CN101847716A - Method for preparing spherical lithium titanate cathode material - Google Patents
Method for preparing spherical lithium titanate cathode material Download PDFInfo
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- CN101847716A CN101847716A CN201010177934A CN201010177934A CN101847716A CN 101847716 A CN101847716 A CN 101847716A CN 201010177934 A CN201010177934 A CN 201010177934A CN 201010177934 A CN201010177934 A CN 201010177934A CN 101847716 A CN101847716 A CN 101847716A
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- titanate
- lithium titanate
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000010406 cathode material Substances 0.000 title abstract 3
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000004945 emulsification Methods 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 9
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- -1 tetramethyl ester Chemical class 0.000 claims description 4
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QAZAAZKNSOCPBF-UHFFFAOYSA-N [Li].C(C=C)(=O)O Chemical compound [Li].C(C=C)(=O)O QAZAAZKNSOCPBF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- JCCYXJAEFHYHPP-OLXYHTOASA-L dilithium;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Li+].[Li+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O JCCYXJAEFHYHPP-OLXYHTOASA-L 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229940031993 lithium benzoate Drugs 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 2
- AXHNANAHRZVDHS-KVVVOXFISA-N lithium;(z)-octadec-9-enoic acid Chemical compound [Li].CCCCCCCC\C=C/CCCCCCCC(O)=O AXHNANAHRZVDHS-KVVVOXFISA-N 0.000 claims description 2
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- 229910052719 titanium Inorganic materials 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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 method for preparing a spherical lithium titanate cathode material, which comprises the following steps of: dissolving an organic lithium salt in an alcohol solvent, adding a certain amount of titanate in a molar ratio of Li to Ti of 0.8-0.9 for uniformly mixing to obtain lithium-containing and titanium-containing mixed solution; adding the lithium-containing and titanium-containing mixed solution into an organic dispersing agent to perform emulsification to obtain spherical liquid drops; raising the temperature to make the spherical liquid drops undergo in-situ polymerization so as to solidify and shape the liquid drops; performing solid-liquid separation to obtain spherical lithium titanate precursor particles; and drying and sintering the particles to obtain the spherical lithium titanate cathode material. Through the method, raw materials in the molecular level can be uniformly mixed and the electrical conductivity of the material is improved by adding various doped elements in the preparation process; the prepared material has the advantages of high electrochemical property and sphericity, narrow particle size distribution and high processability; and the method has the advantages of readily available raw materials, simple process, convenient operation and easy realization of industrialization.
Description
Technical field
The present invention relates to lithium ion battery negative material, particularly the preparation method of spherical lithium titanate anode material.
Background technology
Along with petering out of fossil fuel, under an urgent demand of sustainable development, the lithium ion battery that is used for power or large-scale energy storage is just becoming one of research focus.And high security and low price are the keys of lithium ion battery large-scale application.Present commercial lithium ion battery uses MCMB (carbonaceous mesophase spherules) or hard carbon as negative pole mostly.Though have many advantages, also still have many deficiencies.Though low as the MCMB cost, capacity is high, its cycle performance, cryogenic property and fills poor-performing soon; Though hard carbon power density height, have extended cycle life, low temperature and security performance be better, energy density and first charge-discharge efficiency are lower, and have tangible voltage delay phenomenon.Current potential that the more important thing is the current potential of carbon negative pole and lithium is very approaching, and during over-charging of battery, lithium metal may be separated out in the carbon negative terminal surface and be caused safety problem.
The lithium titanate of spinel structure has the higher embedding lithium current potential of 1.55V, is difficult for causing that lithium metal separates out, and can not form the SEI film of poor heat stability with the electrolyte reaction, and is higher as the fail safe of battery cathode.Spinel lithium titanate skeleton structure in charge and discharge process changes (brilliant inclusion is long-pending to be changed less than 0.1%) hardly, the cyclical stability excellence.This material also has higher coulombic efficiency and lithium ion diffusion coefficient (2 * 10
-8Cm
2/ s) wait good characteristic, possessed the characteristic that the essential charging times of lithium ion battery of future generation is more, charging process is faster, more economical, safer, be widely used at power or large-scale energy-storage battery field.Simultaneously, spinel lithium titanate also can be applicable to ultracapacitor, is used in electric motor car or field of hybrid electric vehicles, satisfies the high power requirement of fast charging and discharging.But energy density is low to be the major defect of the lithium titanate of spinel structure, has limited the application of this material.
The raising of energy density will improve the capacity performance of material at battery system on the one hand, will improve the compacted density of electrode plates on the other hand.Adopt the lithium titanate of the synthetic high electrochemical performance of methods such as traditional high temperature solid-state method, sol-gal process, high-energy ball milling method to be the submicron powder particle.Improve the lithium titanate powdery grain graininess, then can sacrifice its charge/discharge capacity and high rate performance.The submicron powder grain graininess is little, granule-morphology is irregular, specific area is big, causes problems such as pole piece processing difficulties, pole piece compacted density be low, can't overcome the major defect of lithium titanate.By the synthetic secondary spherical lithium titanate particle of forming by nanocrystal, can not only keep the original high electrochemical performance of material, can also improve the energy density of pole piece processing characteristics, raising material.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing spherical lithium titanate anode material, realize the lithium ion battery negative material of high electrochemical performance and excellent machinability.
The method that the present invention prepares spherical lithium titanate anode material comprises the steps:
1) organic lithium salt is dissolved in the alcohols solvent, and by Li: the Ti mol ratio is 0.8～0.9 to add a certain amount of titanate esters, and mixing makes and contains lithium titanium mixed liquor;
2) the lithium titanium mixed liquor that contains that step 1) is made joins in the immiscible with it organic dispersing agent, stirring makes and contains lithium titanium mixed liquor emulsification formation spherical droplets, be warming up to 60～90 ℃ subsequently and keep 10min～2h, spherical droplets generation in-situ polymerization and curing molding, carry out Separation of Solid and Liquid then, obtain spherical lithium titanate precursor particle;
3) with step 2) the spherical lithium titanate precursor particle that makes carries out presintering under 200～600 ℃ of temperature, and sintering 1～20h under 650～850 ℃ of high temperature obtains spherical lithium titanate material again.
Above-mentioned steps 1) in, described organic lithium salt is preferably one or more in lithium oxalate, lithium formate, lithium acetate, lithium citrate, lithium tartrate, lithium benzoate, oleic acid lithium, lithium stearate, acrylic acid lithium, lithium methoxide and the lithium ethoxide; Described titanate esters is preferably one or more in metatitanic acid tetramethyl ester, butyl titanate, iso-butyl titanate and the tetraisopropyl titanate; Described alcohols solvent is one or more in methyl alcohol, ethanol, isopropyl alcohol and the n-butanol normally.
Step 1) make contain lithium titanium mixed liquor after, can be to wherein adding a certain amount of curing agent, to improve step 2) curing rate.Described curing agent can be the aqueous solution of urea of deionized water or 0.1～50wt%, and the addition of curing agent is to contain below the 5wt% of lithium titanium mixed liquor;
Above-mentioned steps 2) the immiscible organic dispersing agent described in can be one or more in toluene, paraffin, silicone oil, kerosene and the carbon tetrachloride.For promoting to contain the dispersion of lithium titanium mixed liquor, in described organic dispersing agent, add surfactant, spendable surfactant has one or more among Tween80, Tween60, the Span80, and addition generally is 0.1～15% of an organic dispersing agent weight.
The atmosphere of high temperature sintering is not particularly limited in step 3), can be air atmosphere, inert atmosphere or reducing atmosphere, is preferably inert atmosphere or reducing atmosphere, for example nitrogen, argon gas, hydrogen.200～600 ℃ of presintering times of step 3) generally are 3～8h, 650～850 ℃ of preferred 3～12h of high temperature sintering time.
Further, for improving the electric conductivity of prepared material, can also prepare in the process that contains lithium titanium mixed liquor in step 1) and add Mg
2+, Al
3+, Zn
2+, Zr
4+, Co
3+, V
5+Deng in one or more ions.
Method of the present invention has realized the even mixing of raw material in the molecular level level, in preparation process, also be easy to add the conductivity that various doped chemicals improve material, prepare spherical lithium titanate anode material and have excellent electrochemical properties, good sphericity, narrow particle size distribution has good processing properties.The inventive method raw material is easy to get, and technology is simple, and is easy to operate, is easy to realize industrialization.
Description of drawings
Fig. 1 is the SEM figure of the spherical lithium titanate anode material of the embodiment of the invention four preparations.
Fig. 2 is the first charge-discharge curve of the embodiment of the invention three preparation lithium titanate anode materials.
Embodiment
Below in conjunction with accompanying drawing, by embodiment the present invention is described in further detail, but the scope that does not limit the present invention in any way.
Embodiment one
Take by weighing the 30g lithium acetate and be dissolved in the 100ml ethanol, add the 126g butyl titanate, stir formation and contain lithium titanium mixed liquor uniformly.The lithium titanium mixed liquor that contains that will prepare under the magnetic agitation condition is scattered in the kerosene that contains 1.5wt%Span80.Continue to stir, be heated to 80 ℃, be incubated 40 minutes.Suction filtration separates, and obtains spherical lithium titanate precursor.Behind 400 ℃ of pre-burning 6h, 800 ℃ of sintering 8h obtain spherical lithium titanate powdery material in the nitrogen protection stove with spherical lithium titanate precursor.Measuring this sample granularity D50 with laser particle size analyzer is 15 μ m.Take by weighing this sample of 120mg, with sample powder, acetylene black and PTFE (Polytetrafluoro ethylene, polytetrafluoroethylene) with the mixed of 8: 1: 1 (mass ratio), be pressed into electrode slice, as anodal, make negative pole with the pure metal lithium sheet after vacuumize, recording the specific discharge capacity of this sample when 0.2C discharges and recharges is 157mAh/g, first charge-discharge efficiency is 95%, and the specific discharge capacity when 1C discharges and recharges is 148mAh/g.
Embodiment two
Take by weighing the 30g lithium acetate and be dissolved in the 100ml ethanol, add the 122g butyl titanate, stir formation and contain lithium titanium mixed liquor uniformly.The lithium titanium mixed liquor that contains that will prepare under the magnetic agitation condition is scattered in the kerosene that contains 1.5wt%Span80.Continue to stir, be heated to 80 ℃, be incubated 30 minutes.Suction filtration separates, and obtains spherical lithium titanate precursor.Behind 400 ℃ of pre-burning 6h, 800 ℃ of sintering 8h obtain spherical lithium titanate powdery material in the nitrogen protection stove with spherical lithium titanate precursor.Measuring this sample granularity D50 with laser particle size analyzer is 15 μ m.Take by weighing this sample of 120mg, with sample powder, acetylene black and PTFE mixed with 8: 1: 1 (mass ratio), be pressed into electrode slice, conduct is anodal after vacuumize, make negative pole with the pure metal lithium sheet, recording the specific discharge capacity of this sample when 0.2C discharges and recharges is 159mAh/g, and first charge-discharge efficiency is 95.6%, and the specific discharge capacity when 1C discharges and recharges is 150mAh/g.
Embodiment three
The method identical with embodiment two preparation earlier contains lithium titanium mixed liquor.To contain lithium titanium mixed liquor under the high speed ball milling condition is scattered in the paraffin oil that contains 5wt%Span80.Continue ball milling, be heated to 80 ℃, be incubated 30 minutes.Suction filtration separates, and obtains spherical lithium titanate precursor.Behind 400 ℃ of pre-burning 6h, 800 ℃ of sintering 8h obtain spherical lithium titanate powdery material in the nitrogen protection stove with spherical lithium titanate precursor.Measuring this sample granularity D50 with laser particle size analyzer is 12 μ m.Take by weighing this sample of 120mg, with sample powder, acetylene black and PTFE mixed with 8: 1: 1 (mass ratio), be pressed into electrode slice, conduct is anodal after vacuumize, make negative pole with the pure metal lithium sheet, adhesive adopts Kynoar, and barrier film adopts polypropylene microporous film, electrolyte is 1.0mol/L LiPF6, and solvent is that EC-DEC-DMC (1: 1: 1 volume ratio) (annotates: the EC-ethylene carbonate; The DEC-diethyl carbonate; The DMC-dimethyl carbonate), voltage range is 1.0～2.5V, constant current charge-discharge electric current 0.2C, measurement result as shown in Figure 2, the specific discharge capacity of this sample when 0.2C discharges and recharges is 172mAh/g, first charge-discharge efficiency is 96.5%, and the specific discharge capacity when 1C discharges and recharges is 151mAh/g, has excellent electrochemical properties.
Embodiment four
The method identical with embodiment three be the spherical lithium titanate precursor of preparation earlier, and behind 300 ℃ of pre-burning 6h, 800 ℃ of sintering 8h obtain spherical lithium titanate powdery material in air atmosphere.Measuring this sample granularity D50 with laser particle size analyzer is 10 μ m.Take by weighing this sample of 120mg, with sample powder, acetylene black and PTFE mixed with 8: 1: 1 (mass ratio), be pressed into electrode slice, conduct is anodal after vacuumize, make negative pole with the pure metal lithium sheet, recording the specific discharge capacity of this sample when 0.2C discharges and recharges is 165mAh/g, and first charge-discharge efficiency is 94.6%, and the specific discharge capacity when 1C discharges and recharges is 150mAh/g.
The A of Fig. 1 and B are the prepared SEM figure of spherical lithium titanate powdery material under different amplification, and as can be seen from Figure 1 prepared lithium titanate particle is the spherical morphology of rule, even particle size distribution, the about 10 μ m of particle diameter.
Embodiment five
Take by weighing the 30g lithium acetate and be dissolved in the 100ml methyl alcohol, add the 125g iso-butyl titanate, slowly drip 20wt% aqueous solution of urea 2ml under stirring condition, continuation is stirred to form and is contained lithium titanium mixed liquor uniformly.The lithium titanium mixed liquor that contains that will prepare under the high-speed stirred condition is scattered in the paraffin oil that contains 1.5wt%Span80.Continue to stir, be heated to 80 ℃, be incubated 15 minutes.Suction filtration separates, and obtains spherical lithium titanate precursor.Behind 350 ℃ of pre-burning 6h, 800 ℃ of sintering 8h obtain spherical lithium titanate powdery material in the nitrogen protection stove with spherical lithium titanate precursor.Measuring this sample granularity D50 with laser particle size analyzer is 10 μ m.Take by weighing this sample of 120mg, with sample powder, acetylene black and PTFE mixed with 8: 1: 1 (mass ratio), be pressed into electrode slice, conduct is anodal after vacuumize, make negative pole with the pure metal lithium sheet, recording the specific discharge capacity of this sample when 0.2C discharges and recharges is 167mAh/g, and first charge-discharge efficiency is 96%, and the specific discharge capacity when 1C discharges and recharges is 148mAh/g.
Embodiment six
Take by weighing 30g lithium acetate and 0.6g magnesium nitrate and be dissolved in the 100ml ethanol, add the 122g butyl titanate, slowly drip the 2ml deionized water under stirring condition, continuation is stirred to form and is contained lithium titanium mixed liquor uniformly.The lithium titanium mixed liquor that contains that will prepare under the high-speed stirred condition is scattered in the kerosene that contains 1.5wt%Span80 and 1.5wt%Tween60.Continue to stir, be heated to 80 ℃, be incubated 30 minutes.Suction filtration separates, and obtains spherical lithium titanate precursor.Behind 300 ℃ of pre-burning 4h, 800 ℃ of sintering 8h obtain spherical lithium titanate powdery material in the nitrogen protection stove with spherical presoma.Measuring this sample granularity D50 with laser particle size analyzer is 13 μ m.Take by weighing this sample of 120mg, with sample powder, acetylene black and PTFE mixed with 8: 1: 1 (mass ratio), be pressed into electrode slice, conduct is anodal after vacuumize, make negative pole with the pure metal lithium sheet, recording the specific discharge capacity of this sample when 0.2C discharges and recharges is 165mAh/g, and first charge-discharge efficiency is 96%, and the specific discharge capacity when 1C discharges and recharges is 158mAh/g.
Claims (10)
1. the preparation method of a spherical lithium titanate anode material comprises the steps:
1) organic lithium salt is dissolved in the alcohols solvent, and by Li: the Ti mol ratio is 0.8～0.9 to add a certain amount of titanate esters, and mixing makes and contains lithium titanium mixed liquor;
2) the lithium titanium mixed liquor that contains that step 1) is made joins in the immiscible with it organic dispersing agent, stirring makes and contains lithium titanium mixed liquor emulsification formation spherical droplets, be warming up to 60～90 ℃ subsequently and keep 10min～2h, spherical droplets generation in-situ polymerization and curing molding, carry out Separation of Solid and Liquid then, obtain spherical lithium titanate precursor particle;
3) with step 2) the spherical lithium titanate precursor particle that makes is 200～600 ℃ of presintering, at 650～850 ℃ of sintering 1～20h, obtains spherical lithium titanate anode material again.
2. preparation method as claimed in claim 1, it is characterized in that organic lithium salt described in the step 1) is selected from one or more in lithium oxalate, lithium formate, lithium acetate, lithium citrate, lithium tartrate, lithium benzoate, oleic acid lithium, lithium stearate, acrylic acid lithium, lithium methoxide and the lithium ethoxide.
3. preparation method as claimed in claim 1 is characterized in that, titanate esters described in the step 1) is selected from one or more in metatitanic acid tetramethyl ester, butyl titanate, iso-butyl titanate and the tetraisopropyl titanate.
4. preparation method as claimed in claim 1 is characterized in that alcohols solvent described in the step 1) is selected from one or more in methyl alcohol, ethanol, isopropyl alcohol and the n-butanol.
5. preparation method as claimed in claim 1 is characterized in that, carry out step 2 again after step 1) is added the following curing agent of 5wt% at containing in the lithium titanium mixed liquor of making).
6. preparation method as claimed in claim 5 is characterized in that, described curing agent is the aqueous solution of urea of deionized water or 0.1～50wt%.
7. preparation method as claimed in claim 1 is characterized in that step 2) described in organic dispersing agent be selected from toluene, paraffin, silicone oil, kerosene and the carbon tetrachloride one or more.
8. preparation method as claimed in claim 1 is characterized in that, is added with surfactant in the described organic dispersing agent.
9. preparation method as claimed in claim 8 is characterized in that described surfactant is selected from one or more among Tween80, Tween60, the Span80.
10. preparation method as claimed in claim 1 is characterized in that, prepares in the process that contains lithium titanium mixed liquor in step 1) and adds Mg
2+, Al
3+, Zn
2+, Zr
4+, Co
3+And V
5+In one or more ions.
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| CN102328953A (en) * | 2011-07-28 | 2012-01-25 | 华南农业大学 | Preparation method of lithium titanate with special morphology |
| CN102997651A (en) * | 2012-11-30 | 2013-03-27 | 龙能科技（苏州）有限公司 | Pusher furnace for preparing lithium titanate negative electrode materials of lithium ion battery and method |
| CN103700816A (en) * | 2013-12-12 | 2014-04-02 | 天津巴莫科技股份有限公司 | Preparation method of silicon-based composite of lithium ion battery |
| CN104882597A (en) * | 2015-03-29 | 2015-09-02 | 南阳师范学院 | Simple, efficient and low-cost preparation method for nano lithium titanate |
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| CN102328953A (en) * | 2011-07-28 | 2012-01-25 | 华南农业大学 | Preparation method of lithium titanate with special morphology |
| CN102328953B (en) * | 2011-07-28 | 2013-11-13 | 华南农业大学 | Preparation method of lithium titanate with special morphology |
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| CN103700816A (en) * | 2013-12-12 | 2014-04-02 | 天津巴莫科技股份有限公司 | Preparation method of silicon-based composite of lithium ion battery |
| CN103700816B (en) * | 2013-12-12 | 2016-02-03 | 天津巴莫科技股份有限公司 | A kind of preparation method of lithium ion battery silicon based composite material |
| CN104882597A (en) * | 2015-03-29 | 2015-09-02 | 南阳师范学院 | Simple, efficient and low-cost preparation method for nano lithium titanate |
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| CN113921806A (en) * | 2020-07-10 | 2022-01-11 | 精工爱普生株式会社 | Precursor solution and powder of negative electrode active material, and method for producing negative electrode active material |
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