CN102386384B - Spherical hard carbon lithium ion battery cathode material and preparation method thereof - Google Patents
Spherical hard carbon lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN102386384B CN102386384B CN2011103839240A CN201110383924A CN102386384B CN 102386384 B CN102386384 B CN 102386384B CN 2011103839240 A CN2011103839240 A CN 2011103839240A CN 201110383924 A CN201110383924 A CN 201110383924A CN 102386384 B CN102386384 B CN 102386384B
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000010406 cathode material Substances 0.000 title abstract description 16
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 3
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a spherical hard carbon lithium ion battery cathode material and a preparation method thereof, aiming to solve the technical problem of improving the capacity retention ratio and rapid charging/discharging capacity of the material. The spherical hard carbon lithium ion battery cathode material adopts hard carbon as a basal body, carbon material is coated outside the basal body, and the 002 peak is at 22.6-23.8 degrees. The preparation method comprises ball milling a hard carbon precursor to granules, placing the granules into a water solution containing surfactant, ball milling to obtain a dispersion of the hard carbon precursor, drying, coating, and carrying out pyrolytic decomposition treatment. Compared with the prior art, the prepared spherical hard carbon material has a compacted density greater than 1.1 g/cm<3>, an initial coulombic efficiency greater than 80%, capacity retention ratio after 500 cycles greater than 85%, and 30C/1C capacity retention ratio greater than 98%, and has excellent rapid lithium ion intercalation and deintercalation capacity, and simple preparation method.
Description
Technical field
The present invention relates to a kind of lithium ion battery cathode material and its preparation method, particularly a kind of hard carbon cathode material and preparation method thereof.
Background technology
Hard carbon material has the high power capacity that is higher than graphite theoretical capacity (372mAh/g), excellent high rate performance and cycle performance.With current electric tool, electric motor car at matching in the desired high-energy-density of lithium ion battery electrode material, high security, big electric current fast charging and discharging, long useful life, obtain paying close attention to of the whole world.At present, utilize the hard carbon material of resinae and plant class feedstock production to be irregular sheet or bulk, Chinese patent publication number CN1169249C, CN101916845A disclose the method for utilizing the irregular hard carbon material of plant class feedstock production, Chinese patent publication number CN101887966A discloses the method for the irregular hard carbon material of resinae feedstock production, and it is the preparation method of the irregular hard carbon of raw material that patent WO2005/098999A1 discloses with the asphaltic base.But the irregular hard carbon material compacted density of prior art is lower, only is 1.0g/cm
3, it is lower to cause planting thus the energy content of battery density that material makes, and simultaneously, lithium storage performance is lower fast.
Summary of the invention
The purpose of this invention is to provide a kind of spherical hard carbon lithium ion battery cathode material and its preparation method, the technical problem that solve is to improve capability retention and the fast charging and discharging ability of material.
The present invention is by the following technical solutions: a kind of spherical hard carbon lithium ion battery negative material, described spherical hard carbon lithium ion battery negative material is matrix with the hard carbon, matrix is coated with material with carbon element, the material with carbon element precursor is 1～15% of substrate quality, and spherical hard carbon lithium ion battery negative material is shaped as sphere, and particle size range is 1～30 μ m, described spherical hard carbon cathode material is amorphous carbon, 002 peak is at 22.6 °～23.8 °, and the diffraction maximum broadening, the interlamellar spacing D of 002 crystal face
002Between 0.360～0.480nm, specific area is 1.0～73.2m
2/ g, real density is 1.50～2.20g/cm
3, tap density is 0.95～1.52g/cm
3, compacted density is 1.08～1.63g/cm
3
A kind of preparation method of spherical hard carbon lithium ion battery negative material may further comprise the steps: be 100～300r/min with the hard carbon presoma with rotating speed one,, ball milling 3～40h obtains the particle that average grain diameter is 1.3～4.5 μ m; Described hard carbon presoma is resinae hard carbon presoma and/or plant class hard carbon presoma; Two, press particle: surfactant: the mass ratio of water 100: 0.2～10: 200～1500, particle is placed the aqueous solution that contains surfactant, rotating speed is 100～300r/min, ball milling 0.5～20h, and obtaining average grain diameter is the dispersion of 0.9～4.0 μ m hard carbon presoma; Described surfactant be the HLB value at the anion surfactant between 30～40 or HLB value the non-ionic surface active agent between 30～40; Three, dispersion is carried out drying, obtaining D50 is 0.5～25 μ m, and sphericity is 90～95% spherical hard carbon presoma; Four, be 1～15% of spherical hard carbon presoma quality by the coating presoma, add the coating presoma in spherical hard carbon presoma, rotating speed is 600～3500r/min, and incorporation time is 30～180min; Or the coating presoma placed solvent, add spherical hard carbon presoma, the mass ratio of spherical hard carbon presoma and coating precursor quality sum and solvent is 1: 2～10, rotating speed 800～3000r/min, disperse to carry out drying behind 0.5～5h, obtain the mixture of spherical hard carbon presoma and coating presoma; Described coating precursor is pitch, epoxy resin, phenolic resins, furane resins, acrylic resin, the ethyl-methyl carbonic ester, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, polyvinyl chloride, polyethylene, poly-to benzene, poly(ethylene oxide), PPOX, polyethylene glycol succinate, poly-decanedioic acid ethylene glycol, the polyethylene glycol imines, polyacetylene, polyaniline, polypyrrole, poly-acene, polythiophene, poly m-phenylene diamine, poly-phenylene vinylene (ppv), polyimides, polyphenylene sulfide, PVP; more than one in butadiene-styrene rubber and the carboxymethyl cellulose; Described solvent is water, ethanol, methyl alcohol, acetone, oxolane, N-methyl pyrrolidone, n-butanol, ether, benzinum, carrene or chloroform; Five, with the heating rate of 1～15 ℃/min, to 600～1500 ℃, temperature retention time is 1～8h, carries out pyrolysis processing, naturally cools to room temperature in the stove, and obtaining D50 is 1～30 μ m, and sphericity is 90～95% spherical hard carbon lithium ion battery negative material.
The preparation method of resinae hard carbon presoma of the present invention: press the thermoplastic resin quality＞0 to≤75% add curing agent, the thermoplastic resin that will add curing agent solidifies 3～50h, obtain solid precursor, with presoma with heating rate to 150～450 of 0.1～3 ℃/min ℃, low temperature presintering 2～24h, naturally cool to room temperature in the stove, again with heating rate to 560～1500 of 0.3～10 ℃/min ℃, pyrolysis 0.5～7.5h, naturally cool to room temperature in the stove, make resinae hard carbon presoma; Described thermoplastic resin is acrylic resin, polyvinyl chloride, Merlon, epoxy resin, more than one in phenolic resins and the polyformaldehyde; Described curing agent is hexamethylene diamine, m-phenylene diamine (MPD), aniline-formaldehyde resin, polyamide, more than one in phthalic anhydride and the benzene sulfonic acid.
The preparation method of plant class hard carbon presoma of the present invention: add 80～300mL acid or alkali by every 100g plant material, soak 3～50h, extremely neutral with the pure water washing, under 80～140 ℃ of conditions, dry 10～40h, naturally be down to room temperature, with heating rate to 200～500 of 0.1～10 ℃/min ℃, low temperature presintering 3～20h, naturally cool to room temperature in the stove, again with heating rate to 500～1300 of 0.1～10 ℃/min ℃, pyrolysis 1～10h naturally cools to room temperature in the stove, make plant class hard carbon presoma; Described plant material is pollen, rice hulls, sugarcane bar, walnut shell, bamboo, more than one in vinasse and the wood chip; Described acid is hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid or nitric acid; Described alkali is potassium hydroxide, calcium hydroxide or NaOH.
The ball that step 1 ball milling of the present invention adopts is more than one in zirconia ball, stainless steel ball or the agate ball, and diameter is 0.2～2.5cm, and the mass ratio of ball and hard carbon presoma is 1: 80～300.
The ball that step 2 ball milling of the present invention adopts is more than one in zirconia ball, stainless steel ball or the agate ball, and the diameter of ball is 0.02～1cm, and the mass ratio of ball and particle is 1: 10～200.
Surfactant of the present invention is lauryl sodium sulfate, pure NaLS or sodium carboxymethylcellulose.
Drying of the present invention is spray drying, and the constant current pump speed is 10～100r/min, and inlet temperature is 150～300 ℃, and outlet temperature is 80～130 ℃.
Pyrolysis processing of the present invention is under protective gas or vacuum environment, and protective gas is more than one in nitrogen, argon gas, neon, helium, hydrogen and the water-gas, and vacuum environment is below the vacuum degree 0.1MPa.
The present invention places solvent with the coating presoma, adds spherical hard carbon presoma, behind dispersion 0.5～5h, and spray drying, the constant current pump speed is 10～100r/min, and inlet temperature is 150～300 ℃, and outlet temperature is 80～130 ℃; Or directly place baking oven under 80～180 ℃ of conditions, to dry 8～40h, naturally cool to room temperature in the stove.
The present invention compared with prior art, the spherical hard carbon material compacted density for preparing is greater than 1.1g/cm
3, and have good quick lithium storage performance, and reversible specific capacity is greater than 400mAh/g, and coulombic efficiency is greater than 80% first, and 500 capability retentions that circulate are that the preparation method is simple greater than 98% greater than 85%, 30C/1C capability retention.
Description of drawings
Fig. 1 is the stereoscan photograph () of the spherical hard carbon cathode material of the embodiment of the invention 1.
Fig. 2 is the stereoscan photograph (two) of the spherical hard carbon cathode material of the embodiment of the invention 1.
Fig. 3 is the XRD figure of the spherical hard carbon cathode material of the embodiment of the invention 1.
Fig. 4 is the first charge-discharge curve of the embodiment of the invention 1 spherical hard carbon cathode material under 0.2C.
Fig. 5 is the first charge-discharge curve of the embodiment of the invention 1 spherical hard carbon cathode material under 1.0C.
Fig. 6 is the first charge-discharge curve of the embodiment of the invention 1 spherical hard carbon cathode material under 20C.
Fig. 7 is the first charge-discharge curve of the embodiment of the invention 1 spherical hard carbon cathode material under 30C.
Fig. 8 is the cycle performance curve of the embodiment of the invention 1.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.Spherical hard carbon lithium ion battery negative material of the present invention, be matrix with the hard carbon, matrix is coated with material with carbon element, the material with carbon element precursor is 1～15% of substrate quality, and spherical hard carbon lithium ion battery negative material is shaped as sphere, and particle size range is 1～30 μ m, described hard carbon cathode material is amorphous carbon, 002 peak is at 22.6 °～23.8 °, and the diffraction maximum broadening, the interlamellar spacing D of 002 crystal face
002Between 0.360～0.480nm, specific area is 1.0～73.2m
2/ g, real density is 1.50～2.20g/cm
3, tap density is 0.95～1.52g/cm
3, compacted density is 1.08～1.63g/cm
3
The preparation method of spherical hard carbon lithium ion battery negative material of the present invention may further comprise the steps:
One, with the hard carbon presoma, put into the ball grinder of BXQM-20L planetary ball mill, rotating speed is 100～300r/min, ball milling 3～40h, obtaining average grain diameter is the particle of the hard carbon presoma of 1.3～4.5 μ m, grain shape is sheet or bulk.The ball that ball milling adopts is more than one in zirconia ball, stainless steel ball or the agate ball, and diameter is 0.2～2.5cm, and the mass ratio of ball and hard carbon presoma is 1: 80～300.
The hard carbon presoma is for being the resinae hard carbon presoma that feedstock production obtains with the resin, and/or is the plant class hard carbon presoma that feedstock production obtains with the plant.
The preparation method of resinae hard carbon presoma: press the thermoplastic resin quality＞0 to≤75% add curing agent, the thermoplastic resin that will add curing agent solidifies 3～50h in air, under the normal temperature, obtain solid precursor, with presoma with heating rate to 150～450 of 0.1～3 ℃/min ℃, low temperature presintering 2～24h, naturally cool to room temperature in the stove, again with heating rate to 560～1500 of 0.3～10 ℃/min ℃, pyrolysis 0.5～7.5h, naturally cool to room temperature in the stove, make resinae hard carbon presoma.
Thermoplastic resin is acrylic resin, polyvinyl chloride, Merlon, epoxy resin, more than one in phenolic resins and the polyformaldehyde.
Curing agent is hexamethylene diamine, m-phenylene diamine (MPD), aniline-formaldehyde resin, polyamide, more than one in phthalic anhydride and the benzene sulfonic acid.
The preparation method of plant class hard carbon presoma: add 80～300mL acid or alkali by every 100g plant material, soak 3～50h, extremely neutral with the pure water washing, directly under 80～140 ℃ of conditions, dry 10～40h, naturally be down to room temperature in the stove, with heating rate to 200～500 of 0.1～10 ℃/min ℃, low temperature presintering 3～20h, naturally cool to room temperature in the stove, again with heating rate to 500～1300 of 0.1～10 ℃/min ℃, pyrolysis 1～10h naturally cools to room temperature in the stove, make plant class hard carbon presoma.
Plant material is pollen, rice hulls, sugarcane bar, walnut shell, bamboo, more than one in vinasse and the wood chip.
Acid is hydrofluoric acid, boric acid, and sulfuric acid, hydrochloric acid or nitric acid, alkali are potassium hydroxide, calcium hydroxide or NaOH.
Two, by particle: surfactant: the mass ratio of water is 100: 0.2～10: 200～1500, particle is placed the aqueous solution that contains surfactant, rotating speed is 100～300r/min, ball milling 0.5～20h, and obtaining average grain diameter is the dispersion of 0.5～4.0 μ m hard carbon presoma.The ball that ball milling adopts is more than one in zirconia ball, stainless steel ball or the agate ball, and the diameter of ball is 0.02～1cm, and the mass ratio of ball and particle is 1: 10～200.
Surfactant is the HLB value between 30～40 and anion surfactant or the non-ionic surface active agent of HLB value between 30～40 with strong degree of ionization, is specially: lauryl sodium sulfate, pure NaLS or sodium carboxymethylcellulose CMC.
Three, dispersion is transferred in the container, utilized LPG-5 type spray dryer to carry out spray drying, spray-dired parameter is set to: the constant current pump speed is 10～100r/min, and inlet temperature is 150～300 ℃, and outlet temperature is 80～130 ℃, obtains D
50Be 1.0～25 μ m, sphericity is 90～95% spherical hard carbon presoma, is conducive to improve the compacted density of material.Sphericity=with the surface area of the surface area/spherical hard carbon presoma of the spheroid of spherical hard carbon presoma equal volume.
Four, be 1～15% of spherical hard carbon presoma quality by the coating presoma, in spherical hard carbon presoma, add the coating presoma, mix by SBH-5 three-dimensional mixer or VH-8 mixer, rotating speed is 600～3500r/min, incorporation time is 30～180min, obtains the mixture of spherical hard carbon presoma and coating presoma.
The coating precursor is pitch, epoxy resin, phenolic resins, furane resins, acrylic resin, the ethyl-methyl carbonic ester, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, polyvinyl chloride, polyethylene, poly-to benzene, poly(ethylene oxide), PPOX, polyethylene glycol succinate, poly-decanedioic acid ethylene glycol, the polyethylene glycol imines, polyacetylene, polyaniline, polypyrrole, poly-acene, polythiophene, poly m-phenylene diamine, poly-phenylene vinylene (ppv), polyimides, polyphenylene sulfide, PVP; more than one in butadiene-styrene rubber and the carboxymethyl cellulose.
Or the coating presoma placed solvent, speed of agitator is that 200～800r/min makes its dissolving, then to wherein adding spherical hard carbon presoma, the coating presoma is 1～15% of spherical hard carbon presoma quality, the mass ratio of spherical hard carbon presoma and coating precursor quality sum and solvent is 1: 2～10, with BS-200 type high speed dispersor, rotating speed is 800～3000r/min, disperse 0.5～5h, carry out drying with LPG-5 type spray dryer then, spray-dired parameter is set to: the constant current pump speed is 10～100r/min, inlet temperature is 150～300 ℃, outlet temperature is 80～130 ℃, obtains the mixture of spherical hard carbon presoma and coating presoma.
Solvent is water, ethanol, methyl alcohol, acetone, oxolane, N-methyl pyrrolidone, n-butanol, ether, benzinum, carrene or chloroform.
Or the coating presoma placed solvent, stir speed (S.S.) is that 200～800r/min makes its dissolving, then to wherein adding spherical hard carbon presoma, the coating presoma is 1～15% of spherical hard carbon presoma quality, the quality of spherical hard carbon presoma and coating precursor quality sum and solvent is 1: 2～10, with BS-200 type high speed dispersor, rotating speed is 800～3000r/min, disperse 0.5～5h, directly place baking oven under 80～180 ℃ of conditions, to dry 8～40h then, naturally cool to room temperature in the stove, obtain the mixture of spherical hard carbon presoma and coating presoma.
Five, mixture is placed the atmosphere box type furnace; under protective gas or vacuum environment; heating rate with 1～15 ℃/min; to 600～1500 ℃; temperature retention time is 1～8h, carries out pyrolysis processing, naturally cools to room temperature in the stove; obtaining D50 is 1～30 μ m, and sphericity is 90～95% spherical hard carbon lithium ion battery negative material.Protective gas is more than one in nitrogen, argon gas, neon, helium, hydrogen and the water-gas, and vacuum environment is below the vacuum degree 0.1MPa.
The spherical hard carbon lithium ion battery negative material that method of the present invention prepares, adopting the S-4700 of Hitachi field emission scanning electron microscope to observe sphericity is 90～95%.X ' Pert PRO X-ray diffractometer with Dutch PANalytical company records D
002Be between 0.360～0.480nm.Recording D50 with the MS2000 laser particle size analyzer of Britain Ma Erwen Instr Ltd. is 1～30 μ m, and adopting U.S. health tower NOVA2000 to record specific area is 1.0～73.2m
2/ g, adopting the full-automatic real density analyzer of U.S.'s health tower UltraPYC 1200e type to record real density is 1.50～2.20g/cm
3, it is 0.95～1.52g/cm that the Autotap of employing U.S. Kang Ta records tap density
3, adopting Boulder permanent 4350 compacted density measuring instruments of pleasing scientific ﹠ trading Co., Ltd. in Beijing to record compacted density is 1.10～1.63g/cm
3
Spherical hard carbon lithium ion battery negative material with method preparation of the present invention, mix according to 92: 5: 3 mass ratio with binding agent polyvinylidene fluoride PVDF, conductive agent Super-P, add N-methyl pyrrolidone NMP as dispersant furnishing slurry, evenly be coated on the thick Copper Foil of 10 μ m, compacting is made the circular carbon membrane of diameter 1cm in flakes then.120 ℃ of oven dry 12h are standby in drying box.As to electrode, use 1mol/L LiPF with metal lithium sheet
6Three component mixed solvents are pressed EC: DMC: EMC=1: the electrolyte that 1: 1 volume ratio mixes, the employing microporous polypropylene membrane is barrier film, is assembled into 2016 type button cells in being full of the German Braun inert atmosphere glove box MB200B of the System Co., Ltd type glove box of argon gas.The charge-discharge test of button cell is on the BTS-5V 100mA of the new prestige battery detecting equipment Co., Ltd battery testing system of Shenzhen, and charging/discharging voltage is limited in 0.001～2.0V, 0.2C, and 1C, 20C, 30C tests reversible capacity and enclosed pasture efficient first first.Enclosed pasture efficient=initial charge capacity/first discharge capacity first.
The technological parameter of embodiment 1～9 is asked for an interview table 1.The testing of materials data of embodiment 1～9 are asked for an interview table 2.(the different of Comparative Examples 1 and Comparative Examples 2 please be described with carbosphere with Delanium, because it is the same making the method materials of 2016 type button cells, might allow the auditor think that Comparative Examples 1 is the same with Comparative Examples 2) make the negative material of Comparative Examples 1 and Comparative Examples 2 respectively, assemble 2016 type button cells with said method, the electric performance test result of embodiment 1～9 and Comparative Examples 1～2 is please with table 3.
As depicted in figs. 1 and 2, the spherical hard carbon lithium ion battery negative material of embodiment 1 is the sphere of rule, uniform particles.
As shown in Figure 3, the spherical hard carbon lithium ion battery negative material of embodiment 1 is impalpable structure, and 002 peak is about 23 °, and the diffraction maximum broadening, the interlamellar spacing D of 002 crystal face
002Between 0.360～0.480nm, particle size range is 1～30 μ m, and specific area is 1.0～73.2m
2/ g, real density is 1.50～2.20g/cm
3, tap density is 0.95～1.52g/cm
3, compacted density is 1.08～1.63g/cm
3
As shown in Figure 4, the spherical hard carbon lithium ion battery negative material of embodiment 1, charging and discharging currents density is 74.4mA/g during 0.2C, and reversible capacity is 446.2mAh/g first, and enclosed pasture efficient is 80.1% first, is coated with to be beneficial to the material raising of enclosed pasture efficient first.
As shown in Figure 5, the spherical hard carbon lithium ion battery negative material of embodiment 1, the reversible capacity first of 1C is 444.5mAh/g, efficient is 80.3%.
As shown in Figure 6, the spherical hard carbon lithium ion battery negative material of embodiment 1, the reversible capacity first of 20C is 442.6mAh/g, the capability retention of 20C/1C is 99.2%.
As shown in Figure 7, the spherical hard carbon lithium ion battery negative material of embodiment 1, the reversible capacity first of 30C is 440.8mAh/g, the capability retention of 30C/1C is 98.8%.From the data of Fig. 4～Fig. 7 and charging and discharging curve as can be seen, along with the raising of charge-discharge magnification, the capacity attenuation of material is very little, and the capability retention of 30C/1C is 98.8% still, illustrates that spherical hard carbon material of the present invention has excellent high rate performance.
As shown in Figure 8, the spherical hard carbon lithium ion battery negative material of embodiment 1, capability retention is 92.5% after the 0.2C circulation 500 times, has excellent cycle performance.
Table 1 embodiment 1～9 technological parameter
The testing of materials data of table 2 embodiment 1～9
The electric performance test result of table 3 embodiment 1～9 and Comparative Examples 1～2
Claims (9)
1. the preparation method of a spherical hard carbon lithium ion battery negative material, may further comprise the steps: be 100 ~ 300r/min with the hard carbon presoma with rotating speed one,, ball milling 3 ~ 40h obtains the particle that average grain diameter is 1.3 ~ 4.5 μ m; Described hard carbon presoma is resinae hard carbon presoma and/or plant class hard carbon presoma; Two, press particle: surfactant: mass ratio 100:0.2 ~ 10:200 ~ 1500 of water, particle is placed the aqueous solution that contains surfactant, rotating speed is 100 ~ 300r/min, ball milling 0.5 ~ 20h, and obtaining average grain diameter is the dispersion of 0.9 ~ 4.0 μ m hard carbon presoma; Described surfactant be the HLB value at the anion surfactant between 30 ~ 40 or HLB value the non-ionic surface active agent between 30 ~ 40; Three, dispersion is carried out drying, obtain D
50Be 0.5 ~ 25 μ m, sphericity is 90 ~ 95% spherical hard carbon presoma; Four, be 1 ~ 15% of spherical hard carbon presoma quality by the coating presoma, add the coating presoma in spherical hard carbon presoma, rotating speed is 600 ~ 3500r/min, and incorporation time is 30 ~ 180min; Or the coating presoma placed solvent, add spherical hard carbon presoma, the mass ratio of spherical hard carbon presoma and coating precursor quality sum and solvent is 1:2 ~ 10, rotating speed 800 ~ 3000r/min, disperse to carry out drying behind 0.5 ~ 5h, obtain the mixture of spherical hard carbon presoma and coating presoma; Described coating precursor is pitch, epoxy resin, phenolic resins, furane resins, acrylic resin, the ethyl-methyl carbonic ester, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, polyvinyl chloride, polyethylene, poly-to benzene, poly(ethylene oxide), PPOX, polyethylene glycol succinate, poly-decanedioic acid ethylene glycol, the polyethylene glycol imines, polyacetylene, polyaniline, polypyrrole, poly-acene, polythiophene, poly m-phenylene diamine, poly-phenylene vinylene (ppv), polyimides, polyphenylene sulfide, PVP; more than one in butadiene-styrene rubber and the carboxymethyl cellulose; Described solvent is water, ethanol, methyl alcohol, acetone, oxolane, N-methyl pyrrolidone, n-butanol, ether, benzinum, carrene or chloroform; Five, with the heating rate of 1 ~ 15 ℃/min, to 600 ~ 1500 ℃, temperature retention time is 1 ~ 8h, carries out pyrolysis processing, naturally cools to room temperature in the stove, obtains D
50Be 1 ~ 30 μ m, sphericity is 90 ~ 95% spherical hard carbon lithium ion battery negative material.
2. the preparation method of spherical hard carbon lithium ion battery negative material according to claim 1, it is characterized in that: the preparation method of described resinae hard carbon presoma: press the thermoplastic resin quality＞0 to≤75% add curing agent, the thermoplastic resin that will add curing agent solidifies 3 ~ 50h, obtain solid precursor, with presoma with heating rate to 150 ~ 450 of 0.1 ~ 3 ℃/min ℃, low temperature presintering 2 ~ 24h, naturally cool to room temperature in the stove, again with heating rate to 560 ~ 1500 of 0.3 ~ 10 ℃/min ℃, pyrolysis 0.5 ~ 7.5h, naturally cool to room temperature in the stove, make resinae hard carbon presoma; Described thermoplastic resin is acrylic resin, polyvinyl chloride, Merlon, epoxy resin, more than one in phenolic resins and the polyformaldehyde; Described curing agent is hexamethylene diamine, m-phenylene diamine (MPD), aniline-formaldehyde resin, polyamide, more than one in phthalic anhydride and the benzene sulfonic acid.
3. the preparation method of spherical hard carbon lithium ion battery negative material according to claim 1, it is characterized in that: the preparation method of described plant class hard carbon presoma: add 80 ~ 300mL acid or alkali by every 100g plant material, soak 3 ~ 50h, extremely neutral with the pure water washing, under 80 ~ 140 ℃ of conditions, dry 10 ~ 40h, naturally be down to room temperature, with heating rate to 200 ~ 500 of 0.1 ~ 10 ℃/min ℃, low temperature presintering 3 ~ 20h, naturally cool to room temperature in the stove, again with heating rate to 500 ~ 1300 of 0.1 ~ 10 ℃/min ℃, pyrolysis 1 ~ 10h, naturally cool to room temperature in the stove, make plant class hard carbon presoma; Described plant material is pollen, rice hulls, sugarcane bar, walnut shell, bamboo, more than one in vinasse and the wood chip; Described acid is hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid or nitric acid; Described alkali is potassium hydroxide, calcium hydroxide or NaOH.
4. the preparation method of spherical hard carbon lithium ion battery negative material according to claim 1, it is characterized in that: the ball that described step 1 ball milling adopts is more than one in zirconia ball, stainless steel ball or the agate ball, diameter is 0.2 ~ 2.5cm, and the mass ratio of ball and hard carbon presoma is 1:80 ~ 300.
5. the preparation method of spherical hard carbon lithium ion battery negative material according to claim 1, it is characterized in that: the ball that described step 2 ball milling adopts is more than one in zirconia ball, stainless steel ball or the agate ball, the diameter of ball is 0.02 ~ 1cm, and the mass ratio of ball and particle is 1:10 ~ 200.
6. the preparation method of spherical hard carbon lithium ion battery negative material according to claim 1, it is characterized in that: described surfactant is lauryl sodium sulfate, pure NaLS or sodium carboxymethylcellulose.
7. the preparation method of spherical hard carbon lithium ion battery negative material according to claim 1, it is characterized in that: the drying described in described step 3 and the step 4 is spray drying, the constant current pump speed is 10 ~ 100r/min, and inlet temperature is 150 ~ 300 ℃, and outlet temperature is 80 ~ 130 ℃.
8. the preparation method of spherical hard carbon lithium ion battery negative material according to claim 1; it is characterized in that: described pyrolysis processing is under protective gas or vacuum environment; protective gas is more than one in nitrogen, argon gas, neon, helium, hydrogen and the water-gas, and vacuum environment is below vacuum degree 0.1 MPa.
9. the preparation method of spherical hard carbon lithium ion battery negative material according to claim 1, it is characterized in that: described the coating presoma is placed solvent, add spherical hard carbon presoma, after disperseing 0.5 ~ 5h, carry out drying, this drying is: spray drying, constant current pump speed are 10 ~ 100r/min, inlet temperature is 150 ~ 300 ℃, and outlet temperature is 80 ~ 130 ℃; Or directly place baking oven under 80 ~ 180 ℃ of conditions, to dry 8 ~ 40h, naturally cool to room temperature in the stove.
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| CN102237513A (en) * | 2010-04-29 | 2011-11-09 | Tcl集团股份有限公司 | Negative active material and preparation method thereof as well as negative electrode and lithium battery using negative active material |
| CN101887966A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Composite hard carbon cathode material of lithium ion battery and preparation method thereof |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
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