating speed of 500r/min, then mixture is added in the citric acid solution, stirred 1 hour at 90 ℃ of following constant temperature, until reacting completely.
With above-mentioned sample ball milling 0.5 hour under the rotating speed of 500r/min, spray-drying process under 360 ℃ of conditions places product then under the argon shield and handled 4 hours down at 200 ℃ at tube furnace, obtains the presoma of phosphoric acid vanadium lithium behind the natural cooling.
The presoma of gained phosphoric acid vanadium lithium is adopting fusion machine fusion treatment after 0.5 hour under the rotating speed of 1100r/min; place under the argon shield and handled 5 hours down for 950 ℃ at tube furnace; naturally cool to room temperature, through the 1100r/min fusion treatment after 0.5 hour through obtaining cathode material lithium vanadium phosphate of lithium ion battery after pulverizing, shaping, the classification.With above-mentioned phosphoric acid vanadium lithium and 2wt% epoxy resin, the 0.5wt.% nano Cu powder is mixed coating and was handled 4.5 hours, mechanical fusion treatment was carried out 3 hours with above-mentioned material, the modified phosphate vanadium lithium material for preparing 550 ℃ of following carbonization treatment 12 hours in the back under the rotating speed of 600r/min.Synthetic phosphoric acid vanadium lithium positive electrode particle mean size d
50=7.54 μ m, specific area is 14.47m
2/ g.Carried out electrochemical property test after grinding 200 mesh sieves, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery (method and embodiment 1 are together), with the 0.25C rate charge-discharge, when charging/discharging voltage is 3.0-4.3V, 3.0-4.9V, maximum discharge capacity reaches 127.05mAh/g and 177.8mAh/g respectively, coulombic efficiency is respectively 96.1% and 95.5% first, and the capability retention after 30 weeks of circulating is respectively 97.3% and 87.6%.
Comparative example
Get commodity cobalt acid lithium and make simulated battery according to embodiment 1 described simulated battery manufacture method as positive electrode, with the 0.25C rate charge-discharge, when charging/discharging voltage is 3.0-4.3V, maximum discharge capacity is 146.35mAh/g, cobalt acid lithium only has discharge platform zone between the 3.0-4.3, and average discharge volt is 3.7, and the charging cut-ff voltage does not have capacity to increase when being higher than 4.3V, coulombic efficiency is respectively 92.3% first, and the capability retention after 30 weeks of circulating is 96.2%.This shows that phosphoric acid vanadium lithium is at maximum discharge capacity, effect all is better than the lithium cobaltate cathode material of prior art aspect coulombic efficiency, average discharge volt and the circulation volume conservation rate first.
The present invention adopts nano particle (precursor) liquid phase reactor to prepare cathode material lithium vanadium phosphate of lithium ion battery.Nano particle has solved synthetic middle maximum difficult point---the homogeneity question of dispersing and mixing of material, feasible synthetic material high conformity, the synthetic phosphoric acid vanadium lithium of liquid phase method has guaranteed that reactant can carry out hybrid reaction on the molecule rank, sufficient reacting, need not the pH value of strict control solution, the primary particle granularity of synthetic material is at the nanometer or the sub-micron order of magnitude, and second particle is spherical in shape or class is spherical, even particle size distribution.Complexing agent plays the reducing agent effect in the roasting reaction, unnecessary complexing agent then evenly is coated on the effect of playing enhancing conductivity on the active material after the carbonization.By adding nanoscale Al, Mg, Cr, Co, Mn, Zn, Cu, Au, Ni, the conductive carbon material of Ag or Nb metallic element simple substance and oxide composition and high-specific surface area, as conductive acetylene carbon black Super-P, carbon fiber, carbon nano-tube or nano-sized carbon microballoon etc. carry out doping vario-property to material, perhaps material being carried out surface coating modification handles, but clad material is the organic substance of charing, as furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile; styrene butadiene rubber sbr; cellulose CMC; coke; coal tar pitch or petroleum asphalt, covering amount are 0.1～3wt.%.The synthetic phosphoric acid vanadium lithium of liquid phase method has been simplified operation sequence, has reduced production cost, has been helped the purity that synthetic material was controlled and improved to processing procedure.
Li source compound only give an example out lithium hydroxide LiOH, lithium carbonate Li among the embodiment
2CO
3, lithium acetate LiCH
3COO and lithium oxalate, because lithium chloride, lithium sulfate, lithium nitrate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 has and above-mentioned four kinds of chemical property that material is similar, the chemical reaction type that participates in is identical, in preparation method's of the present invention reaction, all can provide the lithium ion of target compound phosphoric acid vanadium lithium, and then Li source compound is suitable for the present invention.
The vanadium source compound vanadic oxide V that only gives an example out among the same embodiment
2O
5, vanadium trioxide V
2O
3, ammonium metavanadate NH
4VO
3, because vanadium dioxide VO
2, sodium metavanadate is identical with above-mentioned three kinds of materials with electrochemical properties with the reaction type that the carbonic acid vanadium participates in chemical reaction in the method for the invention, all can provide the target compound phosphoric acid vanadium lithium required v element, and then the vanadium source compound is suitable for the present invention.
The P source compound phosphoric acid H that only gives an example out among the embodiment
3PO
4, ammonium dihydrogen phosphate NH
4H
2PO
4, phosphorus pentoxide P
2O
5, because ammonium phosphate (NH
4)
3PO
4, diammonium hydrogen phosphate (NH
4)
2HPO
4, that triammonium phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate or dipotassium hydrogen phosphate participate in the reaction type of chemical reaction in the present invention is identical with above-mentioned three kinds of materials with electrochemical properties, and the PO of target compound phosphoric acid vanadium lithium all can be provided by reaction
4 3-Group, and then P source compound is suitable for the present invention.
Only give an example out glucose, citric acid, urea, tartaric acid of complex compound among the embodiment, because it is identical with above-mentioned four kinds of materials with role that sucrose, acrylic acid, fructose, ascorbic acid, polyethylene glycol or glycerol participate in the reaction type of chemical reaction in the present invention, and then complexing agent is suitable for the present invention.
Only give an example out among the embodiment conductive agent nanoscale Ag, Al, Cu, Au, CuO, nano-sized carbon microballoon, carbon fiber, carbon nano-tube and nano-sized carbon microballoon, nanoscale Cr, Co, Mn, Zn, Mg, Ni or Nb metallic element simple substance and oxide thereof, conductive acetylene carbon black Super-P have the effect that improves the phosphoric acid vanadium lithium performance equally, so be suitable for the present invention.
Only give an example out styrene butadiene rubber sbr, cellulose CMC, pitch, polyacrylonitrile, epoxy resin of clad material among the embodiment, because furane resins, Lauxite, ethyl-amine resin, phenolic resins, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, coke product in carbonization reaction are identical or similar with above-mentioned five kinds of materials, can improve the electronic conductance of preparation material, and then improve the chemical property of material, so be suitable for the present invention.
Claims (9)
1. the preparation method of a cathode material lithium vanadium phosphate of lithium ion battery may further comprise the steps: one, the preparation of nano particle: respectively Li source compound, vanadium source compound, P source compound and complexing agent are passed through the wet method super-fine ball-milling treatment to nano-scale particle; Two, liquid-phase mixing reaction: by the ratio Li of amount of substance: V: P: complexing agent=3.0～3.3: 2: 3: 1.5～2.2 take by weighing Li source compound, vanadium source compound, P source compound and complexing agent is dissolved in 40～90 ℃ of deionized waters, stirs and obtains composite material in 1～3 hour; Three, the preparation of precursor: with composite material ball milling 0.5～24 hour under the rotating speed of 200～500r/min, spray drying obtains anode material precursor under 100～360 ℃ of conditions then, precursor be shaped as almost spherical that sphere, major axis and minor axis are 5～50 μ m, rhombus, taper, sheet, stratiform or/and block post forming particle; Four, preliminary treatment: the post forming particle under inert atmosphere protection, 200～450 ℃ of preliminary treatment 2～12 hours, is obtained the preliminary treatment powder behind the natural cooling; Five, calcination process: in corundum or graphite saggar, calcination process is 5～24 hours under inert atmosphere protection, in 600～950 ℃ with the preliminary treatment powder packing, is cooled to room temperature then naturally, obtains Li
3V
2(PO
4)
3Matrix; Six, with Li
3V
2(PO
4)
3Matrix surface clad nano composite conducting material was handled under 500～1200 ℃ temperature 1～12 hour then; Described nano combined electric conducting material is nano combined conductive agent, nano metal or nano-metal-oxide conductive agent, and covering amount is 0.1～3wt.% of matrix; Described nano combined conductive agent is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile; butadiene-styrene rubber (SBR); cellulose; the pyrolytic carbon that coal tar pitch or petroleum asphalt organic substance form; conductive acetylene carbon black; carbon nano-fiber; carbon nano-tube or nano-sized carbon microballoon conduction raw material of wood-charcoal material; nano metal is Al; Mg; Cr; Co; Mn; Zn; Cu; Au; Ni; Ag or Nb metallic element simple substance, and nano-metal-oxide is Al; Mg; Cr; Co; Mn; Zn; Cu; Au; Ni; the metal oxide of Ag or Nb; Seven, the material that step 6 is made carried out mechanical fusion treatment 0.5～4 hour under the rotating speed of 200～1100r/min, obtained spherical compound phosphoric acid vanadium lithium anode material.
2. the preparation method of cathode material lithium vanadium phosphate of lithium ion battery according to claim 1, it is characterized in that: described Li source compound is lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, tert-butyl alcohol lithium, lithium benzoate, lithium formate, four water citric acid lithium or lithium oxalates; Described vanadium source compound is vanadic oxide, vanadium trioxide, vanadium dioxide, ammonium metavanadate or carbonic acid vanadium; Described P source compound is phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or phosphorus pentoxide; Described complexing agent is sucrose, glucose, tartaric acid, citric acid, urea, acrylic acid, fructose, ascorbic acid, polyethylene glycol or glycerol.
3. the preparation method of cathode material lithium vanadium phosphate of lithium ion battery according to claim 2, it is characterized in that: described ratio Li by amount of substance: V: P: complexing agent=3.0～3.3: 2: 3: 1.5～2.2 take by weighing Li source compound, vanadium source compound, P source compound and complexing agent, earlier Li source compound, vanadium source compound and P source compound solids are mixed, complexing agent is dissolved in 40～90 ℃ of deionized waters, the solids that mixes is dissolved in the enveloping agent solution, 40～90 ℃ were stirred 1～3 hour down again; Or P source compound is dissolved in 40～90 ℃ of deionized waters, again complexing agent, Li source compound, vanadium source compound solids are added in the P source compound solution successively, 40～90 ℃ were stirred 1～3 hour down; Or be dissolved in 40～90 ℃ of deionized waters respectively Li source compound, vanadium source compound, P source compound and complexing agent and stirring, contain Li source compound, vanadium source compound and the enveloping agent solution that will prepare then add in the P source compound solution, and 40～90 ℃ were stirred 1～3 hour down.
4. the preparation method of cathode material lithium vanadium phosphate of lithium ion battery according to claim 3, it is characterized in that: described composite material ball milling under the rotating speed of 200～500r/min adopts stirring ball mill, circulating agitating ball mill, sand mill, colloid mill, planetary ball mill or impact type micro mist balling machine, and ball grinder and abrading-ball material are stainless steel, corundum, zirconia or agate.
5. the preparation method of cathode material lithium vanadium phosphate of lithium ion battery according to claim 4 is characterized in that: described under 100～360 ℃ of conditions spray drying, in centrifugal spray granulating and drying machine, carry out.
6. the preparation method of cathode material lithium vanadium phosphate of lithium ion battery according to claim 5, it is characterized in that: before preliminary treatment under the inert atmosphere protection, fusion treatment is 0.5～2 hour under the rotating speed of 200～1100r/min with the post forming particle.
7. the preparation method of cathode material lithium vanadium phosphate of lithium ion battery according to claim 6, it is characterized in that: before the described calcination process, on the fusion machine, fusion treatment is 0.5～4 hour under the rotating speed of 200～1100r/min with the preliminary treatment powder; The phosphoric acid vanadium lithium that obtains after the calcination process is with fusion machine fusion treatment 0.5～4 hour under the rotating speed of 200～1100r/min.
8. the preparation method of cathode material lithium vanadium phosphate of lithium ion battery according to claim 7 is characterized in that: pulverize after described roasting and the fusion treatment with classification and handle.
9. the preparation method of cathode material lithium vanadium phosphate of lithium ion battery according to claim 8, it is characterized in that: described clad nano composite conducting material adopts matrix and nano combined electric conducting material to mix on fusion machine, blade paddle mixer, conical agitator, twin-shaft mixer or planetary stirring machine mixing mixing plant and coated 0.5～6 hour, afterwards compound is handled under 500～1200 ℃ temperature 1～12 hour.
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