CN105118977B - V with the three-dimensional winding arrangement of nano wire2O5Hollow micron thread ball and its preparation method and application - Google Patents

V with the three-dimensional winding arrangement of nano wire2O5Hollow micron thread ball and its preparation method and application Download PDF

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CN105118977B
CN105118977B CN201510558250.1A CN201510558250A CN105118977B CN 105118977 B CN105118977 B CN 105118977B CN 201510558250 A CN201510558250 A CN 201510558250A CN 105118977 B CN105118977 B CN 105118977B
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nano wire
thread ball
winding arrangement
preparation
hollow micron
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CN105118977A (en
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麦立强
张鹏飞
赵露滋
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Wuhan University of Technology WUT
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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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

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Abstract

The present invention relates to a kind of V with the three-dimensional winding arrangement of nano wire2O5Hollow micron thread ball and preparation method thereof, is made using following methods, includes following steps：1) measure vanadium pentoxide sol and be diluted in deionized water and obtain solution；2) in step 1) in resulting solution, add organic solution and be used as solvent；3) in step 2) in resulting solution, add trishydroxymethylaminomethane, ultrasonic 0.5 2h；4) by step 3) obtained by reactant be transferred to hydro-thermal reaction in reactor, take out reactor, naturally cool to room temperature；5) by step 4) products therefrom centrifugal filtration, and washed with absolute ethyl alcohol, dry in an oven, that is, obtain the precursor powder of blueness；6) by step 5) products therefrom be placed in Muffle furnace be calcined, produce.The beneficial effects of the invention are as follows：Excellent cyclical stability and high-rate characteristics is shown, is high magnification, the potential application material of extended-life lithium ion battery.

Description

V with the three-dimensional winding arrangement of nano wire2O5Hollow micron thread ball and preparation method thereof And application
Technical field
The invention belongs to nanometer material and electrochemical technology field, and in particular to one kind has the three-dimensional winding arrangement of nano wire V2O5Hollow micron thread ball and preparation method thereof, the material can be used as high multiplying power lithium ion battery positive electrode active materials.
Background technology
Lithium ion battery with high operating voltage, high energy density and the service life of length in the energy due to depositing In storage field to being widely applied.But its application in the extensive energy stores such as electric vehicle remains unchanged forthright by its times The limitation of energy and power density.These can be realized by constructing the electrode material with special construction.In positive electrode, The V of layer structure2O5Due to can with reversible deintercalate lithium ions, and with aboundresources, the high advantage of theoretical capacity and obtain It is widely applied.But it, which remains unchanged, has two large problems, i.e., poor caused by slow dynamics and structural instability High rate performance and stable circulation sex chromosome mosaicism.
In recent years, many studies have shown that constructing nano material such as nano wire, nanobelt etc. can be on nanoscale effectively Reduction lithium ion diffusion length, improve the high rate performance of material from the high dynamics that improves.But these nano materials are existed The low shortcoming of tap density, and can occur in cyclic process agglomeration.And the structure assembled by monodimension nanometer material Such as ball of string structure can also improve vibration density due to can both retain the good characteristic of monodimension nanometer material on three dimension scale Degree is so as to improve volume energy density and be widely studied.
The content of the invention
The technical problems to be solved by the invention are to propose that one kind is wound by nano wire three-dimensional for above-mentioned prior art V2O5Hollow micron thread ball and preparation method thereof, its raw material sources are wide, and preparation technology is simple, and cost is low, gained by receiving The V that rice noodles three-dimensional is entwined2O5Hollow micron thread ball has excellent chemical property.
The present invention solves the technical scheme that is used of above-mentioned technical problem：V with the three-dimensional winding arrangement of nano wire2O5 Hollow micron thread ball, its is a diameter of 4-10 microns, is entwined by nano wire, and forms hollow porous structure, using following sides Method is made, and includes following steps：
1) measure vanadium pentoxide sol and be diluted in deionized water and obtain solution；
2) in step 1) in resulting solution, add organic solution and be used as solvent；
3) in step 2) in resulting solution, add trishydroxymethylaminomethane, ultrasonic 0.5-2h；
4) by step 3) obtained by reactant be transferred to hydro-thermal reaction in reactor, take out reactor, naturally cool to room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed with absolute ethyl alcohol, dry in an oven, that is, obtain blueness Precursor powder；
6) by step 5) products therefrom is placed in Muffle furnace and is calcined, that is, obtains the V with the three-dimensional winding arrangement of nano wire2O5 Hollow micron thread ball.
By such scheme, step 1) described in vanadic anhydride mole be 0.3-0.7mmol, after dilution gained vanadium it is molten The volume of glue is 6-14mL；Step 2) described in organic solvent volume be 40-60mL；Step 3) described in trihydroxy methyl amino first The amount of alkane is 1.0-3.0g.
By such scheme, step 2) described in organic solvent be isopropanol or normal propyl alcohol.
By such scheme, step 4) in hydrothermal temperature be 180-220 DEG C, the time is 1-24h.
By such scheme, step 6) described in calcining heat be 350-600 DEG C, the time is 1-8h.
The described V with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, includes following step Suddenly：
1) measure vanadium pentoxide sol and be diluted in deionized water and obtain solution；
2) in step 1) in resulting solution, add organic solution and be used as solvent；
3) in step 2) in resulting solution, add trishydroxymethylaminomethane, ultrasonic 0.5-2h；
4) by step 3) obtained by reactant be transferred to hydro-thermal reaction in reactor, take out reactor, naturally cool to room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed with absolute ethyl alcohol, dry in an oven, that is, obtain blueness Precursor powder；
6) by step 5) products therefrom is placed in Muffle furnace and is calcined, that is, obtains the V with the three-dimensional winding arrangement of nano wire2O5 Hollow micron thread ball.
The described V with the three-dimensional winding arrangement of nano wire2O5Hollow micron thread ball is used as the active material of lithium ion cell positive The application of material.
The present invention highly shortened lithium ion diffusion length on 1-dimention nano linear content, and utilize its hollow porous knot Structure buffering lithium ion ensures its structural stability in the Volume Changes of deintercalation process, so as to effectively improve the electrochemistry of material Performance.When the material is as lithium battery anode active material, the constant current charge-discharge test result table under 100mA/g high current densities Bright, its first discharge specific capacity, up to 145.3mAh/g, is 137.2mAh/g after 50 circulations, capability retention is 94.4%. Under 2000mA/g high current densities, its capacity can reach 129.3mAh/g after overactivation.The result shows this by nano wire The V that three-dimensional is entwined2O5Hollow micron thread ball has excellent cyclical stability and high-rate characteristics, is high power, long-life The potential application material of lithium battery.
In addition, the assembling mode of this unique one-dimensional nano structure drastically increases the tap density of nano material, The structural stability of material is effectively improved, is significantly lifted so that its high rate performance has.
The beneficial effects of the invention are as follows：It is porous by solvent heat-annealing heat-treats two-step method obtains three-dimensional hollow V2O5A ball of string.This three-dimensional line unity structure not only remains the good characteristic of monodimension nanometer material, is significantly improved while also showing Tap density.When as anode active material of lithium ion battery, the V2O5A ball of string show excellent cyclical stability with High-rate characteristics, are high magnification, the potential application material of extended-life lithium ion battery.Reaction condition of the present invention is gentle, technique letter It is single, meet the requirement of Green Chemistry, it is low for equipment requirements, be conducive to market-oriented popularization.
Brief description of the drawings
Fig. 1 is the V with the three-dimensional winding arrangement of nano wire of the embodiment of the present invention 12O5The XRD of hollow micron thread ball；
Fig. 2 is the V with the three-dimensional winding arrangement of nano wire of the embodiment of the present invention 12O5The SEM figures of hollow micron thread ball；
Fig. 3 is the V with the three-dimensional winding arrangement of nano wire of the embodiment of the present invention 12O5The TEM figures of hollow micron thread ball；
Fig. 4 is the V with the three-dimensional winding arrangement of nano wire of the embodiment of the present invention 12O5The synthesis mechanism of hollow micron thread ball Figure；
Fig. 5 is the V with the three-dimensional winding arrangement of nano wire of the embodiment of the present invention 12O5The BET of hollow micron thread ball and hole Footpath distribution map；
Fig. 6 is the V with the three-dimensional winding arrangement of nano wire of the embodiment of the present invention 12O5Hollow micron thread ball is close in high current Spend (100mA g-1) under constant current charge-discharge circulation figure；
Fig. 7 is the V with the three-dimensional winding arrangement of nano wire of the embodiment of the present invention 12O5Hollow micron thread ball is close in high current Spend (2000mA g-1) under constant current charge-discharge circulation figure；
Fig. 8 is the V with the three-dimensional winding arrangement of nano wire of the embodiment of the present invention 12O5Hollow micron thread ball is close in low current Spend (100mA g-1) charging, the multiplying power figure that discharges under different current density.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention Content is not limited solely to the following examples.
Embodiment 1：
V with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, it comprises the following steps：
1) 0.5mmol V is measured2O5Colloidal sol simultaneously adds deionized water and is diluted to 10mL；
2) in step 1) in resulting solution, add 50mL isopropanols and be used as solvent；
3) in step 2) in resulting solution, add 2.0g trishydroxymethylaminomethanes, ultrasonic 30min；
4) by step 3) obtained by reactant be transferred to 200 DEG C of hydro-thermal reaction 2h in reactor, take out reactor, natural cooling To room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed 3-5 times with absolute ethyl alcohol, dry, that is, obtain in an oven The precursor powder of blueness；
6) by step 5) products therefrom is placed in Muffle furnace 400 DEG C of calcining 5h, that is, obtains being entwined by nano wire three-dimensional V2O5Hollow micron thread ball.
As shown in figure 4, the synthesis mechanism of the present invention is：Building-up process includes solvent heat and the calcining in later stage two of early stage Process.Nano wire is formed due to charge interaction and into nuclear reaction in ultrasonic procedure, due to the reduction of surface energy, nanometer Line is self-assembly of thread ball structure, and the V being entwined by nano wire three-dimensional is thermally treated resulting in finally by calcining2O5Hollow micron Thread ball.This mixed structure can not only retain the good characteristic of nano wire, the effective diffusion length for shortening lithium ion, The dilation of its hollow porous effective buffer electrode material charge and discharge process of structure can also be utilized simultaneously, and in three-dimensional structure On effectively improve its tap density, so as to obtain long-life, powerful chemical property.
The V being entwined with this example product by nano wire three-dimensional2O5Exemplified by hollow micron thread ball, its structure is spread out by X-ray Penetrate instrument determination.As shown in figure 1, X ray diffracting spectrum (XRD) shows, three-dimensional porous structure barium oxide is V2O5(JCPDS cards Number be 01-089-0611), without other dephasigns.As shown in Fig. 2 field emission scanning electron microscope (FESEM) test shows, should be by nanometer The V that line three-dimensional is entwined2O54-10 microns of hollow micron thread ball diameter, is entwined by one-dimensional nano line.As shown in figure 3, thoroughly Radio mirror (TEM), high-resolution transmission electrode (HRTEM) test show that the nanostructured has hollow porous structure.Such as Fig. 4 institutes Show, the V that should be entwined by nano wire three-dimensional2O5The nano wire formation of the main experience early stage of formation of hollow micron thread ball and Self assembly and later stage calcining heat treatment several processes of the later stage due to the reduction of surface energy.As shown in figure 5, three-dimensional by nano wire The V being entwined2O5The N2 adsorption detachment assays of hollow micron thread ball show that its specific surface area reaches 20.2m2/g。
The V being entwined by nano wire three-dimensional prepared by the present invention2O5Hollow micron thread ball is lived as lithium ion cell positive Property material, remaining step of the preparation method of lithium ion battery is identical with common preparation method.The preparation method of positive plate is as follows, Using the V being entwined by nano wire three-dimensional2O5Hollow micron thread ball is used as conductive agent, polytetrafluoro as active material, acetylene black Ethene is as binding agent, and active material, acetylene black, the mass ratio of polytetrafluoroethylene (PTFE) are 60:30:10；They are abundant in proportion After mixing, a small amount of isopropanol is added, grinding is uniform, the electrode slice for pressing about 0.2mm thick on twin rollers；The positive plate pressed is placed in 70 DEG C of oven drying is standby after 24 hours.With 1M LiPF6It is dissolved in vinyl carbonate (EC) and dimethyl carbonate (DMC) As electrolyte, lithium piece is negative pole, and the type stainless steels of CR 2016 are that battery case is assembled into fastening lithium ionic cell.
With three-dimensional porous V2O5Exemplified by, when the material is as lithium battery anode active material, as shown in fig. 6, in 100mA/g Constant current charge-discharge test under current density, its first discharge specific capacity, up to 145.3mAh/g, is 137.2mAh/ after 50 circulations G, capability retention is 94.4%.When current density increases to 2000mA/g, its capacity can reach after overactivation 129.3mAh/g, capacity, which remains unchanged, after 100 circulations is maintained at 112.2mAh/g (as shown in Figure 7).In low current density (100mA g-1) charging, discharge under different current density in the case of, when discharge current is up to 9750mA/g, its specific discharge capacity remains unchanged Up to 94.8mAh/g (as shown in Figure 8), the result shows the V being entwined by nano wire three-dimensional2O5Hollow micron thread ball has Excellent cycle performance and multiplying power property, are high power, the potential application material of extended-life lithium ion battery.
Embodiment 2：
V with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, it comprises the following steps：
1) 0.3mmol V is measured2O5Colloidal sol simultaneously adds deionized water and is diluted to 10mL；
2) in step 1) in resulting solution, add 50mL isopropanols and be used as solvent；
3) in step 2) in resulting solution, add 1.0g trishydroxymethylaminomethanes, ultrasonic 30min；
4) by step 3) obtained by reactant be transferred to 200 DEG C of hydro-thermal reaction 24h in reactor, take out reactor, it is naturally cold But to room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed 3-5 times with absolute ethyl alcohol, dry, that is, obtain in an oven The precursor powder of blueness；
6) by step 5) products therefrom is placed in Muffle furnace 400 DEG C of calcining 5h, that is, obtains being entwined by nano wire three-dimensional V2O5Hollow micron thread ball.
With the V being entwined by nano wire three-dimensional obtained by the present embodiment2O5Exemplified by hollow micron thread ball, the material conduct During lithium battery anode active material, the constant current charge-discharge test under 100mA/g current densities, its first capacity be 142mAh/g, It is 133.2mAh/g after 50 circulations, capability retention is 93.8%.
Embodiment 3：
V with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, it comprises the following steps：
1) 0.5mmol V is measured2O5Colloidal sol simultaneously adds deionized water and is diluted to 10mL；
2) in step 1) in resulting solution, add 40mL isopropanols and be used as solvent；
3) in step 2) in resulting solution, add 2.0g trishydroxymethylaminomethanes, ultrasonic 30min；
4) by step 3) obtained by reactant be transferred to 220 DEG C of hydro-thermal reaction 1h in reactor, take out reactor, natural cooling To room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed 3-5 times with absolute ethyl alcohol, dry, that is, obtain in an oven The precursor powder of blueness；
6) by step 5) products therefrom is placed in Muffle furnace 425 DEG C of calcining 3h, that is, obtains being entwined by nano wire three-dimensional V2O5Hollow micron thread ball.
With the V being entwined by nano wire three-dimensional obtained by the present embodiment2O5Exemplified by hollow micron thread ball, the material conduct During lithium battery anode active material, the constant current charge-discharge test under 100mA/g current densities, its first capacity be 144.1mAh/ G, is 132.3mAh/g after 50 circulations, capability retention is 91.8%.
Embodiment 4：
V with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, it comprises the following steps：
1) 0.5mmol V is measured2O5Colloidal sol simultaneously adds deionized water and is diluted to 10mL；
2) in step 1) in resulting solution, add 60mL isopropanols and be used as solvent；
3) in step 2) in resulting solution, add 3.0g trishydroxymethylaminomethanes, ultrasonic 30min；
4) by step 3) obtained by reactant be transferred to 200 DEG C of hydro-thermal reaction 6h in reactor, take out reactor, natural cooling To room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed 3-5 times with absolute ethyl alcohol, dry, that is, obtain in an oven The precursor powder of blueness；
6) by step 5) products therefrom is placed in Muffle furnace 400 DEG C of calcining 5h, that is, obtains being entwined by nano wire three-dimensional V2O5Hollow micron thread ball.
With the V being entwined by nano wire three-dimensional obtained by the present embodiment2O5Exemplified by hollow micron thread ball, the material conduct During lithium battery anode active material, the constant current charge-discharge test under 100mA/g current densities, its first capacity be 141.8mAh/g It is 133.2mAh/g after 50 circulations, capability retention is 93.9%.
Embodiment 5：
V with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, it comprises the following steps：
1) 0.7mmol V is measured2O5Colloidal sol simultaneously adds deionized water and is diluted to 10mL；
2) in step 1) in resulting solution, add 50mL isopropanols and be used as solvent；
3) in step 2) in resulting solution, add 3.0g trishydroxymethylaminomethanes, ultrasonic 30min；
4) by step 3) obtained by reactant be transferred to 200 DEG C of hydro-thermal reaction 2h in reactor, take out reactor, natural cooling To room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed 3-5 times with absolute ethyl alcohol, dry, that is, obtain in an oven The precursor powder of blueness；
6) by step 5) products therefrom is placed in Muffle furnace 375 DEG C of calcining 7h, that is, obtains being entwined by nano wire three-dimensional V2O5Hollow micron thread ball.
With the V being entwined by nano wire three-dimensional obtained by the present embodiment2O5Exemplified by hollow micron thread ball, the material conduct During lithium battery anode active material, the constant current charge-discharge test under 100mA/g current densities, its first capacity be 139mAh/g It is 129.8mAh/g after 50 circulations, capability retention is 93.4%.
Embodiment 6：
V with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, it comprises the following steps：
1) 0.5mmol V is measured2O5Colloidal sol simultaneously adds deionized water and is diluted to 10mL；
2) in step 1) in resulting solution, add 50mL isopropanols and be used as solvent；
3) in step 2) in resulting solution, add 2.0g trishydroxymethylaminomethanes, ultrasonic 30min；
4) by step 3) obtained by reactant be transferred to 180 DEG C of hydro-thermal reaction 24h in reactor, take out reactor, it is naturally cold But to room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed 3-5 times with absolute ethyl alcohol, dry, that is, obtain in an oven The precursor powder of blueness；
6) by step 5) products therefrom is placed in Muffle furnace 425 DEG C of calcining 5h, that is, obtains being entwined by nano wire three-dimensional V2O5Hollow micron thread ball.
With the V being entwined by nano wire three-dimensional obtained by the present embodiment2O5Exemplified by hollow micron thread ball, the material conduct During lithium battery anode active material, the constant current charge-discharge test under 100mA/g current densities, its first capacity be 143.7mAh/g It is 133.2mAh/g after 50 circulations, capability retention is 92.7%.
Embodiment 7：
V with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, it comprises the following steps：
1) 0.5mmol V is measured2O5Colloidal sol simultaneously adds deionized water and is diluted to 10mL；
2) in step 1) in resulting solution, add 50mL normal propyl alcohols and be used as solvent；
3) in step 2) in resulting solution, add 2.0g trishydroxymethylaminomethanes, ultrasonic 30min；
4) by step 3) obtained by reactant be transferred to 200 DEG C of hydro-thermal reaction 24h in reactor, take out reactor, it is naturally cold But to room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed 3-5 times with absolute ethyl alcohol, dry, that is, obtain in an oven The precursor powder of blueness；
6) by step 5) products therefrom is placed in Muffle furnace 400 DEG C of calcining 5h, that is, obtains being entwined by nano wire three-dimensional V2O5Hollow micron thread ball.
With the V being entwined by nano wire three-dimensional obtained by the present embodiment2O5Exemplified by hollow micron thread ball, the material conduct During lithium battery anode active material, the constant current charge-discharge test under 100mA/g current densities, its first capacity be 144mAh/g It is 135.8mAh/g after 50 circulations, capability retention is 94.3%.

Claims (5)

1. the V with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, includes following steps：
1) measure vanadium pentoxide sol and be diluted in deionized water and obtain solution；
2) in step 1) in resulting solution, add organic solution and be used as solvent；
3) in step 2) in resulting solution, add trishydroxymethylaminomethane, ultrasonic 0.5-2h；
4) by step 3) obtained by reactant be transferred to hydro-thermal reaction in reactor, take out reactor, naturally cool to room temperature；
5) by step 4) products therefrom centrifugal filtration, and washed with absolute ethyl alcohol, dry in an oven, that is, obtain the preceding body of blueness Body powder；
6) by step 5) products therefrom is placed in Muffle furnace and calcines, that is, obtains the V with the three-dimensional winding arrangement of nano wire2O5It is hollow Micron thread ball, the described V with the three-dimensional winding arrangement of nano wire2O5Hollow micron thread ball, its is a diameter of 4-10 microns, by receiving Rice noodles are entwined, and form hollow porous structure.
2. the V according to claim 1 with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, its Be characterised by step 1) described in vanadic anhydride mole be 0.3-0.7mmol, after dilution gained vanadium colloidal sol volume be 6-14mL；Step 2) described in organic solvent volume be 40-60mL；Step 3) described in the amount of trishydroxymethylaminomethane be 1.0-3.0g。
3. the V according to claim 1 with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, its Be characterised by step 2) described in organic solvent be isopropanol or normal propyl alcohol.
4. the V according to claim 1 with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, its Be characterised by step 4) in hydrothermal temperature be 180-220 DEG C, the time is 1-24h.
5. the V according to claim 1 with the three-dimensional winding arrangement of nano wire2O5The preparation method of hollow micron thread ball, its Be characterised by step 6) described in calcining heat be 350-600 DEG C, the time is 1-8h.
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