CN104577046A - Application of graphene/lithium titanate composite - Google Patents
Application of graphene/lithium titanate composite Download PDFInfo
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- CN104577046A CN104577046A CN201410848158.4A CN201410848158A CN104577046A CN 104577046 A CN104577046 A CN 104577046A CN 201410848158 A CN201410848158 A CN 201410848158A CN 104577046 A CN104577046 A CN 104577046A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
Tetrabutyl titanate, graphene, P123 and tertiary butanol are prepared into a titanium source dispersion liquid, lithium acetate dehydrate, deionized water and tertiary butanol are prepared into a lithium source solution, the mixed titanium source dispersion liquid is transferred into a microwave reactor and heated until flows back, the lithium source solution is added, cooling is carried out after the mixture reacts for certain period of time, solvents are removed, and then drying is carried out to obtain a graphene-based lithium titanate precursor. The obtained graphene-based lithium titanate precursor is placed in a tube furnace and roasted at a certain temperature for certain period of time under inertia gas protection to obtain the graphene/lithium titanate composite. An obtained active material, acetylene black and PVDF are uniformly mixed and coated on an aluminum foil to prepare a button cell electrode plate, a half-cell is finally assembled in a glovebox, the charging-discharging performance of the half-cell is tested, the active material is made into another half-cell, and the performance of the half-cell is detected. Detection shows that the capacity of graphene/lithium titanate is still 140mAh/g under 1C multiplying power, can still be kept for more than 99% after being cycled for 1000 times, and has excellent performance.
Description
Technical field
The preparation method of a kind of graphene/lithium titanate composite material of the present invention and application thereof, belong 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.
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 2630 m
2/ g), higher, the mechanical strength of electron conduction does, stable chemical performance (Alexander A. Balandin, Suchismita Ghosh, Wenzhong Bao, Irene Calizo, Desalegne Teweldebrhan, Feng Miao and Chun Ning Lau. Superior thermal conductivity of single-layer graphene. Nano Letters, 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, its conductivity can reach 106 Sm-1(Keun Soo Kim, Yue Zhao, Houk Jang, Sang Yoon Lee, Jong Min Kim, Kwang S. Kim, Jong-Hyun Ahn, Philip Kim, Jae-Young Choi & Byung Hee Hong.Large-scal pattern growth of graphene films for stretchable transparent electrodes. Nature, 2009,457 (7230): 706-710), so it is the ideal electrode material of chemical energy source.
Lithium-titanium composite oxide Li
4ti
5o
12there is spinel structure, the 70's of 20th century 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 175 mAh/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.But until before and after 1999, people are just to Li
4ti
5o
12negative material as lithium-ions battery starts large quantifier elimination.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
-9s/cm, 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.
Prepare the lithium titanate of nanometer particle size, mainly through sol-gel process preparation, nanoscale, the uniform lithium titanate particle of Granular composite can be obtained, but its complex process, and cost is higher, is unfavorable for industrialization, and degree of widely using is low.
Effectively can improve electric conductivity and the high-rate charge-discharge capability of this material as the lithium titanate of the template synthesis hollow structure of template with surfactant.
At present, the method improving the high rate performance of lithium titanate also has material with carbon element phase compounds such as lithium titanate and Graphene, carbon nano-tube, carbon nanocoils, these methods can well improve its high rate performance, but because lithium titanate wherein exists with three dimensional particles, cannot fully contact in peacekeeping two-dimensional material such as compound tense carbon nano-tube, Graphenes, contact area is restricted, limits the further raising of its performance.
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, 140mAh/g is had under 1C 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 technical scheme that the present invention takes is:
A preparation method for graphene/lithium titanate composite material, comprises the following steps:
1) with titanium source 0.027 ~ 0.33 mol, Graphene, surfactant 0.1 ~ 10g, organic solvent 10-1000mL ultrasonic disperse is mixed with titanium source dispersion liquid, with lithium source 0.021 ~ 0.027 mol, deionized water 1 ~ 50 mL, tert-butyl alcohol preparation 10-1000 mL becomes lithium source solution.
2) being transferred to by titanium source dispersion liquid in microwave reactor and being heated to backflow, adding lithium source solution, cooling after reaction, remove solvent, then drying obtains graphene-based lithium titanate precursor;
3) by step 2) in obtained graphene-based lithium titanate precursor place in tube furnace, under inert gas shielding after calcining, obtain graphene/lithium titanate composite material.
Further, mol ratio in titanium in described step 1) in the dispersion liquid of titanium source and lithium source solution is: 4.5 ~ 5.5:3.5 ~ 4.5, the mass percent of Graphene addition is the quality 1-20% finally obtaining graphene/lithium titanate composite material, ultrasonic disperse time 1 ~ 30 min.
Further, described step 2) in the microwave reaction time be 1 ~ 3h, step 3) calcining heat and time are respectively 400 ~ 1000 DEG C and 8 ~ 48h.
Further, the titanium source of described titanium source dispersion liquid is one or more the mixture in butyl titanate, titanium propanolate, iso-butyl titanate, tetraethyl titanate.
Further, described lithium source is one or more the mixture in lithium acetate, lithium nitrate, lithium hydroxide, lithium sulfate.
Further, described organic solvent is one or more the mixture in the tert-butyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, glycerine, chloroform, acetonitrile, carbon tetrachloride.
Further, described surfactant is P123(poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer), CTAB(softex kw), SDS(lauryl sodium sulfate), SDBS(neopelex) in one or more mixture.
Again further, by graphene/lithium titanate composite material: acetylene black: PVDF=8:1:1 mixing is film on aluminium foil uniformly, prepares button cell electrode slice.
The present invention is made into titanium source dispersion liquid with butyl titanate, Graphene, 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 to be transferred in microwave reactor and to be heated to backflow, add lithium source solution, reaction certain hour, cooling, remove solvent, then drying obtains graphene-based lithium titanate precursor.The graphene-based lithium titanate precursor obtained is placed in tube furnace, uniform temperature calcining certain hour under inert gas shielding, obtain graphene/lithium titanate composite material, by the active material obtained, acetylene black and PVDF mixing film on aluminium foil uniformly, 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 1C multiplying power still has 140mAh/g, circulate after 1000 times and still can keep more than 99%, there is 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 three orders of magnitude, and this is to the lifting of the composite property of entirety, is indispensable, and 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 as 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, 0.15g Graphene, 0.5g surfactant joins in 500 milliliters of special microwave reaction flasks, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15 minutes, 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, make 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, 12h is complete prepares 3g graphene/lithium titanate composite material for sintering, 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
0.03mol butyl titanate, 0.15g Graphene, 1g surfactant joins in 500 milliliters of special microwave reaction flasks, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15 minutes, 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, make 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, 12h is complete prepares 3g graphene/lithium titanate composite material for sintering, 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 butyl titanate, 0.3g Graphene, 0.3g surfactant joins in 500 milliliters of special microwave reaction flasks, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 20 minutes, 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, make 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, 12h is complete prepares 3g graphene/lithium titanate composite material for sintering, 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, 0.15g Graphene, 0.3g surfactant is in 500 milliliters of special microwave reaction flasks, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15 minutes, 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, make 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 1000 DEG C, 12h is complete prepares 3g graphene/lithium titanate composite material for sintering, 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, 0.15g Graphene, 0.3g surfactant joins in 500 milliliters of special microwave reaction flasks, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15 minutes, 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, make 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 600 DEG C, 12h is complete prepares 3g graphene/lithium titanate composite material for sintering, 0.3g graphene/lithium titanate composite material and 37.5mg acetylene black and 37.5mgPVDF are dissolved in NMP, after magnetic agitation 1h, 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, 0.15g Graphene, 0.4g surfactant joins in 500 milliliters of special microwave reaction flasks, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15 minutes, 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, make 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 500 DEG C, 12h is complete prepares 3g graphene/lithium titanate composite material for sintering, 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, 0.15g Graphene, 0.3g surfactant joins in 500 milliliters of special microwave reaction flasks, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15 minutes, 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, make 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 700 DEG C, 14h is complete prepares 3g graphene/lithium titanate composite material for sintering, 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, 0.15g Graphene, 0.3g surfactant joins in 500 milliliters of special microwave reaction flasks, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15 minutes, 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, make 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, 24h is complete prepares 3g graphene/lithium titanate composite material for sintering, 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, 0.15g Graphene, 0.3g surfactant joins in 500 milliliters of special microwave reaction flasks, and add the tert-butyl alcohol dispersion of 200mL, insert in supersonic generator and shake 15 minutes, be made into titanium source solution, 0.024mol Lithium acetate dihydrate is added in the beaker of 500mL, add the deionized water dissolving of 20mL, and add the tert-butyl alcohol dilution of 200mL, be made into lithium source solution, microwave reactor is put in titanium source heat up, make 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, 48h is complete prepares 3g graphene/lithium titanate composite material for sintering, 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 (1)
1. an application for graphene/lithium titanate composite material, is characterized in that, by graphene/lithium titanate composite material: acetylene black: PVDF=8:1:1 mixing is film on aluminium foil uniformly, prepares button cell electrode slice.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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