CN101320809B - Lithium ion battery anode material manganese lithium phosphate and preparation method thereof - Google Patents
Lithium ion battery anode material manganese lithium phosphate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a manganese/lithium phosphate of lithium iron battery positive pole material and a production method thereof, the technical issue to be solved is to improve electrochemical performances of the positive pole material. The material of the invention includes substrates of manganese/lithium phosphate which are covered by a carbon material covering layer, the lithium covering the manganese/lithium phosphate behind the carbon material covering layer is spherical and has microscopic characteristics of being near spherical, rhombic, tapered, tabular, layered or/and block-shaped as well as of having 0.5-30 mum long and short axles. The production method comprises the following steps of: production of nanometer particles, liquid phase mixed reaction, production of precursor, sintering treatment, covering organic substances. Compared with the prior art, the invention improves the electron conductivity of the manganese/lithium phosphate by covering with carbon liquid phase, the carbon sufficiently covers active materials to efficiently prevent particle aggregation, the invention has the characteristics of about 4V of discharge voltage, high discharge and charge capacitance, excellent circulation stability, high safety, simple process, low cost and little influence on the environment.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, particularly a kind of lithium manganese phosphate material and preparation method thereof.
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 is successfully realized commercially producing of lithium rechargeable battery for Sony company, 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 the 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, ternary material and LiFePO 4.Lithium and cobalt oxides uses 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 burning, the relatively poor shortcoming of fail safe, and its discharge voltage is lower, and average discharge volt is about 3.6V, and capacity is lower than 150mAh/g.Lithium manganese oxide anode material aboundresources, cost are low, but its electrochemistry capacitance is lower, and its application of high-temperature behavior official post 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, lithium manganese phosphate has the following advantages: higher discharge voltage plateau, average discharge volt is near 4.0V, has higher charge/discharge capacity, theoretical capacity is 170mAh/g, and reversible capacity can reach more than the 140mAh/g, excellent cyclical stability, good fail safe and low cost, thereby be expected to become anode material for lithium-ion batteries of new generation.
At present, few to the research of lithium ion battery anode material manganese lithium phosphate report, domestic still do not have a patent report.Known lithium manganese phosphate synthetic method mainly contains solid phase method, synthesized the olivine-type lithium manganese phosphate as Zhang Bao etc. with solid phase method, sample discharge capacity was first rolled up 6 phase 960-964 pages or leaves in 2005 36 near 100mAh/g[Central South University journal (natural science edition)], Chang Xiaoyan etc. have also obtained similar result [2004 20 volumes of Acta PhySico-Chimica Sinica, 10 phase 1249-1252 pages or leaves].These synthetic lithium salts, manganese salt, phosphate and four kinds of primary raw materials of material with carbon element of all using.The raw material that high temperature solid-state method adopts is lithium salts, manganese salt and phosphate, through pre-burning, adds carbon reduction or hydrogen reducing roasting again, operates more loaded down with trivial detailsly, exists the purity of sintetics low, chemical property difference and the high problem of production cost.
Summary of the invention
The purpose of this invention is to provide a kind of lithium ion battery anode material manganese lithium phosphate and preparation method thereof, the technical problem that solve is to improve the chemical property of lithium manganese phosphate positive electrode.
The present invention is by the following technical solutions: a kind of lithium ion battery anode material manganese lithium phosphate, described lithium ion battery anode material manganese lithium phosphate has the lithium manganese phosphate matrix, matrix is coated with the material with carbon element coating layer, covering amount is 1～3wt.% of matrix, the almost spherical that lithium manganese phosphate lithium tool sphere behind the carbon coated material coating layer, major and minor axis are 0.5～30 μ m, rhombus, taper, sheet, stratiform are or/and block microscopic feature, and specific area is 5～40m
2/ g, tap density is 1.0～1.6g/ml.
The granularity of lithium ion battery anode material manganese lithium phosphate of the present invention is 0.5～30 μ m.
A kind of preparation method of lithium ion battery anode material manganese lithium phosphate may further comprise the steps: one, the preparation of nano particle: respectively Li source compound, water-insoluble manganese source compound, P source compound and water-insoluble simple substance carbon are handled to sub-micron or nano-scale particle; Two, liquid-phase mixing reaction: by the ratio Li of amount of substance: Mn: P: C=0.90～1.20: 1: 0.95～1.10: 0.5～2.0 are water-soluble or be distributed to and obtain composite material in the water with Li source compound, water-insoluble manganese source compound, P source compound and water-insoluble simple substance carbon; Three, the preparation of precursor: with composite material ball milling 0.5～12 hour under the rotating speed of 200～500r/min, spray drying obtains anode material precursor under 100～360 ℃ of conditions then; Four, calcination process: with the programming rate of precursor with 1～10 ℃/min, calcination process is 5～12 hours in 600～950 ℃, is cooled to room temperature then naturally, obtains the lithium manganese phosphate matrix; Five, after but the lithium manganese phosphate matrix surface coats the organic substance of the charing that accounts for matrix 1～3wt.%, programming rate with 1～10 ℃/min, carbonization treatment is 1～12 hour under 500～1200 ℃ temperature, naturally be cooled to room temperature, obtain being coated with on the lithium manganese phosphate matrix lithium ion battery anode material manganese lithium phosphate of material with carbon element coating layer.
The Li source compound of the inventive method is lithium hydroxide, lithium carbonate, lithium acetate, 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, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or lithium oxalate.
The water-insoluble manganese source compound of the inventive method is manganese acetate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide or manganous hydroxide.
The P source compound of the inventive method is phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate or dipotassium hydrogen phosphate.
The water-insoluble simple substance carbon of the inventive method is conductive acetylene carbon black Super P, conductive acetylene carbon black Ensaco or conductive nano carbon dust.
But the organic substance of the charing of the inventive method is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, butadiene-styrene rubber, cellulose, coke, coal tar pitch or petroleum asphalt.
Li source compound, water-insoluble manganese source compound, P source compound and water-insoluble simple substance carbon being handled of the inventive method to sub-micron or nano-scale particle employing wet method super-fine ball grinding method.
The Li source compound of the inventive method, water-insoluble manganese source compound, P source compound and water-insoluble simple substance carbon are dissolved in or are scattered in 20～90 ℃ of deionized waters, stir to obtain composite material in 0.5～3 hour.
The inventive method with composite material under the rotating speed of 200～500r/min before the ball milling, add the doping vario-property agent that accounts for composite material 0.1～3wt.%, described doping vario-property agent is compound, conductive acetylene carbon black Super-P, carbon nano-fiber, carbon nano-tube or the nano-sized carbon microballoon of Fe, Zr, Zn, Ti, Al, Mg, Cu, Cr, Ni, Ge or Nb element.
Carry out preliminary treatment before the inventive method calcination process: under protective gas helium, argon gas or nitrogen, with the programming rate of 1～10 ℃/min, at 200～450 ℃ of preliminary treatment 2～6 hours, natural cooling.
Before the preliminary treatment of the inventive method, fusion treatment is 0.5～2 hour under the rotating speed of 200～1100r/min.
After the preliminary treatment of the inventive method, fusion treatment is 0.5～2 hour under the rotating speed of 200～1100r/min.
The calcination process of the inventive method is carried out under protective gas helium, argon gas or nitrogen protection.
After the calcination process of the inventive method, fusion treatment is 0.5～4 hour under the rotating speed of 200～1100r/min.
After the fusion treatment after the inventive method calcination process, pulverize with classification and handle.
But the inventive method coats the organic substance of charing, and rotating speed 200～1000r/min coated 0.5～6 hour.
A kind of preparation method of lithium ion battery anode material manganese lithium phosphate may further comprise the steps: one, the preparation of nano particle: adopt the wet method super-fine ball grinding method to handle to sub-micron or nano-scale particle Li source compound and P source compound respectively; Two, liquid-phase mixing reaction: by the ratio Li of amount of substance: Mn: P: C=0.90～1.20: 1: 0.95～1.10: 0.5～2.0 are dissolved in Li source compound, water-soluble manganese source compound, P source compound and water-soluble carbon compound or be scattered in the water, obtain composite material; Three, the preparation of precursor: with composite material ball milling 0.5～12 hour under the rotating speed of 200～500r/min, spray drying obtains anode material precursor under 100～360 ℃ of conditions then; Four, preliminary treatment: under protective gas helium, argon gas or nitrogen, with 1～10 ℃/min programming rate, at 200～450 ℃ of preliminary treatment 2～6 hours, natural cooling; Five, calcination process: under protective gas helium, argon gas or nitrogen protection, with the programming rate of 1～10 ℃/min, calcination process is 5～12 hours in 600～950 ℃, is cooled to room temperature then naturally, obtains the lithium manganese phosphate matrix with the preliminary treatment powder; Six, after but the lithium manganese phosphate matrix surface coats the organic substance of the charing that accounts for matrix 1～3wt.%, programming rate with 1～10 ℃/min, carbonization treatment is 1～12 hour under 500～1200 ℃ temperature, naturally be cooled to room temperature, obtain being coated with on the lithium manganese phosphate matrix lithium ion battery anode material manganese lithium phosphate of material with carbon element coating layer.
The Li source compound of the inventive method is lithium hydroxide, lithium carbonate, lithium acetate, 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, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or lithium oxalate.
The water-soluble manganese source compound of the inventive method is manganese acetate, four water manganese acetates, manganese carbonate, manganous chloride, four water manganous chloride, manganese tetrachloride, manganese sulfate, manganese sulfate monohydrate, sulfate dihydrate manganese, three water manganese sulfates, four water manganese sulfates, Manganese sulfate pentahydrate, six water manganese sulfates, seven water manganese sulfate or manganese nitrates.
The P source compound of the inventive method is phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate or dipotassium hydrogen phosphate.
The water-soluble carbon compound of the inventive method is sucrose, glucose, tartaric acid, citric acid, urea, acrylic acid, fructose, ascorbic acid, polyethylene glycol or glycerol.
But the organic substance of the charing of the inventive method is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, butadiene-styrene rubber, cellulose, coke, coal tar pitch or petroleum asphalt.
The present invention compared with prior art, coat the electronic conductance that improves lithium manganese phosphate by the carbon liquid phase, adopt the synthetic cathode material lithium manganese phosphate of nano particle post forming method of liquid-solid phase combination, little and the epigranular dispersion of particle, carbon is full and uniform to the coating of active material, stoped particle agglomeration effectively, this lithium manganese phosphate positive electrode has the discharge voltage about 4V, higher charge/discharge capacity, excellent cyclical stability, safe, and preparation technology's program is simple, and production cost is low, helps the purity of program control and raising synthetic material, influence to environment is little, is applicable to the suitability for industrialized production of cleaning.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of the lithium manganese phosphate of embodiment 1 preparation.
Fig. 2 is the stereoscan photograph of the lithium manganese phosphate presoma of embodiment 1 preparation.
Fig. 3 is the stereoscan photograph of the lithium manganese phosphate of embodiment 1 preparation.
Fig. 4 is the one-shot forming particulate scan electromicroscopic photograph of the lithium manganese phosphate of embodiment 1 preparation.
Fig. 5 is the charging and discharging curve of lithium manganese phosphate in 2.75-4.50V charging/discharging voltage scope of embodiment 1 preparation.
Fig. 6 be the lithium manganese phosphate of embodiment 1 preparation in 2.75-4.50V charging/discharging voltage scope, 0.20mA/cm
2Charging and discharging currents density under the capacity cyclic curve.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further details.
Lithium ion battery anode material manganese lithium phosphate of the present invention has lithium manganese phosphate LiMnPO
4Matrix, matrix is coated with the material with carbon element coating layer, covering amount is 1～3wt.% of matrix, described anode material for lithium-ion batteries tool sphere, major and minor axis are that the almost spherical, rhombus, taper, sheet, stratiform of 0.5～30 μ m is or/and block microscopic feature, its granularity is 0.5～30 μ m, and specific area is 5～40m
2/ g, tap density is 1.0～1.6g/ml, with 0.20mA/cm
2Charging and discharging currents density discharge and recharge, when charging/discharging voltage was 2.75-4.50V, capacity was higher than 120mAh/g first, maximum discharge capacity is higher than 135mAh/g, coulombic efficiency is higher than 90% first, the capability retention after 40 weeks of circulating is higher than 98%.
The preparation method of lithium ion battery anode material manganese lithium phosphate of the present invention, adopt following steps:
One, the preparation of nano particle: respectively Li source compound, manganese source compound, P source compound and material with carbon element are passed through the wet method super-fine ball-milling treatment to sub-micron or nano-scale particle, be the one-shot forming particle, water miscible manganese source compound and material with carbon element then need not pass through this step process.The wet method super-fine ball-milling treatment adopts the circulating agitating ball mill of SX-2 type of Wuxi Xinguang Powder Processing Technology Co., Ltd., can also adopt other ball millings or disintegrating apparatus: 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.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, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or lithium oxalate.The manganese source compound is non-water-soluble manganese source compound manganese acetate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide or manganous hydroxide, or water miscible manganese source compound manganese acetate, four water manganese acetates, manganese carbonate, manganous chloride, four water manganous chloride, manganese tetrachloride, manganese sulfate, manganese sulfate monohydrate, sulfate dihydrate manganese, three water manganese sulfates, four water manganese sulfates, Manganese sulfate pentahydrate, six water manganese sulfates, seven water manganese sulfate or manganese nitrates.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.Material with carbon element is non-water-soluble simple substance carbon conductive acetylene carbon black Super P, conductive acetylene carbon black Ensaco or conductive nano carbon dust, or water miscible carbon compound sucrose, glucose, tartaric acid, citric acid, urea, acrylic acid, fructose, ascorbic acid, polyethylene glycol or glycerol.
Two, liquid-phase mixing reaction: with Li source compound, manganese source compound, P source compound and the material with carbon element of sub-micron or nano-scale particle, press amount of substance than Li: Mn: P: C=0.90～1.20: 1: 0.95～1.10: 0.5～2.0, be dissolved in 20～90 ℃ of deionized waters, stir and obtained composite material in 0.5～3 hour.
Three, the preparation of precursor: add the doping vario-property agent that accounts for composite material 0.1～3wt.% in composite material, the doping vario-property agent is compound, conductive acetylene carbon black Super-P, carbon nano-fiber, carbon nano-tube or the nano-sized carbon microballoon of Fe, Zr, Zn, Ti, Al, Mg, Cu, Cr, Ni, Ge or Nb element.Adopt the QM-1SP4 type planetary ball mill of Nanjing Univ. Instrument Factory, can also adopt stirring ball mill, circulating agitating ball mill, sand mill, colloid 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 0.5～12 hour under the rotating speed of 200～500r/min, then under 100～360 ℃ of conditions, obtain anode material precursor with centrifugal spray granulating and drying machine spray drying, precursor be shaped as almost spherical that sphere, major and minor axis are 5～30 μ m, rhombus, taper, sheet, stratiform or/and block post forming particle.
Four, the fusion treatment before the preliminary treatment:, adopt Luoyang to open the star technological development IQM-50 of Co., Ltd type and merge machine with post forming particle fusion treatment 0.5～2 hour under the rotating speed of 200～1100r/min.
Five, preliminary treatment: in protective gas helium He, argon Ar or nitrogen N
2Protection with the programming rate of 1～10 ℃/min, 200～450 ℃ of preliminary treatment 2～6 hours, obtains the preliminary treatment powder down behind the natural cooling, improve material moisture content; Preliminary treatment is adopted and is flown to reach the SXQ20-14-45 of electric furnace Co., Ltd type box type furnace, can also adopt enclosed vacuum drying oven, vacuum drier, tube furnace, vacuum furnace, bell jar stove, rotary furnace or tunnel cave.
Six, pretreated 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 particle size uniformity of material, adopts Luoyang to open the star technological development IQM-50 of Co., Ltd type and merges machine.
Seven, calcination process: with the preliminary treatment powder packing after the fusion treatment in corundum or graphite saggar, in protective gas helium He, argon Ar or nitrogen N
2Protection is flying to reach in the SKQ20-8-10 of the electric furnace Co., Ltd type tube furnace down, and with the programming rate of 1～10 ℃/min, calcination process is 5～12 hours in 600～950 ℃, is cooled to room temperature then naturally, obtains lithium manganese phosphate LiMnPO
4Matrix.
Eight, the fusion treatment after the calcination process: with lithium manganese phosphate LiMnPO
4Matrix improves the particle size uniformity of material with fusion machine fusion treatment 0.5～4 hour under the rotating speed of 200～1100r/min, adopts Luoyang to open the star technological development IQM-50 of Co., Ltd type and merges machine.
Nine, pulverizing and classification are handled: obtaining granularity is 0.5-30 μ m, pulverize to adopt earlier and pulverize at a high speed, the method that back low speed is pulverized adopts the AP10 type airslide disintegrating mill of Shandong elite powder technology company, can also be to pulverize at a high speed to adopt airslide disintegrating mill, high pressure flour mill or bar type mechanical crusher; 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.Adopt the MASTERSIZER2000 laser particle analyzer of Ma Erwen company (Malvem Instruments Ltd) that the lithium manganese phosphate matrix is carried out analytical test d
50, d
10, d
90d
50The particle mean size of expression powder, the cumulative particle sizes percentile of a sample reaches 50% o'clock pairing particle diameter, and to be particle diameter account for 50% greater than its particle to its physical significance, also accounts for 50%, d less than its particle
50Also be meso-position radius or median particle diameter.d
10The cumulative particle sizes distribution number that is a sample reaches 10% o'clock pairing particle diameter, its physical significance be particle diameter less than it particle account for 10%.d
90The cumulative particle sizes distribution number that is a sample reaches 90% o'clock pairing particle diameter, its physical significance be particle diameter less than it particle account for 90%.
Ten, at lithium manganese phosphate LiMnPO
4But matrix surface coats the organic substance of the charing that accounts for matrix 1～3wt.%, matrix and coating material are put into the SWFS type high-speed dispersion equipment of Shanghai Solvay, can also be in fusion machine, blade paddle mixer, conical agitator, twin-shaft mixer or the planetary stirring machine mixing mixing plant, rotating speed 200～1000r/min, mix and coat after 0.5～6 hour, programming rate with 1～10 ℃/min, with the carbonization treatment 1～12 hour under 500～1200 ℃ temperature of the material after coating, naturally be cooled to room temperature, obtain lithium ion battery anode material manganese lithium phosphate.But the organic substance of charing is 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.
After the lithium ion battery anode material manganese lithium phosphate that the embodiment of the invention makes ground 200 mesh sieves, adopt X ' the Pert PRO diffractometer of Dutch PANalytical company, the KYKY-2800B type ESEM of Beijing KYKY Technology Development Co., Ltd. that its microscopic feature is analyzed and tested, gas absorption (nitrogen adsorption method) specific area measuring is adopted in the test of specific area, and this method is utilized easy the to be acquired and good reversible adsorption characteristic of nitrogen.By this method the specific area of Ce Dinging we be referred to as " equivalence " specific area, the notion of so-called " equivalence " is meant: the surface area of sample is to characterize by nitrogen molecule quantity and molecule the maximum cross-section area that its surperficial solid matter coats (absorption).Practical measurement goes out nitrogen molecule at sample surfaces balance saturated extent of adsorption (V), calculate individual layer saturated extent of adsorption (Vm) by different theoretical models, and then draw the molecule number, adopt surperficial close-packed hexagonal Model Calculation to go out nitrogen molecule equivalence the maximum cross-section area (Am), can obtain the specific area of sample.The test of tap density is contained in a certain amount of powder in the graduated cylinder, by vibrating device vibration, no longer reduces until the volume of powder, and the volume of the quality of powder after divided by jolt ramming obtains the tap density of sample.
Electrochemical property test is undertaken by the button simulated battery, adopts the new Weir battery testing system in Shenzhen.Be used for material sample that the positive pole of the button simulated battery of electric performance test makes by embodiment, conductive agent acetylene black, binding agent PVdF according to 90: 5: 5 ratio of mass ratio; making solvent with N-methyl pyrrolidone 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 Braun 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.Experimental technique is: with 0.20mA/cm
2Charging and discharging currents density discharge and recharge, when charging/discharging voltage is 2.75～4.50V, test capacity, maximum discharge capacity first, coulombic efficiency (coulombic efficiency=discharge capacity/initial charge capacity) first first first, the capability retention after 40 weeks of circulating (the discharge capacity * 100% in the discharge capacity in capability retention=n week/the 1st week).
Above-mentioned sample was added behind the 0.1wt.%CuO under the rotating speed of 500r/min ball milling 0.5 hour; spray-drying process under 100 ℃ of conditions; fusion treatment is 2 hours under the rotating speed of 200r/min; then product is placed under the argon shield at box type furnace; programming rate with 8 ℃/min; 300 ℃ of following preliminary treatment 4 hours, obtain the preliminary treatment powder behind the natural cooling, both the lithium manganese phosphate presoma.
Gained preliminary treatment powder is in fusion treatment under the rotating speed of 200r/min after 4 hours; programming rate with 2 ℃/min; place under the argon shield 800 ℃ of following calcination process 9 hours; naturally cool to room temperature; process 200r/min fusion treatment 4 hours; obtain the lithium manganese phosphate matrix through pulverizing, shaping, classification, test its granularity d
10=8.98 μ m, d
50=19.03 μ m, d
90=28.70 μ m.
Above-mentioned lithium manganese phosphate matrix is mixed with the 3wt% styrene butadiene rubber sbr, and rotating speed 400r/min coated after 0.5 hour, and with the programming rate of 3 ℃/min, 600 ℃ of following carbonization treatment 10 hours, cooling obtained lithium ion battery anode material manganese lithium phosphate naturally.
The x-ray diffraction pattern of the finished-product material that embodiment 1 makes as shown in Figure 1, by knowing that with the comparative analysis of standard diagram card synthetic material is an olivine structural.As shown in Figure 2, the spheroidization degree height of material presoma, the dispersive property of illustrative material in liquid phase is good.As shown in Figure 4, the stereoscan photograph under 1000 times is observed, the one-shot forming particle of material, and diameter of particle is at 0.1-1.0 μ m.As shown in Figure 3,500 times of stereoscan photographs are observed, and material has the structure of the sphere of post forming, realize that by post forming material evenly disperses.Granularity d
10=2.62 μ m, d
50=12.14 μ m, d
90=23.92 μ m, specific area is 25m
2/ g, tap density is 1.20g/ml.As shown in Figure 5, with 0.20mA/cm
2Charging and discharging currents density discharge and recharge, when charging/discharging voltage is 2.75-4.50V, capacity is 126.627mAh/g first, as shown in Figure 6, the maximum discharge capacity of synthetic material is 136.97mAh/g, and coulombic efficiency is 95.5% first, the capability retention that circulates after 40 weeks is 106.98%, the capacity first of the material of doing is low slightly, and is in rising trend with circulation volume, and above-mentioned experimental data shows that the chemical property of material is good.
With above-mentioned sample and the Al that accounts for sample 2wt.%
2O
3Mix back ball milling 1 hour under the rotating speed of 400r/min; spray-drying process under 360 ℃ of conditions; fusion treatment is 1 hour under the rotating speed of 600r/min; then product is placed under the argon shield at tube furnace; programming rate with 1 ℃/min; 350 ℃ of following preliminary treatment 4 hours, obtain the preliminary treatment powder behind the natural cooling.
Gained preliminary treatment powder is adopting fusion machine fusion treatment after 2.5 hours under the rotating speed of 300r/min; place under the argon shield at tube furnace; programming rate with 10 ℃/min; 850 ℃ of following calcination process 8 hours; naturally cool to room temperature; after 3.5 hours, obtain the lithium manganese phosphate matrix through the 350r/min fusion treatment, test its granularity d through pulverizing, shaping, classification
10=0.634 μ m, d
50=6.142 μ m, d
90=21.442 μ m.
Above-mentioned lithium manganese phosphate matrix is mixed with the 2wt% coal tar pitch, and rotating speed 200r/min coated 4 hours, and with the programming rate of 4 ℃/min, 500 ℃ of following carbonization treatment 12 hours, cooling obtained lithium ion battery anode material manganese lithium phosphate naturally.
The lithium manganese phosphate material for preparing carried out electrochemical property test after grinding 200 mesh sieves, synthetic lithium manganese phosphate positive electrode for the almost spherical spherical, that major and minor axis is 0.5～30 μ m, rhombus, taper, sheet, stratiform or/and block granularity d
10=0.56 μ m, d
50=6.53 μ m, d
90=18.92 μ m, specific area is 32.52m
2/ g, tap density is 1.12g/ml, and itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, and simulated battery is with 0.20mA/cm
2Charging and discharging currents density discharge and recharge, when charging/discharging voltage was 2.75-4.50V, capacity was 127.23mAh/g first, maximum discharge capacity is 142.42mAh/g, coulombic efficiency is 94.8% first, the capability retention after 40 weeks of circulating is 100.3%.
Embodiment 3, and raw material lithium carbonate, manganese dioxide and the ball mill grinding of ammonium dihydrogen phosphate process to sub-micron and nanoscale, are accurately taken by weighing lithium carbonate 70.64 grams, manganese dioxide 162.3 grams, ammonium dihydrogen phosphate 219.96 grams and glucose 63.2 grams.Glucose is dissolved in 1000 milliliters of 50 ℃ of deionized waters, and constant temperature stirred 1 hour; Lithium carbonate, manganese dioxide and ammonium dihydrogen phosphate are added in the above-mentioned solution successively, and the rotating speed of 300r/min stirs 2 hours down until mixing.
Above-mentioned solution is added the carbon nano-fiber that accounts for sample 3wt.%; ball milling is 2 hours under the rotating speed of 300r/min; spray-drying process under 130 ℃ of conditions; fusion treatment is 0.5 hour under the rotating speed of 1100r/min; then product is placed under the nitrogen protection at box type furnace; with the programming rate of 6 ℃/min,, obtain the preliminary treatment powder behind the natural cooling 200 ℃ of following preliminary treatment 6 hours.
Gained preliminary treatment powder is adopting fusion machine fusion treatment after 1.5 hours under the rotating speed of 600r/min; place under the nitrogen protection at tube furnace; programming rate with 4 ℃/min; 750 ℃ of following calcination process 11 hours; naturally cool to room temperature; after the 500r/min fusion treatment 3 hours, obtain the lithium manganese phosphate matrix, test its granularity d through pulverizing, shaping, classification
10=3.12 μ m, d
50=11.58 μ m, d
90=24.74 μ m.
Above-mentioned lithium manganese phosphate matrix is mixed with 1wt.% epoxy resin, and rotating speed 500r/min coated 6 hours, and with the programming rate of 3 ℃/min, 1200 ℃ of following carbonization treatment 1 hour, cooling obtained lithium ion battery anode material manganese lithium phosphate naturally.
The lithium manganese phosphate material for preparing was done physical property test and electrochemical property test after grinding 200 mesh sieves.Synthetic lithium manganese phosphate positive electrode for the almost spherical spherical, that major and minor axis is 0.5～30 μ m, rhombus, taper, sheet, stratiform or/and bulk, d
10=4.25 μ m, d
50=17.14 μ m, d
90=25.36 μ m, specific area is 20.214m
2/ g, tap density is 1.452g/ml, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, with 0.20mA/cm
2Charging and discharging currents density discharge and recharge, when charging/discharging voltage was 2.75-4.50V, capacity was 128.57mAh/g first, maximum discharge capacity reaches 140.21mAh/g, coulombic efficiency is 93.8% first, the capability retention after 40 weeks of circulating is 98.7%.
Embodiment 4, it is nanometer scale that feed hydrogen lithia, manganese dioxide, ammonium dihydrogen phosphate are crushed to granularity respectively, accurately take by weighing lithium hydroxide 883.9 grams, manganese dioxide 1623.0 grams, ammonium dihydrogen phosphate 2207.0 grams and glucose 1264.0 grams, add successively in 2500 milliliters of 40 ℃ of deionized waters, constant temperature stirred 2 hours.
Above-mentioned sample was added behind the 0.5wt.%CuO under the rotating speed of 200r/min ball milling 12 hours; spray-drying process under 150 ℃ of conditions; fusion treatment is 2 hours under the rotating speed of 200r/min; then product is placed under the argon shield at box type furnace; programming rate with 1 ℃/min; 450 ℃ of following preliminary treatment 2 hours, obtain the preliminary treatment powder behind the natural cooling, both the lithium manganese phosphate presoma.
Gained preliminary treatment powder is in fusion treatment under the rotating speed of 1100r/min after 0.5 hour; programming rate with 2 ℃/min; place under the argon shield 600 ℃ of following calcination process 12 hours; naturally cool to room temperature; process 400r/min fusion treatment 2 hours; obtain the lithium manganese phosphate matrix through pulverizing, shaping, classification, test its granularity d
10=6.181 μ m, d
50=14.384 μ m, d
90=27.861 μ m.
Above-mentioned lithium manganese phosphate matrix is mixed with the 1wt% styrene butadiene rubber sbr, and rotating speed 400r/min coated after 0.5 hour, and with the programming rate of 2 ℃/min, 750 ℃ of following carbonization treatment 5 hours, cooling obtained lithium ion battery anode material manganese lithium phosphate naturally.
The lithium manganese phosphate material for preparing was done physical property test and electrochemical property test after grinding 200 mesh sieves.Synthetic lithium manganese phosphate positive electrode for the almost spherical spherical, that major and minor axis is 0.5～30 μ m, rhombus, taper, sheet, stratiform or/and bulk, d
10=3.52 μ m, d
50=15.24 μ m, d
90=21.52 μ m, specific area is 26.247m
2/ g, tap density is 1.364g/ml, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, with 0.20mA/cm
2Charging and discharging currents density discharge and recharge, when charging/discharging voltage was 2.75-4.50V, capacity was 126.925mAh/g first, maximum discharge capacity reaches 137.67mAh/g, coulombic efficiency is 94.8% first, the capability retention after 40 weeks of circulating is 99.8%.
Embodiment 5, with feed hydrogen lithia and manganese acetate through ball mill grinding to submicron-scale, accurately take by weighing lithium hydroxide 802.6 grams, manganese acetate 4688.0 grams, phosphoric acid 2205.2 grams and glucose 1266.0 grams.Glucose is dissolved in 3000 milliliters of 35 ℃ of deionized waters, and constant temperature stirred 0.5 hour; Lithium hydroxide and manganese acetate are added in the above-mentioned solution successively, add phosphoric acid at last, the rotating speed of 150r/min stirred 3 hours down.
With above-mentioned sample and the Zr that accounts for sample 2wt.%
2O
3Mix back ball milling 2 hours under the rotating speed of 300r/min; spray-drying process under 260 ℃ of conditions; fusion treatment is 1.5 hours under the rotating speed of 500r/min; then product is placed under the argon shield at box type furnace; programming rate with 3 ℃/min; 250 ℃ of following preliminary treatment 6 hours, obtain the preliminary treatment powder behind the natural cooling.
Gained preliminary treatment powder is adopting fusion machine fusion treatment after 2.5 hours under the rotating speed of 400r/min; place under the argon shield at tube furnace; programming rate with 5 ℃/min; 950 ℃ of following calcination process 5 hours; naturally cool to room temperature; after 2 hours, obtain the lithium manganese phosphate matrix through the 300r/min fusion treatment, test its granularity d through pulverizing, shaping, classification
10=1.543 μ m, d
50=7.852 μ m, d
90=19.114 μ m.
Above-mentioned lithium manganese phosphate matrix is mixed with the 1wt% coal tar pitch, and rotating speed 600r/min coated 3 hours, and with the programming rate of 3 ℃/min, 500 ℃ of following carbonization treatment 10 hours, cooling obtained lithium ion battery anode material manganese lithium phosphate naturally.
The lithium manganese phosphate material for preparing carried out electrochemical property test after grinding 200 mesh sieves, synthetic lithium manganese phosphate positive electrode for the almost spherical spherical, that major and minor axis is 0.5～30 μ m, rhombus, taper, sheet, stratiform or/and bulk, granularity d
10=0.757 μ m, d
50=8.395 μ m, d
90=20.718 μ m, specific area is 26.74m
2/ g, tap density is 1.21g/ml, and itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, and simulated battery is with 0.20mA/cm
2Charging and discharging currents density discharge and recharge, when charging/discharging voltage was 2.75-4.50V, capacity was 126.75mAh/g first, maximum discharge capacity is 138.24mAh/g, coulombic efficiency is 94.9% first, the capability retention after 40 weeks of circulating is 100.2%.
By the foregoing description 1-5 as seen, lithium ion battery anode material manganese lithium phosphate of the present invention has the discharge platform voltage about 4V, be higher than the present lithium iron phosphate positive material of industrialization, its discharge platform voltage only is 3.4V, and prepared lithium manganese phosphate positive electrode has higher discharge capacity, about 140mAh/g, in addition, the cycle performance excellence of this material, preceding 40 all capacity are decayed hardly, are therefore using very advantageous aspect hybrid electric vehicle HEV, electric motor car EV and the electric tool.
The present invention uses lithium salts, manganese salt, phosphate and material with carbon element to be primary raw material, adopts the prepared lithium ion battery anode material manganese lithium phosphate of nano particle liquid-solid phase combination.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 lithium manganese phosphate of liquid-solid phase combined techniques 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.Carbon plays the reducing agent effect in the roasting reaction, and unnecessary carbon compound evenly is being coated on the effect of playing enhancing conductivity on the active material after the carbonization.By adding Fe, Zr, Zn, Ti, Al, Mg, Cu, Cr, Ni, Ge or the compound of Nb element and the conductive carbon material of high-specific surface area, conductive acetylene carbon black Super-P, carbon nano-fiber, carbon nano-tube or nano-sized carbon microballoon carry out doping vario-property to material, material is carried out surface coating modification handle, handle charge/discharge capacity, the multiplying power discharging property that improves material and the cyclical stability that can improve by doping vario-property or coating modification.
Li source compound lithium hydroxide (LiOH) lithium carbonate (Li that only gives an example out among the embodiment
2CO
3), because 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, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or lithium oxalate can provide target compound required lithium by reacting equal in the methods of the invention, identical with above-mentioned two kinds of materials, and then Li source compound is applicable to the present invention.
The P source compound phosphoric acid H that only gives an example out among the embodiment
3PO
4With ammonium dihydrogen phosphate NH
4H
2PO
4, because ammonium phosphate (NH
4)
3PO
4, diammonium hydrogen phosphate (NH
4)
2HPO
4, phosphorus pentoxide P
2O
5, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate or dipotassium hydrogen phosphate etc. can provide target compound required phosphate radical by reacting equal in the methods of the invention, and be identical with above-mentioned two kinds of materials, and then P source compound is applicable to the present invention.
The manganese source compound titanium dioxide two manganese MnO that only give an example out among the embodiment
2, manganese acetate, because mangano-manganic oxide, manganese sesquioxide managnic oxide, manganous hydroxide, manganese carbonate, manganous chloride, four water manganous chloride, manganese tetrachloride, manganese sulfate, manganese sulfate monohydrate, sulfate dihydrate manganese, three water manganese sulfates, four water manganese sulfates, Manganese sulfate pentahydrate, six water manganese sulfates, seven water manganese sulfates, manganese nitrate etc. all can provide the target compound lithium manganese phosphate required bivalent manganese by redox reaction in the method for the invention, above-mentioned two kinds of materials are same or similar, and then the manganese source compound is suitable for the present invention.
Only give an example out conductive acetylene carbon black Super P, glucose of material with carbon element among the embodiment, sucrose, Ensaco carbon dust, conductive nano carbon dust, tartaric acid, citric acid, urea, acrylic acid, fructose, ascorbic acid, polyethylene glycol or glycerol form carbon in preparation method of the present invention, in chemical reaction, play simultaneously the effect of reducing agent, unnecessary carbon then is dispersed in the lithium manganese phosphate material with the conductive agent form, role is identical with above-mentioned two kinds of materials, so be suitable for the present invention.
Only give an example out among the embodiment doping vario-property agent Cu, the compound of Al, Zr, carbon nano-fiber, since compound, conductive acetylene carbon black Super-P, carbon nano-tube or the nano-sized carbon microballoon of Fe, Zn, Ti, Mg, Cr, Ni, Ge or Nb element can by self conductivity or form the conductivity that new conductive material improves material, have equally raising charge/discharge capacity, improve the effect of the multiplying power discharging property and the cyclical stability of material, so be suitable for the present invention.
Only give an example out styrene butadiene rubber sbr, pitch, epoxy resin of clad material among the embodiment, because furane resins, cellulose CMC, Lauxite, polyvinyl alcohol, ethyl-amine resin, phenolic resins, polyacrylonitrile, 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.
Prior art mainly adopts lithium salts, as lithium carbonate, lithium hydroxide, manganese salt, as manganese dioxide, phosphate, prepare lithium manganese phosphate as diammonium hydrogen phosphate, ammonium dihydrogen phosphate and four kinds of raw materials of material with carbon element by high-temperature process, carbon is insufficient evenly to the coating of active material, it is former because raw material passes through nanometer processing or liquid phase ultra fine, solid carbonaceous material itself can not be to playing the effect of abundant coating to active material, do not adopt the organic carbon material to coat processing, powder body material itself has the trend that easy generation is reunited, and the more little reunion of particle is serious more.
It is raw material that the present invention adopts Li source compound, manganese source compound, P source compound and material with carbon element, nano particle post forming method by the liquid-solid phase combination prepares lithium manganese phosphate, little and the even dispersion of product particle, the purity height of product, carbon is full and uniform to the coating of active material, stoped particle agglomeration effectively, the chemical property of product is good, and is little to the pollution of environment.
Claims (24)
1. lithium ion battery anode material manganese lithium phosphate, described lithium ion battery anode material manganese lithium phosphate has the lithium manganese phosphate matrix, matrix is coated with the material with carbon element coating layer, covering amount is the 1-3wt.% of matrix, the almost spherical that lithium manganese phosphate tool sphere behind the carbon coated material coating layer, major and minor axis are 0.5～30 μ m, rhombus, taper, sheet, stratiform are or/and block microscopic feature, and specific area is 5-40m
2/ g, tap density is 1.0-1.6g/ml, wherein, described cathode material lithium manganese phosphate employing is prepared as follows method and prepares:
This preparation method may further comprise the steps:
One, the preparation of nano particle: respectively Li source compound, water-insoluble manganese source compound, P source compound and water-insoluble simple substance carbon are handled to sub-micron or nano-scale particle;
Two, liquid-phase mixing reaction: the ratio Li that presses amount of substance: Mn: P: C=0.90-1.20: 1: 0.95-1.10: 0.5-2.0, Li source compound, water-insoluble manganese source compound, P source compound and water-insoluble simple substance carbon is water-soluble or be distributed to and obtain composite material in the water;
Three, the preparation of precursor: with composite material under the rotating speed of 200-500r/min ball milling 0.5-12 hour, spray drying obtained anode material precursor under 100～360 ℃ of conditions then;
Four, calcination process: with the programming rate of precursor with 1-10 ℃/min, in 600-950 ℃ calcination process 5-12 hour, be cooled to room temperature then naturally, obtain the lithium manganese phosphate matrix;
Five, after but the lithium manganese phosphate matrix surface coats the organic substance of the charing that accounts for matrix 1-3wt.%, programming rate with 1-10 ℃/min, under 500-1200 ℃ temperature carbonization treatment 1-12 hour, naturally be cooled to room temperature, obtain being coated with on the lithium manganese phosphate matrix lithium ion battery anode material manganese lithium phosphate of material with carbon element coating layer; Perhaps,
This preparation method may further comprise the steps:
One, the preparation of nano particle: adopt the wet method super-fine ball grinding method to handle Li source compound and P source compound respectively to sub-micron or nano-scale particle, wherein, described wet method super-fine ball grinding method is meant, Li source compound and P source compound is water-soluble or be scattered in water and get its composite material, and described wet method super-fine ball-milling treatment adopts circulating agitating ball mill, 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 to carry out ultra-fine ball-milling treatment;
Two, liquid-phase mixing reaction: the ratio Li that presses amount of substance: Mn: P: C=0.90-1.20: 1: 0.95-1.10: 0.5-2.0, Li source compound, water-soluble manganese source compound, P source compound and water-soluble carbon compound are dissolved in or are scattered in the water, obtain composite material;
Three, the preparation of precursor: with composite material under the rotating speed of 200-500r/min ball milling 0.5-12 hour, spray drying obtained anode material precursor under 100～360 ℃ of conditions then;
Four, preliminary treatment: under protective gas helium, argon gas or nitrogen, with the programming rate of 1-10 ℃/min, at 200-450 ℃ of preliminary treatment 2-6 hour, natural cooling;
Five, calcination process: with the preliminary treatment powder under protective gas helium, argon gas or nitrogen protection, with the programming rate of 1-10 ℃/min, in 600-950 ℃ calcination process 5-12 hour, be cooled to room temperature then naturally, obtain the lithium manganese phosphate matrix;
Six, after but the lithium manganese phosphate matrix surface coats the organic substance of the charing that accounts for matrix 1-3wt.%, programming rate with 1-10 ℃/min, under 500-1200 ℃ temperature carbonization treatment 1-12 hour, naturally be cooled to room temperature, obtain being coated with on the lithium manganese phosphate matrix lithium ion battery anode material manganese lithium phosphate of material with carbon element coating layer.
2. lithium ion battery anode material manganese lithium phosphate according to claim 1, the granularity of described lithium ion battery anode material manganese lithium phosphate are 0.5-30 μ m.
3. the preparation method of a lithium ion battery anode material manganese lithium phosphate may further comprise the steps:
One, the preparation of nano particle: respectively Li source compound, water-insoluble manganese source compound, P source compound and water-insoluble simple substance carbon are handled to sub-micron or nano-scale particle;
Two, liquid-phase mixing reaction: the ratio Li that presses amount of substance: Mn: P: C=0.90-1.20: 1: 0.95-1.10: 0.5-2.0, Li source compound, water-insoluble manganese source compound, P source compound and water-insoluble simple substance carbon is water-soluble or be distributed to and obtain composite material in the water;
Three, the preparation of precursor: with composite material under the rotating speed of 200-500r/min ball milling 0.5-12 hour, spray drying obtained anode material precursor under 100～360 ℃ of conditions then;
Four, calcination process: with the programming rate of precursor with 1-10 ℃/min, in 600-950 ℃ calcination process 5-12 hour, be cooled to room temperature then naturally, obtain the lithium manganese phosphate matrix;
Five, after but the lithium manganese phosphate matrix surface coats the organic substance of the charing that accounts for matrix 1-3wt.%, programming rate with 1-10 ℃/min, under 500-1200 ℃ temperature carbonization treatment 1-12 hour, naturally be cooled to room temperature, obtain being coated with on the lithium manganese phosphate matrix lithium ion battery anode material manganese lithium phosphate of material with carbon element coating layer.
4. preparation method according to claim 3, described Li source compound is lithium hydroxide, lithium carbonate, lithium acetate, 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, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or lithium oxalate.
5. preparation method according to claim 3, described water-insoluble manganese source compound is mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide or manganous hydroxide.
6. preparation method according to claim 3, described P source compound is phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate or dipotassium hydrogen phosphate.
7. preparation method according to claim 3, described water-insoluble simple substance carbon is conductive acetylene carbon black Super P, conductive acetylene carbon black Ensaco or conductive nano carbon dust.
8. preparation method according to claim 3, but the organic substance of described charing is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, butadiene-styrene rubber, cellulose, coke, coal tar pitch or petroleum asphalt.
9. according to each described preparation method of claim 3-8, with Li source compound, water-insoluble manganese source compound, P source compound and water-insoluble simple substance carbon are water-soluble or be scattered in the 20-90 ℃ of deionized water, stir and obtained composite material in 0.5-3 hour, adopt the wet method super-fine ball grinding method to handle the gained composite material to sub-micron or nano-scale particle, wherein, described wet method super-fine ball-milling treatment adopts circulating agitating ball mill, stirring ball mill, sand mill, colloidal mill, airslide disintegrating mill, the impact type micro ball-mill, air-flow spiral pulverizing mill, impact grinder or bar type mechanical crusher carry out ultra-fine ball-milling treatment.
10. preparation method according to claim 9, described with composite material under the rotating speed of 200-500r/min before the ball milling, add the doping vario-property agent that accounts for composite material 0.1-3wt.%, described doping vario-property agent is compound, conductive acetylene carbon black Super-P, carbon nano-fiber, carbon nano-tube or the nano-sized carbon microballoon of Fe, Zr, Zn, Ti, Al, Mg, Cu, Cr, Ni, Ge or Nb element.
11., carry out preliminary treatment before the described calcination process according to each described preparation method of claim 3-8: under protective gas helium, argon gas or nitrogen, with the programming rate of 1-10 ℃/min, at 200-450 ℃ of preliminary treatment 2-6 hour, natural cooling.
12. according to each described preparation method of claim 3-8, before the described preliminary treatment, under the rotating speed of 200-1100r/min fusion treatment 0.5-2 hour.
13. according to each described preparation method of claim 3-8, after the described preliminary treatment, under the rotating speed of 200-1100r/min fusion treatment 0.5-2 hour.
14. according to each described preparation method of claim 3-8, described calcination process is carried out under protective gas helium, argon gas or nitrogen protection.
15. according to each described preparation method of claim 3-8, after the described calcination process, under the rotating speed of 200-1100r/min fusion treatment 0.5-4 hour.
16. preparation method according to claim 15 after the fusion treatment after the described calcination process, pulverizes with classification and handles.
17. according to each described preparation method of claim 3-8, but describedly coat the organic substance of the charing account for matrix 1-3wt.%, under rotating speed 200～1000r/min condition, coated 0.5～6 hour at the lithium manganese phosphate matrix surface.
18. the preparation method of a lithium ion battery anode material manganese lithium phosphate may further comprise the steps:
One, the preparation of nano particle: adopt the wet method super-fine ball grinding method to handle Li source compound and P source compound respectively to sub-micron or nano-scale particle, wherein, described wet method super-fine ball grinding method is meant, Li source compound and P source compound is water-soluble or be scattered in water and get its composite material, and described wet method super-fine ball-milling treatment adopts circulating agitating ball mill, 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 to carry out ultra-fine ball-milling treatment;
Two, liquid-phase mixing reaction: the ratio Li that presses amount of substance: Mn: P: C=0.90-1.20: 1: 0.95-1.10: 0.5-2.0, Li source compound, water-soluble manganese source compound, P source compound and water-soluble carbon compound are dissolved in or are scattered in the water, obtain composite material;
Three, the preparation of precursor: with composite material under the rotating speed of 200-500r/min ball milling 0.5-12 hour, spray drying obtained anode material precursor under 100～360 ℃ of conditions then;
Four, preliminary treatment: under protective gas helium, argon gas or nitrogen, with the programming rate of 1-10 ℃/min, at 200-450 ℃ of preliminary treatment 2-6 hour, natural cooling;
Five, calcination process: with the preliminary treatment powder under protective gas helium, argon gas or nitrogen protection, with the programming rate of 1-10 ℃/min, in 600-950 ℃ calcination process 5-12 hour, be cooled to room temperature then naturally, obtain the lithium manganese phosphate matrix;
Six, after but the lithium manganese phosphate matrix surface coats the organic substance of the charing that accounts for matrix 1-3wt.%, programming rate with 1-10 ℃/min, under 500-1200 ℃ temperature carbonization treatment 1-12 hour, naturally be cooled to room temperature, obtain being coated with on the lithium manganese phosphate matrix lithium ion battery anode material manganese lithium phosphate of material with carbon element coating layer.
19. preparation method according to claim 18, described Li source compound is lithium hydroxide, lithium carbonate, lithium acetate, 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, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or lithium oxalate.
20. preparation method according to claim 18, described water-soluble manganese source compound is manganese acetate, manganous chloride, manganese tetrachloride, manganese sulfate or manganese nitrate.
21. preparation method according to claim 18, described water-soluble manganese source compound is four water manganese acetates, four water manganous chloride, manganese sulfate monohydrate, sulfate dihydrate manganese, three water manganese sulfates, four water manganese sulfates, Manganese sulfate pentahydrate, six water manganese sulfates or seven water manganese sulfates.
22. preparation method according to claim 18, described P source compound is phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate or dipotassium hydrogen phosphate.
23. preparation method according to claim 18, described water-soluble carbon compound is sucrose, glucose, tartaric acid, citric acid, urea, acrylic acid, fructose, ascorbic acid, polyethylene glycol or glycerol.
24. preparation method according to claim 18, but the organic substance of described charing is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, butadiene-styrene rubber, cellulose, coke, coal tar pitch or petroleum asphalt.
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| CN102983334A (en) * | 2012-12-18 | 2013-03-20 | 中国科学院宁波材料技术与工程研究所 | Positive pole material of lithium ion battery and preparation method of material |
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