CN102820460A - Electrostatic spinning method for preparing rare-earth metal doped nanometer lithium titanate - Google Patents

Electrostatic spinning method for preparing rare-earth metal doped nanometer lithium titanate Download PDF

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CN102820460A
CN102820460A CN2012102969824A CN201210296982A CN102820460A CN 102820460 A CN102820460 A CN 102820460A CN 2012102969824 A CN2012102969824 A CN 2012102969824A CN 201210296982 A CN201210296982 A CN 201210296982A CN 102820460 A CN102820460 A CN 102820460A
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acid
electrostatic spinning
lithium
earth metal
rare earth
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CN102820460B (en
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张遥遥
张春明
王丹
吴晓燕
余震
汪元元
何丹农
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Shanghai Jiaotong University
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai Jiaotong University
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Abstract

The invention discloses an electrostatic spinning method for preparing a rare-earth metal doped nanometer lithium titanate. The electrostatic spinning method comprises the following steps: preparing a Li4Ti5O12 precursor gel according to a sol gel method; doping rare-earth metal ions and covering carbon on the Li4Ti5O12 precursor gel; after electro-statically spinning, obtaining a nanometer fiber Li4Ti5O12 precursor; and calcining at high temperature under an anaerobic condition, thereby synthesizing a Li4Ti5O12/C fiber. According to the electrostatic spinning method provided by the invention, the nanometer lithium titanate is synthesized on a nanometer carbon fiber skeleton; the particle aggregation is effectively prevented; a carbon covering effect is also achieved by the nanometer carbon fiber skeleton; the rare-earth metal is taken as a doping agent, so that the electrical conductivity of the material is improved and the increase of the electrochemical property under high multiplying power is realized; the obtained cathode material has a better electrochemical property; higher discharging capacity is obtained under the condition of high multiplying power charging/discharging; and the cycle performance is also stable.

Description

Method of electrostatic spinning prepares the nano lithium titanate that rare earth metal mixes
Technical field
The present invention relates to a kind of preparation method of ion secondary battery cathode material lithium, particularly relate to a kind of ion secondary battery cathode material lithium nano lithium titanate fiber preparation method.
Background technology
1991; Sony corporation of japan has been issued first in the world lithium ion battery; Lithium ion battery begins to be widely used in emerging consumer electronic product subsequently; For example on the portable electric products such as mobile phone, camera, notebook computer, to 1997, lithium ion battery occupied the biggest market share of chargeable battery.At present, the negative material that commercially available lithium ion battery adopted is material with carbon element mostly, but there is certain potential safety hazard in this type of negative material.When battery filled soon or overcharges, electrode material surface can the precipitating metal lithium and is formed dendrite and cause short circuit.Along with the rapid increase in lithium ion battery market, press for the better novel negative material of security performance.And spinelle Li 4Ti 5O 12Just begin to receive extensive concern because of its zero strain property, high security.
Spinelle Li 4Ti 5O 12Outstanding feature is a zero strain property, the embedding lithium with take off in the lithium process, its lattice constant and change in volume all are no more than 1%, thereby it has extended cycle life stable performance and safe.Li 4Ti 5O 12Relatively the current potential of lithium electrode is about 1.55V, and discharge platform is mild, and theoretical specific capacity is 175mAh/g, and since its reversible lithium ratio of taking off near 100%, thereby the actual capacity and the theoretical capacity of experiment gained are comparatively approaching, can reach more than the 160mAh/g basically.But because spinelle Li 4Ti 5O 12Be a kind of insulating material, its intrinsic conductivity is merely 10 -9S/cm, so conductivity extreme difference are very limited when being applied as lithium ion battery negative material, and especially under the high-multiplying power discharge condition, the easy enrichment of electronics produces the embedding of electrode polarization and then limiting lithium ion and deviates from, and finally influences the performance of battery.In order to solve this difficult problem, general improvement method is Li 4Ti 5O 12The nanometerization of particle size is perhaps introduced the lifting that conductive materials is realized conductivity.Submicron order and nanometer materials that sol-gal process can preparation scale be evenly distributed; Make reactant on molecule or atomic level, fully contact, mix; The product particle that makes is tiny and even; Purity is high, and can control the form and the performance of product through the change of related process parameter.But traditional sol-gal process building-up process; There is certain particle agglomeration phenomenon; Can not form desirable gel three-dimensional net structure, the size of its specific area and the degree of scatter of active component receive the restriction of agglomeration, thereby the chemical property under high magnification is performed poor.The present invention is with electrostatic spinning assisting sol gel method, with Li 4Ti 5O 12Particle synthesizes on the carbon nano-fiber skeleton, prevents that product from reuniting, and simultaneously with carbon as surperficial covering, rare earth metal improves material conductivity as dopant, realizes the lifting of the chemical property under the high magnification.
Summary of the invention
The objective of the invention is to overcome and have the particle agglomeration phenomenon in the Prepared by Sol Gel Method lithium titanate anode material,, obtain a kind of rare earth metal Li doped that the carbon nano-fiber skeleton is supported that has through electrostatic spinning assisting sol gel technique 4Ti 5O 12Negative material, the even dispersion and the carbon covered effect of realization active material particle obtain under high magnification, to have high charge-discharge capacity and excellent cycle performance.
For reaching above-mentioned intended purposes, the present invention adopts following technical scheme:
A kind of preparation method of ion secondary battery cathode material lithium nano lithium titanate is characterized in that: with Prepared by Sol Gel Method Li 4Ti 5O 12Aqueous precursor gel mixes and the carbon coating through rare earth ion, obtains nanofiber Li behind the electrostatic spinning 4Ti 5O 12Presoma carries out the synthetic Li of high-temperature calcination under oxygen-free environment 4Ti 5O 12/ C fiber.This technology comprises the steps:
A. in absolute ethyl alcohol, dissolve macromolecule organic, the mass concentration of high molecular polymer is 0.05 ~ 0.2g/mL, and magnetic agitation is until the colloidal sol that is transparent clarification.
B. in the Polymer Solution that step a joins; Mol ratio according to Li:Ti=0.8～1.0:1, thulium: Ti=0.001 ~ 0.2:1; The slightly soluble of adding lithium and titanium or soluble compound and rare earth compound are (if rare earth compound is the indissoluble thing; Need add the acid dissolving), and drop into the hydrolysis inhibitor of acid as the Ti compound.Add chelating agent again, the mol ratio of chelating agent and metal ion is 0 ~ 1.5:1, and under the normal temperature condition, magnetic agitation to solution is clarified.
C. in the colloidal sol of step b gained, add volume fraction and be 0.05% ~ 2% conductive agent, continue to stir.
D. the colloidal sol with step c gained carries out electrostatic spinning with electrostatic spinning machine, obtains the thick white film of 0.2 ~ 2mm, and is dry stable under the room temperature.
E. the lithium titanate precursor film is put into tube furnace, calcining in inert atmosphere (in argon gas, nitrogen, the helium a kind of), temperature is 700～1000 ℃, obtains the nano lithium titanate fiber that carbon coats, rare earth metal mixes.
Described slightly soluble or soluble lithium compounds are a kind of in lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, isopropyl alcohol lithium, long-chain or the short-chain alkyl lithium.
Described soluble titanium compound is a tetra-n-butyl titanate, or tetraisopropyl titanate, or the chloride of titanium, and wherein titanium compound is titanium compound: alcohol=1:1～10 with the volume ratio of alcohol.
Described rare earth compound is one or more in lanthana, lanthanum nitrate, lanthanum oxalate, lanthanum chloride, neodymia, neodymium nitrate, gadolinium oxide, gadolinium nitrate, gadolinium chloride, Digadolinium trisulfate, Gadolinium monophosphate, scandium oxide, scandium nitrate, scandium chloride, scandium carbonate, dysprosia, praseodymium oxide, praseodymium chloride, the praseodymium sulfide.
Described acid is a kind of or its combination in nitric acid, hydrochloric acid, acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, benzoic acid, salicylic acid, the caffeic acid, and alcohol is alcohol with the volume ratio of acid: acid=1:0.1～0.5.
Described chelating agent is triethanolamine, acetate, laurate, tartaric acid, citric acid, oxalic acid, gluconic acid, 2; 2'-bipyridine, 1, a kind of or its combination in 10-phenanthrolene, aminotriacetic acid, diethylene-triamine pentaacetic acid, ethylenediamine, the ethylenediamine tetra-acetic acid.The conventional method for preparing lithium titanate with method of electrostatic spinning is not added chelating agent usually perhaps with acids hydrolysis inhibitor double as chelating agent; And is no lack of macromolecule organic in the chelating agent of the present invention; This type of chelating agent be added with the even distribution that helps Li, Ti, rare earth ion, form the colloidal sol of high degree of dispersion, metal ion is being dispersed in behind the electrostatic spinning on the macromolecule organic skeleton; After calcining, guarantee that product is pure phase lithium titanate.
Described macromolecule organic is polyvinylpyrrolidone (Mw=600; 000～1; 300,000), a kind of in acetylperoxide nitrate, PLA, PEO, polyvinyl alcohol, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, polyacrylonitrile, polyether sulfone, polylactic acid-glycolic guanidine-acetic acid copolymer, the polyvinyl butyral resin.
Described conductive agent is a kind of in 1-Methyl-2-Pyrrolidone, carrene, methyl alcohol, formic acid, ethanol, acetate, ethylene glycol, acetamide, acetone, chloroform, oxolane, malononitrile, the acetic anhydride.Because there are the situation of poorly conductive in product lithium titanate and reactant thereof, therefore there is the problem that spinning efficiency is low, operating voltage is too high in many colloidal sols to be spun.Introduce conductive agent among the present invention, can increase the electric conductivity of waiting to spin colloidal sol, be easy to control the technological parameter of electrostatic spinning, can effectively improve spinning efficiency, and operating voltage is controlled at zone of reasonableness.
Technological parameter in the described electrostatic spinning process is: flow is 0.2 ~ 1.0mL/hr, and operating voltage is 10 ~ 15KV, and the dash receiver distance is 10 ~ 30cm.
Said the lithium titanate precursor film is put into tube furnace, in inert atmosphere, calcined 5～15 hours, heating rate is 1～15 ℃/min.
Compared with prior art, the present invention adopts electrostatic spinning assisting sol gel method to prepare Li 4Ti 5O 12Negative material, high molecular polymer both can be used as spinning-aid agent, can be used as carbon again and coat the source, and formation is fiber reinforcement, Li with the carbon coated 4Ti 5O 12Unique nanofibrous structures that uniform particles is disperseed obviously improves the particle agglomeration phenomenon of material, and rare earth metal mixes then can effectively improve material conductivity, thereby two aspect actings in conjunction realize the lifting of the chemical property of materials under high magnification.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 1 product;
Fig. 2 is the charge and discharge cycles curves of the embodiment of the invention 2 products under different multiplying;
Fig. 3 is the cyclical stability results of the embodiment of the invention 3 products under different multiplying.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment is that prerequisite is implemented with technical scheme of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
0.6g polyvinylpyrrolidone (PVP K90) is dropped in the 9mL absolute ethyl alcohol, stir until dissolving fully.Again according to the mol ratio of Li:Ti=4.2:5, with 1.702g tetra-n-butyl titanate, 0.277g lithium acetate input join macromolecule polymer solution in, add the 1.778g citric acid simultaneously, stir until the solution clarification, obtain solution A; According to the mol ratio of La:Ti=0.02:5, with obtaining solution B after the dissolving fully in the 0.0033g lanthana adding 3mL nitric acid.Solution A is mixed with solution B, and normal temperature stirred 2 hours down, dropped into 0.1mL 1-Methyl-2-Pyrrolidone continued stirring at normal temperature 1.5 hours, obtained electrostatic spinning solution.Select the electrostatic spinning process parameter to be: flow is 0.3mL/hr, and operating voltage is 15KV, and the dash receiver distance is 15cm, carries out electrostatic spinning, spin behind the 2mm after the white film, vacuumize was at normal temperatures stablized 8 hours.Film is taken off with tube furnace under argon gas atmosphere, and 800 ℃ of calcinings of high temperature obtained the lithium titanate product that lanthanum mixes, carbon coats in 10 hours.Fig. 1 is the XRD figure of gained sample.The Li visible by figure, that the lanthanum that is synthesized mixes, carbon coats 4Ti 5O 12Equal and the Li of the position of each diffraction maximum of XRD figure and relative intensity 4Ti 5O 12Standard card match, do not have any dephasign.
Embodiment 2:
2.48g polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (Pluronic P123) is dropped in the 17.73mL absolute ethyl alcohol, stir until dissolving fully.Again according to the mol ratio of Li:Ti=1:1, with 1.702g tetra-n-butyl titanate, 0.345g lithium nitrate input join macromolecule polymer solution in, add the 2.260g triethanolamine simultaneously, stir until the solution clarification, obtain solution A; According to the mol ratio of Nd:Ti=0.1:5, with obtaining solution B after the dissolving fully in the 0.0168g neodymia adding 7.09mL acetic acid.Solution A is mixed with solution B, and normal temperature stirred 3 hours down, dropped into 0.50mL carrene continued stirring at normal temperature 1 hour, obtained electrostatic spinning solution.Select the electrostatic spinning process parameter to be: flow is 1.0mL/hr, and operating voltage is 15KV, and the dash receiver distance is 30cm, carries out electrostatic spinning, spin behind the 0.2mm after the white film, vacuumize was at normal temperatures stablized 4 hours.Film is taken off with tube furnace under argon gas atmosphere, and 1000 ℃ of calcinings of high temperature obtained the lithium titanate product that neodymium mixes, carbon coats in 5 hours.Fig. 2 is for to do positive pole with this material, and lithium metal is made the button-shaped half-cell that negative pole is assembled into, and the charging and discharging curve under 1～40C different multiplying is visible by figure, the Li that the lanthanum that is synthesized mixes, carbon coats 4Ti 5O 12Charge and discharge platform is smooth, demonstrate embedding lithium performance preferably, and reversible capacity is higher, and discharge capacity can reach 174.15mAh/g during 1C, and discharge capacity also reaches 110.53mAh/g during 20C.
Embodiment 3:
The 4.04g polyvinyl butyral resin is dropped in the 13.46mL absolute ethyl alcohol, stir until dissolving fully.According to the mol ratio of Li:Ti=4.8:5, Gd:Ti=0.001:5, with 1.421g tetraisopropyl titanate, 0.178g lithium carbonate, 0.0004g gadolinium nitrate input join macromolecule polymer solution in, add 6.73mL hydrochloric acid, stir and clarify until solution.Drop into 0.30mL acetone continued stirring at normal temperature at last 1 hour, and obtained electrostatic spinning solution.Select the electrostatic spinning process parameter to be: flow is 0.2mL/hr, and operating voltage is 10KV, and the dash receiver distance is 10cm, carries out electrostatic spinning, spin behind the 1mm after the white film, vacuumize was at normal temperatures stablized 6 hours.Film is taken off with tube furnace under nitrogen atmosphere, and 700 ℃ of calcinings of high temperature obtained the lithium titanate product that gadolinium mixes, carbon coats in 15 hours.Fig. 3 is the discharge cycles curve of this sample under the different multiplying, and is visible by figure, and this material is under different multiplying powers, and repeatedly circulation back capacitance loss is very little, good cycling stability.
Embodiment 4:
0.180g polylactic acid-glycolic guanidine-acetic acid copolymer is dropped in the 1.496mL absolute ethyl alcohol, stir until dissolving fully.Mol ratio according to Li:Ti=4.0:5, Sc:Ti=0.2:5; With 1.421g tetraisopropyl titanate, 0.17g lithium chloride, 0.0464g scandium nitrate input join macromolecule polymer solution in; Add the 0.748mL salicylic acid, stir, add the 1.344g ethylenediamine tetra-acetic acid again until the solution clarification; Normal temperature stirred 2 hours down, clarified until solution.Drop into 0.02mL ethylene glycol continued stirring at normal temperature at last 1 hour, and obtained electrostatic spinning solution.Select the electrostatic spinning process parameter to be: flow is 0.6mL/hr, and operating voltage is 13KV, and the dash receiver distance is 12cm, carries out electrostatic spinning, spin behind the 0.8mm after the white film, vacuumize was at normal temperatures stablized 5 hours.Film is taken off with tube furnace under nitrogen atmosphere, and 900 ℃ of calcinings of high temperature obtained the lithium titanate product that scandium mixes, carbon coats in 8 hours.
Embodiment 5:
1g acetylperoxide nitrate is dropped in the 2.75mL absolute ethyl alcohol, stir until dissolving fully.Again according to the mol ratio of Li:Ti=4.5:5, with 0.950g titanium chloride, 0.423g lithium citrate input join macromolecule polymer solution in, add 0.460g acetate simultaneously, stir until the solution clarification, obtain solution A; According to the mol ratio of Dy:Ti=0.08:5, with obtaining solution B after the dissolving fully in the 0.0148g dysprosia adding 0.55mL oxalic acid.Solution A is mixed with solution B, and normal temperature stirred 1 hour down, dropped into 0.05mL oxolane continued stirring at normal temperature 3 hours, obtained electrostatic spinning solution.Select the electrostatic spinning process parameter to be: flow is 0.8mL/hr, and operating voltage is 14KV, and the dash receiver distance is 18cm, carries out electrostatic spinning, spin behind the 1.5mm after the white film, vacuumize was at normal temperatures stablized 10 hours.Film is taken off with tube furnace under nitrogen atmosphere, and 850 ℃ of calcinings of high temperature obtained the lithium titanate product that dysprosium mixes, carbon coats in 9 hours.
Embodiment 6:
The 0.988g polyvinyl alcohol is dropped in the 5.49mL absolute ethyl alcohol, stir until dissolving fully.Again according to the mol ratio of Li:Ti=4.4:5, with 0.950g titanium chloride, 0.224g lithium oxalate input join macromolecule polymer solution in, add the 2.202g citric acid simultaneously, stir until the solution clarification, obtain solution A; According to the mol ratio of Pr:Ti=0.15:5, with obtaining solution B after the dissolving fully in the 0.0248g praseodymium oxide adding 2.75mL nitric acid.Solution A is mixed with solution B, and normal temperature stirred 2 hours down, dropped into 0.01mL chloroform continued stirring at normal temperature 2 hours, obtained electrostatic spinning solution.Select the electrostatic spinning process parameter to be: flow is 0.6mL/hr, and operating voltage is 12KV, and the dash receiver distance is 20cm, carries out electrostatic spinning, spin behind the 0.6mm after the white film, vacuumize was at normal temperatures stablized 6 hours.Film is taken off with tube furnace under nitrogen atmosphere, and 800 ℃ of calcinings of high temperature obtained the lithium titanate product that praseodymium mixes, carbon coats in 10 hours.
The nano lithium titanate of above embodiment preparation synthesizes on the carbon nano-fiber skeleton; Prevented particle agglomeration effectively; And the carbon nano-fiber skeleton also can reach the effect of carbon coated; While as dopant, has been improved the conductivity of material with rare earth metal jointly, realizes the lifting of the chemical property under the high magnification.The negative material that is obtained all has better electrochemical performance, under the high power charging-discharging condition, can obtain higher discharge capacity, and cycle performance is also highly stable simultaneously.Under the room temperature condition, during the 1C multiplying power its first discharge capacity reached 174.15mAh/g, discharge capacity also reaches 110.53mAh/g during 20C, can predict the nano lithium titanate that this preparation method produces gained and have higher commercial application value.
More than be part embodiment of the present invention,, will be appreciated that above-mentioned description should not be considered to limitation of the present invention although content of the present invention has been done detailed introduction through above-mentioned part embodiment.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute all will be conspicuous.Therefore, protection scope of the present invention should be limited appended claim.

Claims (10)

1. a method of electrostatic spinning prepares the nano lithium titanate that rare earth metal mixes, and it is characterized in that: with Prepared by Sol Gel Method Li 4Ti 5O 12Aqueous precursor gel mixes and the carbon coating through rare earth ion, obtains nanofiber Li behind the electrostatic spinning 4Ti 5O 12Presoma carries out the synthetic Li of high-temperature calcination under oxygen-free environment 4Ti 5O 12/ C fiber; This technology comprises the steps:
A. in absolute ethyl alcohol, dissolve macromolecule organic, the mass concentration of high molecular polymer is 0.05 ~ 0.2g/mL, and magnetic agitation is until the colloidal sol that is transparent clarification;
B. in the Polymer Solution that step a joins; According to the mol ratio of Li:Ti=0.8～1.0:1, thulium: Ti=0.001 ~ 0.2:1, add slightly soluble or the soluble compound and the rare earth compound of lithium and titanium, and drop into the hydrolysis inhibitor of acid as the Ti compound; Add chelating agent again; The mol ratio of chelating agent and metal ion is 0 ~ 1.5:1, and under the normal temperature condition, magnetic agitation to solution is clarified;
C. in the colloidal sol of step b gained, adding into volume fraction is 0.05% ~ 2% conductive agent, continues to stir;
D. the colloidal sol with step c gained carries out electrostatic spinning with electrostatic spinning machine, obtains the thick white film of 0.2 ~ 2mm, and is dry stable under the room temperature;
E. the lithium titanate precursor film is put into tube furnace, in inert atmosphere, calcine, temperature range is 700～1000 ℃, obtains the nano lithium titanate fiber that carbon coats, rare earth metal mixes.
2. method of electrostatic spinning according to claim 1 prepares the nano lithium titanate that rare earth metal mixes; It is characterized in that described slightly soluble or soluble lithium compounds are a kind of in lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, isopropyl alcohol lithium, long-chain or the short-chain alkyl lithium.
3. method of electrostatic spinning according to claim 1 prepares the nano lithium titanate that rare earth metal mixes; It is characterized in that; Described soluble titanium compound is a tetra-n-butyl titanate; Or tetraisopropyl titanate, or the chloride of titanium, wherein titanium compound is titanium compound: alcohol=1:1～10 with the volume ratio of alcohol.
4. method of electrostatic spinning according to claim 1 prepares the nano lithium titanate that rare earth metal mixes; It is characterized in that described rare earth compound is one or more in lanthana, lanthanum nitrate, lanthanum oxalate, lanthanum chloride, neodymia, neodymium nitrate, gadolinium oxide, gadolinium nitrate, gadolinium chloride, Digadolinium trisulfate, Gadolinium monophosphate, scandium oxide, scandium nitrate, scandium chloride, scandium carbonate, dysprosia, praseodymium oxide, praseodymium chloride, the praseodymium sulfide.
5. method of electrostatic spinning according to claim 1 prepares the nano lithium titanate that rare earth metal mixes; It is characterized in that; Described acid is a kind of or its combination in nitric acid, hydrochloric acid, acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, benzoic acid, salicylic acid, the caffeic acid, and alcohol is alcohol with the volume ratio of acid: acid=1:0.1～0.5.
6. method of electrostatic spinning according to claim 1 prepares the nano lithium titanate that rare earth metal mixes; It is characterized in that; Described chelating agent is triethanolamine, acetate, laurate, tartaric acid, citric acid, oxalic acid, gluconic acid, 2; 2'-bipyridine, 1, a kind of or its combination in 10-phenanthrolene, aminotriacetic acid, diethylene-triamine pentaacetic acid, ethylenediamine, the ethylenediamine tetra-acetic acid.
7. method of electrostatic spinning according to claim 1 prepares the nano lithium titanate that rare earth metal mixes; It is characterized in that described macromolecule organic is a kind of in polyvinylpyrrolidone, acetylperoxide nitrate, PLA, PEO, polyvinyl alcohol, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, polyacrylonitrile, polyether sulfone, polylactic acid-glycolic guanidine-acetic acid copolymer, the polyvinyl butyral resin.
8. method of electrostatic spinning according to claim 1 prepares the nano lithium titanate that rare earth metal mixes; It is characterized in that described conductive agent is a kind of in 1-Methyl-2-Pyrrolidone, carrene, methyl alcohol, formic acid, ethanol, acetate, ethylene glycol, acetamide, acetone, chloroform, oxolane, malononitrile, the acetic anhydride.
9. prepare the nano lithium titanate that rare earth metal mixes according to each described method of electrostatic spinning of claim 1-8; It is characterized in that; Technological parameter in the described electrostatic spinning process is: flow is 0.2 ~ 1.0mL/hr, and operating voltage is 10 ~ 15KV, and the dash receiver distance is 10 ~ 30cm.
10. prepare the nano lithium titanate that rare earth metal mixes according to each described method of electrostatic spinning of claim 1-8; It is characterized in that; Said the lithium titanate precursor film is put into tube furnace, in inert atmosphere, calcined 5～15 hours, heating rate is 1～15 ℃/min.
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