CN105098166A - Preparation method for high-performance graphene lithium titanate composite battery material - Google Patents
Preparation method for high-performance graphene lithium titanate composite battery material Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method for a high-performance graphene lithium titanate composite battery material. The preparation method comprises the following steps of preparing a titanium-source dispersion liquid from tetrabutyl titanate, P123 and tert butyl alcohol; preparing a lithium-source solution from a lithium acetate dehydrate, deionized water and the tert butyl alcohol; transferring the mixed titanium-source dispersion liquid into a microwave reactor for microwave heating until backflow; dropping the lithium-source solution; continuously reacting for 1 hour after dropping; cooling and removing a solvent; drying to obtain a dried lithium titanate precursor; placing the obtained lithium titanate precursor in a tube furnace; calcining for 8 hours in an air atmosphere at 800 DEG C to obtain a lithium titanate electrode material; carrying out ultrasonic uniform dispersion of the obtained lithium titanate electrode material and graphene according to a certain proportion; removing the solvent to obtain a graphene/lithium titanate electrode material; uniformly mixing and coating the obtained active material, acetylene black and polyvinylidene fluoride (PVDF) on an aluminum foil to prepare a button battery electrode piece; and finally, assembling a half cell in a glove box, testing the charging and discharging performance of the cell, fabricating the active material into the half cell for performance test. Detection reveals that the capacity of graphene/lithium titanate at 2C rate is still 130 mAh/g, the specific capacity after 1000 times of cycles can be still kept 99% or above, and the graphene/lithium titanate has excellent charging and discharging performance compared with pure-phase lithium titanate.
Description
Technical field
The preparation method of a kind of High-performance graphene/lithium titanate composite material of the present invention, belongs to technical field of electrochemistry.
Background technology
Energy and environment problem is day by day serious, and the development and use of clean energy resource is extremely urgent, and under the prerequisite of the large-scale application of the green novel energy sources such as wind energy, solar energy, geothermal energy, the requirement of people to energy storage device is more and more higher, especially the cycle life of battery.In automobile industry, developing rapidly of hybrid vehicle congratulated by electric automobile, harsher requirement is proposed to providing the lithium ion battery of energy for it, particularly its power-performance and cycle performance, due to other negative materials shortcoming separately, lithium titanate has lot of advantages as a kind of novel negative material, such as security performance is good, long service life, efficiency for charge-discharge are high, Stability Analysis of Structures etc., potentially to be widely used in lithium-ion-power cell field, to be considered to the negative material of most promising lithium-ion-power cell of future generation.
Lithium-titanium composite oxide Li
4ti
5o
12there is spinel structure, 20 century 70s are carried out large quantity research by as superconductor, the end of the eighties, the positive electrode of Zeng Zuowei lithium-ions battery was studied, but because its and specific energy on the low side relative to lithium current potential is also lower (theoretical specific capacity is 170mAh/g), and fail to cause the extensive concern of people.1996, Canadian Studies person K.Zaghib proposed to adopt lithium titanate material to make negative pole first and high-voltage anode forms lithium-ions battery and forms asymmetric super-capacitor with carbon electrode.Afterwards, little bavin letter was fine waits people also to it can be used as ion cathode material lithium to carry out research.Electrochemical diffusion coefficient under spinel lithium titanate normal temperature is 2 × 10
-8cm
2/ s, an order of magnitude larger than carbon negative pole material, charge/discharge rates is faster.But lithium titanate also has its weak point, the intrinsic conductivity of lithium titanate is 10
-7s/m, belong to typical insulator, poorly conductive, heavy-current discharge performance is poor, and therefore preparing high performance lithium titanate electrode material must from the conductivity improving lithium titanate.
In material with carbon element, Graphene causes in scientific circles because of the performance of its excellence and pays close attention to widely.Because Graphene has the following advantages: high conductivity, specific area are large, and (theoretical specific surface area is 2630m
2/ g), higher, the mechanical strength of electron conduction does, stable chemical performance (AlexanderA.Balandin, SuchismitaGhosh, WenzhongBao, IreneCalizo, DesalegneTeweldebrhan, FengMiaoandChunNingLau.Superiorthermalconductivityofsing le-layergraphene.NanoLetters, 2008,8 (3): 902-907), the mobility of electronics in Graphene can reach 2 × 10
5cm
2v
-1s
-1, be about electronics 140 times of mobility in silicon.Graphene is the material that room temperature conductivity can be splendid, and its conductivity can reach 10
6sm
-1(KeunSooKim, YueZhao, HoukJang, SangYoonLee, JongMinKim, KwangS.Kim, Jong-HyunAhn, PhilipKim, Jae-YoungChoi & ByungHeeHong.Large-scalpattemgrowthofgraphenefilmsforstretchabletrans parentelectrodes.Nature, 2009,457 (7230): 706-710), so it improves the desirable electrode material of battery material performance in chemical energy source.In addition, the lithium titanate preparing reduced size also can increase its chemical property, but the lithium titanate that tradition prepares nanometer particle size is prepared mainly through sol-gel process, although nanoscale, the uniform lithium titanate particle of Granular composite can be obtained, but its complex process, cost is higher, is unfavorable for industrialization, and degree of widely using is low.
Find through research widely and test repeatedly, employing microwave shakes, adding surfactant as the template of reaction accesses a kind of lithium titanate composite lithium ion battery negative material of excellent performance with the material with carbon element phase recombination energy such as Graphene, 130mAh/g is had under 2C multiplying power, circulate after 1000 times and still can keep more than 99%, there is very high cycle performance.
Summary of the invention
The technological requirement that the object of the invention is to exist for existing graphene/lithium titanate composite material is high, the conductivity of lithium titanate particle diameter heterogeneity, lithium titanate composite material is not ideal enough, cycle performance is poor, composite material bad dispersibility etc. deficiency, a kind of preparation method of new graphene/lithium titanate composite material is provided.The method substantially increases the conductibility of graphene/lithium titanate composite lithium ion battery negative material, dispersiveness and stability, more saves industrial energy consumption, is conducive to protection of the environment.
The present invention is made into titanium source dispersion liquid with butyl titanate, P123, the tert-butyl alcohol, lithium source solution is made into Lithium acetate dihydrate, deionized water and the tert-butyl alcohol, the titanium source dispersion liquid of mixing is transferred to microwave heating extremely backflow in microwave reactor, instillation lithium source solution, reaction 1h is continued after waiting to instill, cooling, remove solvent, then drying obtains lithium titanate precursor.The lithium titanate precursor obtained is placed in tube furnace, and under air atmosphere, 800 DEG C of calcining 8h, obtain lithium titanate electrode material..Ultrasonic disperse is even in organic solvent with certain proportion for the lithium titanate electrode material obtained and Graphene, removes solvent, obtains graphene/lithium titanate electrode material.By active material, acetylene black and the PVDF mixing film on aluminium foil uniformly obtained, prepare button cell electrode slice, last in glove box, assemble half-cell and charge-discharge performance tested active material made half-cell carry out Performance Detection, detect and find, graphene/lithium titanate capacity under 2C multiplying power still has 130mAh/g, circulate after 1000 times and still can keep more than 99%, have excellent performance, concrete advantage is as follows:
(1) adopt the tert-butyl alcohol as the solvent of this reaction, the tert-butyl alcohol is organic polar solvent, to the formation of product, there is template action, the secondary agglomeration of lithium titanate can be made more regular, simultaneously the adding of organic solvent, the hydrolysis rate of butyl titanate can be made to reduce, make the particle diameter of product less, dispersion evenly.
(2) add surfactant in reaction, for reaction system, adding of surfactant, make the shape regularization more of lithium titanate precursor, this graphene/lithium titanate obtaining better performances for next step provides prerequisite.
(3) the adding of Graphene, make to be the lithium titanate crystal of insulator originally, conductivity improves four orders of magnitude, this is to the lifting of the composite property of entirety, be indispensable, Graphene, as the express network of electron transmission, plays excellent performance.
(4) microwave is in the effect of reaction, on the one hand for the carrying out of reaction backflow provides thermal source, make lithium titanate precursor in reflux course more close to perfect crystal formation, on the other hand, due to the existence of microwave, the macroparticle of the formation being is dispersed into more small-particle, and this is also effective to the lifting of the performance of composite material.
(5) in the proportioning of lithium source solution, add a small amount of water and with the dilution of a large amount of tert-butyl alcohols, this makes the water that at every turn instills in reaction solution less, and hydrolysis rate is lower, and the particle of formation is also conducive to the chemical property improving composite material.
Embodiment
Further illustrate the present invention by embodiment below, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises." room temperature ", " normal pressure " described in the present invention refers to temperature between regular job and air pressure, is generally 25 DEG C, an atmospheric pressure.
In following embodiment, the electrode that the electro-chemical test of battery is used is aluminium foil (diameter: 16mm, thickness: 0.02mm), adopts half-cell as tested object.Electro-chemical test is the blue electric system in Wuhan, and operating voltage is 0.5-3V, charge-discharge magnification is respectively 0.1,0.2,0.5,1,2,5,10,20,50C.
Embodiment 1
0.03mol butyl titanate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment 2
0.028mol butyl titanate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment 3
0.03mol titanium propanolate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment 4
0.03mol butyl titanate, 0.3g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment 5
0.03mol butyl titanate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 100mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment 6
0.03mol butyl titanate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.022mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment 7
0.03mol butyl titanate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 5mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment 8
0.03mol butyl titanate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 2h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment 9
0.03mol butyl titanate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 900 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment 10
0.03mol butyl titanate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 10h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.15g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Embodiment youngster
0.03mol butyl titanate, 0.5g surfactant joins in the special microwave reaction flask of 500mL, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15min, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 10mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, microwave heating makes it reflux, in a bite of flask, lithium source solution is slowly instilled with the dropping funel of 250mL after refluxing, instill complete reaction 1h, the presoma of graphene/lithium titanate composite material is obtained after removing solvent, presoma is put into tube furnace, be warming up to 800 DEG C, 8h is complete prepares 3g lithium titanate for sintering, by the 0.3g lithium titanate electrode material obtained and 0.1g Graphene, ultrasonic disperse in the tert-butyl alcohol evenly, is removed solvent, is obtained graphene/lithium titanate electrode material.0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 2h, film on aluminium foil, dry and cut into slices and obtain the cell piece that diameter is 16mm, in glove box, lithium sheet is negative pole, and active material electrode slice is that positive pole assembling obtains half-cell, and multiplying power is in 1C situation to utilize blue electrical testing system testing to find, graphene/lithium titanate composite material capacity still can reach 140mAh/g, circulates after 1000 times and still can keep more than 99%.
Claims (6)
1. the invention provides a kind of preparation method of High-performance graphene/lithium titanate composite material and the application in lithium ion battery thereof, comprising:
1) be made into the dispersion liquid in mixed with titanium source with a certain amount of titanium-containing compound, surfactant and organic solvent ultrasonic disperse, be made into lithium source solution with a certain amount of lithium-containing compound, deionized water and organic solvent ultrasonic disperse.
2) the titanium source dispersion liquid of mixing is transferred to microwave heating in microwave reactor and, to backflow, slowly drips lithium source solution, after lithium source solution is added dropwise to complete, continue reaction certain hour, cooling, remove solvent, then drying obtains lithium titanate precursor.
3) by 2) lithium titanate precursor that obtains places in tube furnace, and under air atmosphere, uniform temperature calcining certain hour, obtains lithium titanate electrode material.
4) by 3) ultrasonic disperse is even in organic solvent with certain proportion for the lithium titanate electrode material that obtains and Graphene, and remove solvent, obtain graphene/lithium titanate electrode material.
5) by 4) active material, acetylene black and the PVDF that obtain mixing uniform on aluminium foil film, prepare button cell electrode slice, finally in glove box, assemble half-cell and charge-discharge performance is tested.
2. the method for claim 1, it is characterized in that, the proportioning of titanium source dispersion liquid and lithium source solution: titanium lithium atom mol ratio is 4.5 ~ 5.5: 3.5 ~ 4.5, Graphene addition is the 1-20% finally obtaining graphene/lithium titanate composite material, P123 addition is 0.1 ~ 10g, and the volume of organic solvent is at 10 ~ 1000mL, and deionized water addition is 1 ~ 50mL, the microwave reaction time is 1 ~ 3h, and calcining heat and time are respectively 400 ~ 1000 DEG C and 8 ~ 48h.
3. the method for claim 1, is characterized in that, described titanium source dispersion liquid is any one being selected from butyl titanate, titanium propanolate, iso-butyl titanate, tetraethyl titanate, or their mixture.
4. the method for claim 1, is characterized in that, described lithium source is selected from any one in lithium acetate, lithium nitrate, lithium hydroxide, lithium sulfate, or their mixture.
5. the method for claim 1, is characterized in that, described organic solvent is selected from any one in the tert-butyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, glycerine, chloroform, acetonitrile, carbon tetrachloride, or their mixture.
6. the method for claim 1, it is characterized in that: described surfactant is selected from any one in P123 (poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer), CTAB (softex kw), SDS (lauryl sodium sulfate), SDBS (neopelex), or their mixture.
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| CN201410188654.1A Pending CN105098166A (en) | 2014-05-07 | 2014-05-07 | Preparation method for high-performance graphene lithium titanate composite battery material |
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| CN108417824A (en) * | 2018-03-06 | 2018-08-17 | 辽宁大学 | A kind of preparation method of high-performance lithium battery negative material carbon cladding lithium titanate |
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| CN108155372B (en) * | 2016-12-04 | 2020-05-26 | 中国科学院大连化学物理研究所 | Lithium titanate material and preparation and application thereof |
| CN108417824A (en) * | 2018-03-06 | 2018-08-17 | 辽宁大学 | A kind of preparation method of high-performance lithium battery negative material carbon cladding lithium titanate |
| CN108417824B (en) * | 2018-03-06 | 2020-10-09 | 辽宁大学 | Preparation method of high-performance lithium battery cathode material carbon-coated lithium titanate |
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