CN103227317A - V205 quantum dot/graphene composite materials and preparation method thereof and application thereof - Google Patents

V205 quantum dot/graphene composite materials and preparation method thereof and application thereof Download PDF

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CN103227317A
CN103227317A CN2013100993772A CN201310099377A CN103227317A CN 103227317 A CN103227317 A CN 103227317A CN 2013100993772 A CN2013100993772 A CN 2013100993772A CN 201310099377 A CN201310099377 A CN 201310099377A CN 103227317 A CN103227317 A CN 103227317A
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quantum dot
solution
graphene composite
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deionized water
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麦立强
晏梦雨
韩春华
许絮
马鑫萸
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The invention relates to V205 quantum dot/graphene composite materials and a preparation method of the V205 quantum dot/graphene composite materials. The preparation method comprises the following steps: (1) taking V205 sol, diluting the V205 sol into deionized water, obtaining a V205 solution, measuring and taking an aniline solution, dropping the aniline solution into the V205 solution, stirring, (2) adding graphene dispersion liquid in proportion into the solution obtained in the step (1), adding deionized water, stirring at room temperature, (3) carrying out thermostatic water bath heating processing on the even solution obtained in the step (2), (4) carrying out hydrothermal reaction on the solution processed in the step (3), naturally cooling the solution to the room temperature, (5) repetitively scrubbing the products obtained in the step (4) by absolute ethyl alcohol, drying the products, and obtaining the V205 quantum dot/graphene composite materials. The preparation method of the V205 quantum dot/graphene composite materials has the advantages that a water-bath-water-heating two-step method is adopted to synthesize and prepare the V205 quantum dot/graphene composite materials in a liquid phase mode, and the V205 quantum dot/graphene composite materials are high in purity and good in dispersity. The V205 quantum dot/graphene composite materials can be used as active materials of anode materials of lithium ion cells, and show good circulation stability and high reversible capacity.

Description

V 2O 5Quantum dot/graphene composite material and its production and application
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to V 2O 5Quantum dot/graphene composite material and preparation method thereof, this material can be used as anode active material of lithium ion battery.
Background technology
Along with the increase of energy demand, energy memory device is playing more and more important effect aspect the raising energy utilization efficiency.Recently, as the important composition form of energy memory device, lithium ion battery is widely used in hybrid vehicle and the portable equipment owing to its high energy density.Research has long circulation life more, higher reversible capacity, the lithium ion battery electrode material of low production cost more, is one of the forward position of research at present and focus.V 2O 5Has special layer structure, its theoretical capacity is considered to the high-capacity lithium ion cell positive electrode of tool potentiality up to 440mAh/g, but its relatively poor cycle performance, lower electronic conductivity and ionic conductivity seriously restrict the application in lithium ion battery.
In recent years, for improving the diffuser efficiency of lithium ion, V with nanostructure 2O 5Material has been subjected to extensive concern, V 2O 5Quantum dot is little owing to its diameter, surface atom ratio height, and then show excellent chemical property.Graphene is because unique 2D monolayer carbon atomic structure has high-specific surface area (2600m 2/ g), characteristic such as highly electron conductive, favorable mechanical toughness, be widely used in the electrochemical modification to electrode material.But V 2O 5Quantum dot/graphene composite material yet there are no report.
Summary of the invention
The object of the present invention is to provide a kind of V 2O 5Quantum dot/graphene composite material and preparation method thereof, its preparation process is simple, and energy consumption is lower, the V of gained 2O 5Quantum dot/graphene composite material has good electrochemical.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: V 2O 5Quantum dot/graphene composite material, its V 2O 5The diameter of quantum dot is 2-3nm, is evenly distributed on the graphene film, adopts following method to make, and includes following steps:
1) gets the V of 1.1～1.5mmol 2O 5Colloidal sol also is diluted in and obtains 40ml V in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than measuring aniline solution for 0.03:1 2O 5In the solution, stir;
2) in step 1) gained solution, add the Graphene dispersion liquid in proportion, and to add deionized water to overall solution volume be 60ml, at room temperature stir;
3) with step 2) uniform solution of gained is transferred in the thermostat water bath, carries out the water bath with thermostatic control heat treated;
4) solution after the step 3) processing is changed in the 100ml reactor, carry out hydro-thermal reaction, from reactor, take out then, naturally cool to room temperature;
5) with absolute ethyl alcohol cyclic washing step 4) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
Pressing such scheme, step 2) preparation method of described Graphene dispersion liquid includes following steps:
A) in the 250ml conical flask, add the 1g graphite powder and the 23ml concentrated sulfuric acid, at room temperature mix and stirred 24 hours;
B) conical flask is put into thermostat water bath, 40 ℃ of reaction temperatures add 100mgNaNO in step a) gained dispersion liquid 3, stirred 5 minutes, slowly add 500mg KMnO subsequently 4, and keep solution temperature below 45 ℃, stirred 30 minutes;
C) in step b) gained dispersion liquid, add the 3ml deionized water, stir after 5 minutes, add the 3ml deionized water again, stirred subsequently 5 minutes, add the 40ml deionized water again, stirred 15 minutes;
D) conical flask is shifted out water-bath, add 140ml deionized water and 10ml mass percent concentration 30%H 2O 2To stop oxidation reaction;
E) with step d) gained suspension service quality percent concentration 5%HCl solution washing twice, extremely neutral with deionized water wash subsequently, be dispersed in the 100ml deionized water ultrasonic 60 minutes;
F) 5000 rev/mins of step e) gained suspension is centrifugal, the time is 5 minutes, gets supernatant liquor repeatedly, and until isolating uniform Graphene dispersion liquid, concentration is 1mg/ml.
Press such scheme, the described water bath with thermostatic control temperature of step 3) is 70-90 ℃, and the reaction time is 22-26 hour.
Press such scheme, step 2) amount of described Graphene is 10-16mg.
Press such scheme, the described hydrothermal temperature of step 4) is 160-200 ℃, and the time is 36-60 hour.
V 2O 5The preparation method of quantum dot/graphene composite material includes following steps:
1) gets the V of 1.1～1.5mmol 2O 5Colloidal sol also is diluted in and obtains 40mlV in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than measuring aniline solution for 0.03:1 2O 5In the solution, stir;
2) in step 1) gained solution, add the Graphene dispersion liquid in proportion, and to add deionized water to overall solution volume be 60ml, at room temperature stir;
3) with step 2) uniform solution of gained is transferred in the thermostat water bath, carries out the water bath with thermostatic control heat treated;
4) solution after the step 3) processing is changed in the 100ml reactor, carry out hydro-thermal reaction, from reactor, take out then, naturally cool to room temperature;
5) with absolute ethyl alcohol cyclic washing step 4) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
Pressing such scheme, step 2) preparation method of described Graphene dispersion liquid includes following steps:
A) in the 250ml conical flask, add the 1g graphite powder and the 23ml concentrated sulfuric acid, at room temperature mix and stirred 24 hours;
B) conical flask is put into thermostat water bath, 40 ℃ of reaction temperatures add 100mgNaNO in step a) gained dispersion liquid 3, stirred 5 minutes, slowly add 500mg KMnO subsequently 4, and keep solution temperature below 45 ℃, stirred 30 minutes;
C) in step b) gained dispersion liquid, add the 3ml deionized water, stir after 5 minutes, add the 3ml deionized water again, stirred subsequently 5 minutes, add the 40ml deionized water again, stirred 15 minutes;
D) conical flask is shifted out water-bath, add 140ml deionized water and 10ml mass percent concentration 30%H 2O 2To stop oxidation reaction;
E) with step d) gained suspension service quality percent concentration 5%HCl solution washing twice, extremely neutral with deionized water wash subsequently, be dispersed in the 100ml deionized water ultrasonic 60 minutes;
F) 5000 rev/mins of step e) gained suspension is centrifugal, the time is 5 minutes, gets supernatant liquor repeatedly, and until isolating uniform Graphene dispersion liquid, concentration is 1mg/ml.
Press such scheme, the described water bath with thermostatic control temperature of step 3) is 70-90 ℃, and the reaction time is 22-26 hour.
Press such scheme, in step 2) amount of described Graphene is 10-16mg.
Press such scheme, the described hydrothermal temperature of step 4) is 160-200 ℃, and the time is 36-60 hour.
V 2O 5Quantum dot/graphene composite material is as the application of anode active material of lithium ion battery.
The present invention adopts water-bath-hydro-thermal two-step method, by the nucleation and growth process of adjustment control crystal, and control V 2O 5The diameter of nano particle, the synthetic preparation of liquid phase V 2O 5Quantum dot/graphene composite material.The result shows that the present invention can effectively shorten lithium ion diffusion length, V 2O 5The quantum dot favorable dispersibility helps ion transfer, can provide enough spaces to bear at Li +Embed the change in volume that produces in the process, improve the stability of electrode material.Simultaneously, Graphene can play cushioning effect, prevents from that electrode material from embedding and deviating from lithium ion to take place in the process from reuniting, and improves the conductivity of material.Therefore, V provided by the invention 2O 5Quantum dot/graphene composite material preparation technology can significantly improve the lithium ion battery cyclical stability, solves V 2O 5The difficult problem that the positive electrode capacity attenuation is fast has huge development potentiality in the lithium ion battery applications field.
The invention has the beneficial effects as follows: the present invention adopts water-bath-hydro-thermal two-step method, by the nucleation and growth process of adjustment, time and proportion of raw materials control crystal, control V 2O 5The diameter of nano particle, the synthetic preparation of liquid phase V 2O 5Quantum dot/graphene composite material, its purity height, good dispersion.It shows reasonable cyclical stability and higher reversible capacity as the anode material for lithium-ion batteries active material; Secondly, technology of the present invention is simple, at a lower temperature through obtaining V after water bath with thermostatic control and the two steps processing of simple hydro-thermal 2O 5Quantum dot/graphene composite material, energy consumption is lower, helps the marketization and promotes.
Description of drawings
Fig. 1 is the V of the embodiment of the invention 1 2O 5Quantum dot/graphene composite material and V 2O 5The XRD figure of nano wire;
Fig. 2 is the V of the embodiment of the invention 1 2O 5Quantum dot/graphene composite material and V 2O 5The TG-DSC-DTG figure of nano wire;
Fig. 3 is the V of the embodiment of the invention 1 2O 5The SEM figure of quantum dot/graphene composite material;
Fig. 4 is the V of the embodiment of the invention 1 2O 5The TEM figure of quantum dot/graphene composite material;
Fig. 5 is the V of the embodiment of the invention 1 2O 5The AFM figure of quantum dot/graphene composite material;
Fig. 6 is the V of the embodiment of the invention 1 2O 5The synthesis mechanism figure of quantum dot/graphene composite material;
Fig. 7 is the V of the embodiment of the invention 1 2O 5Quantum dot/graphene composite material and V 2O 5The cycle performance of battery figure of nano wire.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
V 2O 5The preparation method of quantum dot/graphene composite material, it comprises the steps:
One, the preparation of Graphene dispersion liquid:
1) in the 250ml conical flask, adds the 1g graphite powder and the 23ml concentrated sulfuric acid, at room temperature mix and stirred 24 hours;
2) conical flask is put into thermostat water bath, reaction temperature is 40 ℃, adds 100mgNaNO in step 1) gained dispersion liquid 3, stirred 5 minutes, slowly add 500mg KMnO subsequently 4, and keep solution temperature below 45 ℃, stirred 30 minutes;
3) to step 2) in the gained dispersion liquid, add the 3ml deionized water, stir after 5 minutes, add the 3ml deionized water again, stirred subsequently 5 minutes, add the 40ml deionized water again, stirred 15 minutes;
4) conical flask is shifted out water-bath, add 140ml deionized water and 10ml mass percent concentration 30%H 2O 2To stop oxidation reaction;
5) with step 4) gained dispersion liquid service quality percent concentration 5%HCl solution washing twice, extremely neutral with deionized water wash subsequently, be dispersed in the 100ml deionized water ultrasonic 60 minutes;
6) 5000 rev/mins of step 5) gained suspension is centrifugal, the time is 5 minutes, gets supernatant liquor repeatedly, and until isolating uniform Graphene dispersion liquid, concentration is 1mg/ml;
Two, V 2O 5The preparation of colloidal sol
7) get V 2O 5Powder is put into ceramic crucible and is placed Muffle furnace, heats and is incubated to molten condition;
8) with step 7) gained fusion V 2O 5Pour quenching in the deionized water at normal temperature rapidly into, gained liquid heat to boiling is not stopped to stir, cooling back suction filtration obtains V with filtrate leaving standstill 2O 5Colloidal sol is demarcated its concentration, and is standby;
Three, V 2O 5The preparation of quantum dot/graphene composite material
9) get the V of 1.3mmol 2O 5Colloidal sol also is diluted in and obtains 40ml V in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than the aniline solution of measuring 0.05mol/L for 0.03:1 2O 5Solution stirred 0.5 hour;
10) set by step 9) add 13ml Graphene dispersion liquid in the gained solution, and to add deionized water to overall solution volume be 60ml, at room temperature stirred 0.5 hour;
11) uniform solution with the step 10) gained is transferred in the thermostat water bath, carries out 80 ℃ of waters bath with thermostatic control, and the time is 24h;
12) solution after step 11) is handled changes in the 100ml reactor, 180 ℃ of following hydro-thermal reactions 48 hours, takes out from reactor then, naturally cools to room temperature;
13) with absolute ethyl alcohol cyclic washing step 12) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
As shown in Figure 6, synthesis mechanism of the present invention is: the present invention adopts water-bath-hydro-thermal two-step method, by the nucleation and growth process of adjustment control crystal, and control V 2O 5The diameter of nano particle, the synthetic preparation of liquid phase V 2O 5Quantum dot/graphene composite material.
Product V with this experiment invention 2O 5Quantum dot/graphene composite material is an example, and its structure determines that by x-ray diffractometer as shown in Figure 1, X-ray diffracting spectrum (XRD) shows V 2O 5Quantum dot/graphene composite material is consistent with vanadic oxide nano wire (being following contrast test) peak position, the diffraction maximum of product all with JCPDS card No.41-1426(Pmnn,
Figure BDA00002968146300055
Figure BDA00002968146300056
), contrast very consistently, belong to orthorhombic system.
V 2O 5The content of quantum dot/graphene composite material determines that by differential thermal analyzer as shown in Figure 2, the content of determining Graphene is 6.45%.
As shown in Figure 3, field emission scanning electron microscope (FESEM) test shows, V 2O 5Quantum dot/graphene composite material totally presents layer structure.As shown in Figure 4, transmission electron microscope (TEM) test can clear view be arrived V 2O 5Quantum dot evenly distributes on the Graphene substrate, and it is of a size of 2-3nm.As shown in Figure 5, atomic force microscope (AFM) has shown supported V equally 2O 5Behind the quantum dot, Graphene thickness is about 2nm, and the thickness greater than pure Graphene substrate (thickness is about 1nm) proves V 2O 5Quantum dot successfully loads on the Graphene substrate.
The V of the present invention's preparation 2O 5Quantum dot/graphene composite material is as anode active material of lithium ion battery, and all the other steps of the preparation method of lithium ion battery are identical with common preparation method.The preparation method of positive plate is as follows, adopts V 2O 5Quantum dot/graphene composite material is as active material, and acetylene black is as conductive agent, and polytetrafluoroethylene is as binding agent, and the mass ratio of active material, acetylene black, polytetrafluoroethylene is 70:20:10; After their abundant in proportion mixing, add a small amount of isopropyl alcohol, grind evenly, on twin rollers, press the thick electrode slice of about 0.5mm; The positive plate that presses places 80 ℃ oven drying standby after 24 hours.LiPF with 1M 6Be dissolved in vinyl carbonate (EC) and the dimethyl carbonate (DMC) as electrolyte, the lithium sheet is a negative pole, and Celgard2325 is a barrier film, and CR2025 type stainless steel is that battery case is assembled into the buckle type lithium-ion battery.
V with the present embodiment gained 2O 5Quantum dot/graphene composite material is an example, and as shown in Figure 7, at 100mA/g, the constant current charge-discharge test result of carrying out under the current density shows that its first discharge specific capacity can reach 245mAh/g, and 100 times the circulation back is 212mAh/g, and capability retention is 86.53%.
The aniline of 1.3mmol vanadium colloidal sol, 0.039mmol is mixed, and adding deionized water to overall solution volume is 60ml, and gained solution is put into the 100ml reactor, 180 ℃ of following hydro-thermals 48 hours, through behind the absolute ethanol washing, drying, be positioned in 450 ℃ the Muffle furnace calcining 4 hours, and obtained V 2O 5Nano wire, by identical accessory and technology assembled battery, experiment as a comparison.V 2O 5Nano wire first with 100 times the circulation after specific discharge capacity be respectively 288mAh/g and 126mAh/g, capability retention is 43.75%.Above-mentioned performance shows, V 2O 5Quantum dot/graphene composite material has the cyclical stability that significantly improves, and is a kind of potential anode material for lithium-ion batteries.
Embodiment 2:
V 2O 5The preparation method of quantum dot/graphene composite material, it comprises the steps:
One, the preparation of Graphene dispersion liquid: identical with embodiment 1;
Two, V 2O 5The preparation of colloidal sol: identical with embodiment 1;
Three, V 2O 5The preparation of quantum dot/graphene composite material:
9) with the V of 1.3mmol 2O 5Colloidal sol also is diluted in and obtains 40ml V in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than the aniline solution of measuring 0.05mol/L for 0.03:1 2O 5Solution stirred 0.5 hour;
10) set by step 9) add 13ml Graphene dispersion liquid in the gained solution, and to add deionized water to overall solution volume be 60ml, at room temperature stirred 0.5 hour;
11) uniform solution with the step 10) gained is transferred in the thermostat water bath, carries out 70 ℃ of waters bath with thermostatic control, and the time is 26h;
12) solution after step 11) is handled changes in the 100ml reactor, 160 ℃ of following hydro-thermal reactions 48 hours, takes out from reactor then, naturally cools to room temperature;
13) with absolute ethyl alcohol cyclic washing step 12) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
With product V of the present invention 2O 5Quantum dot/graphene composite material is an example, its V 2O 5The diameter of quantum dot is 2-3nm, is evenly distributed on the graphene film.
V with the present embodiment gained 2O 5Quantum dot/graphene composite material is an example, and the constant current charge-discharge test result of carrying out under the 100mA/g current density shows that its first discharge specific capacity can reach and be 239mAh/g, and 100 times the circulation back is 202mAh/g, and capability retention is 84.51%.
Embodiment 3:
One, the preparation of Graphene dispersion liquid: identical with embodiment 1;
Two, V 2O 5The preparation of colloidal sol: identical with embodiment 1;
Three, V 2O 5The preparation of quantum dot/graphene composite material:
9) with the V of 1.5mmol 2O 5Colloidal sol also is diluted in and obtains 40ml V in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than the aniline solution of measuring 0.05mol/L for 0.03:1 2O 5Solution stirred 0.5 hour;
10) set by step 9) add 10ml Graphene dispersion liquid in the gained solution, and to add deionized water to overall solution volume be 60ml, at room temperature stirred 0.5 hour;
11) uniform solution with the step 10) gained is transferred in the thermostat water bath, carries out 90 ℃ of waters bath with thermostatic control, and the time is 22h;
12) solution after step 11) is handled changes in the 100ml reactor, 200 ℃ of following hydro-thermal reactions 48 hours, takes out from reactor then, naturally cools to room temperature;
13) with absolute ethyl alcohol cyclic washing step 12) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
With product V of the present invention 2O 5Quantum dot/graphene composite material is an example, its V 2O 5The diameter of quantum dot is 2-3nm, is evenly distributed on the graphene film.
V with the present embodiment gained 2O 5Quantum dot/graphene composite material is an example, and the constant current charge-discharge test result of carrying out under the 100mA/g current density shows that its first discharge specific capacity can reach and be 234mAh/g, and 100 times the circulation back is 198mAh/g, and capability retention is 84.62%.
Embodiment 4:
One, the preparation of Graphene dispersion liquid: identical with embodiment 1;
Two, V 2O 5The preparation of colloidal sol: identical with embodiment 1;
Three, V 2O 5The preparation of quantum dot/graphene composite material:
9) with the V of 1.3mmol 2O 5Colloidal sol also is diluted in and obtains 40ml V in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than the aniline solution of measuring 0.05mol/L for 0.03:1 2O 5Solution stirred 0.5 hour;
10) set by step 9) add 13ml Graphene dispersion liquid in the gained solution, and to add deionized water to overall solution volume be 60ml, at room temperature stirred 0.5 hour;
11) uniform solution with the step 10) gained is transferred in the thermostat water bath, carries out 70 ℃ of waters bath with thermostatic control, and the time is 26h;
12) solution after step 11) is handled changes in the 100ml reactor, 160 ℃ of following hydro-thermal reactions 36 hours, takes out from reactor then, naturally cools to room temperature;
13) with absolute ethyl alcohol cyclic washing step 12) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
With product V of the present invention 2O 5Quantum dot/graphene composite material is an example, its V 2O 5The diameter of quantum dot is 2-3nm, is evenly distributed on the graphene film.
V with the present embodiment gained 2O 5Quantum dot/graphene composite material is an example, and the constant current charge-discharge test result of carrying out under the 100mA/g current density shows that its first discharge specific capacity can reach and be 229mAh/g, and 100 times the circulation back is 194mAh/g, and capability retention is 84.71%.
Embodiment 5:
One, the preparation of Graphene dispersion liquid: identical with embodiment 1;
Two, V 2O 5The preparation of colloidal sol: identical with embodiment 1;
Three, V 2O 5The preparation of quantum dot/graphene composite material:
9) with the V of 1.5mmol 2O 5Colloidal sol also is diluted in and obtains 40mlV in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than the aniline solution of measuring 0.05mol/L for 0.03:1 2O 5Solution stirred 0.5 hour;
10) set by step 9) add 16ml Graphene dispersion liquid in the gained solution, and to add deionized water to overall solution volume be 60ml, at room temperature stirred 0.5 hour;
11) uniform solution with the step 10) gained is transferred in the thermostat water bath, carries out 90 ℃ of waters bath with thermostatic control, and the time is 22h;
12) solution after step 11) is handled changes in the 100ml reactor, 160 ℃ of following hydro-thermal reactions 60 hours, takes out from reactor then, naturally cools to room temperature;
13) with absolute ethyl alcohol cyclic washing step 12) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
With product V of the present invention 2O 5Quantum dot/graphene composite material is an example, its V 2O 5The diameter of quantum dot is 2-3nm, is evenly distributed on the graphene film.
V with the present embodiment gained 2O 5Quantum dot/graphene composite material is an example, and the constant current charge-discharge test result of carrying out under the 100mA/g current density shows that its first discharge specific capacity can reach and be 242mAh/g, and 100 times the circulation back is 193mAh/g, and capability retention is 79.75%.
Embodiment 6:
One, the preparation of Graphene dispersion liquid: identical with embodiment 1;
Two, V 2O 5The preparation of colloidal sol: identical with embodiment 1;
Three, V 2O 5The preparation of quantum dot/graphene composite material:
9) with the V of 1.1mmol 2O 5Colloidal sol also is diluted in and obtains 40ml V in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than the aniline solution of measuring 0.05mol/L for 0.03:1 2O 5Solution stirred 0.5 hour;
10) set by step 9) add 10ml Graphene dispersion liquid in the gained solution, and to add deionized water to overall solution volume be 60ml, at room temperature stirred 0.5 hour;
11) uniform solution with the step 10) gained is transferred in the thermostat water bath, carries out 70 ℃ of waters bath with thermostatic control, and the time is 22h;
12) solution after step 11) is handled changes in the 100ml reactor, 160 ℃ of following hydro-thermal reactions 60 hours, takes out from reactor then, naturally cools to room temperature;
13) with absolute ethyl alcohol cyclic washing step 12) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
With product V of the present invention 2O 5Quantum dot/graphene composite material is an example, its V 2O 5The diameter of quantum dot is 2-3nm, is evenly distributed on the graphene film.
V with the present embodiment gained 2O 5Quantum dot/graphene composite material is an example, and the constant current charge-discharge test result of carrying out under the 100mA/g current density shows that its first discharge specific capacity can reach and be 230mAh/g, and 100 times the circulation back is 194mAh/g, and capability retention is 84.34%.

Claims (11)

1.V 2O 5Quantum dot/graphene composite material, its V 2O 5The diameter of quantum dot is 2-3nm, is evenly distributed on the graphene film, adopts following method to make, and includes following steps:
1) gets the V of 1.1～1.5mmol 2O 5Colloidal sol also is diluted in and obtains 40ml V in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than measuring aniline solution for 0.03:1 2O 5In the solution, stir;
2) in step 1) gained solution, add the Graphene dispersion liquid in proportion, and to add deionized water to overall solution volume be 60ml, at room temperature stir;
3) with step 2) uniform solution of gained is transferred in the thermostat water bath, carries out the water bath with thermostatic control heat treated;
4) solution after the step 3) processing is changed in the 100ml reactor, carry out hydro-thermal reaction, from reactor, take out then, naturally cool to room temperature;
5) with absolute ethyl alcohol cyclic washing step 4) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
2. V as claimed in claim 1 2O 5Quantum dot/graphene composite material is characterized in that step 2) preparation method of described Graphene dispersion liquid includes following steps:
A) in the 250ml conical flask, add the 1g graphite powder and the 23ml concentrated sulfuric acid, at room temperature mix and stirred 24 hours;
B) conical flask is put into thermostat water bath, 40 ℃ of reaction temperatures add 100mgNaNO in step a) gained dispersion liquid 3, stirred 5 minutes, slowly add 500mg KMnO subsequently 4, and keep solution temperature below 45 ℃, stirred 30 minutes;
C) in step b) gained dispersion liquid, add the 3ml deionized water, stir after 5 minutes, add the 3ml deionized water again, stirred subsequently 5 minutes, add the 40ml deionized water again, stirred 15 minutes;
D) conical flask is shifted out water-bath, add 140ml deionized water and 10ml mass percent concentration 30%H 2O 2To stop oxidation reaction;
E) with step d) gained suspension service quality percent concentration 5%HCl solution washing twice, extremely neutral with deionized water wash subsequently, be dispersed in the 100ml deionized water ultrasonic 60 minutes;
F) 5000 rev/mins of step e) gained suspension is centrifugal, the time is 5 minutes, gets supernatant liquor repeatedly, and until isolating uniform Graphene dispersion liquid, concentration is 1mg/ml.
3. V as claimed in claim 1 or 2 2O 5Quantum dot/graphene composite material is characterized in that the described water bath with thermostatic control temperature of step 3) is 70-90 ℃, and the reaction time is 22-26 hour.
4. V as claimed in claim 1 or 2 2O 5Quantum dot/graphene composite material is characterized in that step 2) amount of described Graphene is 10-16mg.
5. V as claimed in claim 1 or 2 2O 5Quantum dot/graphene composite material is characterized in that the described hydrothermal temperature of step 4) is 160-200 ℃, and the time is 36-60 hour.
6. the described V of claim 1 2O 5The preparation method of quantum dot/graphene composite material includes following steps:
1) gets the V of 1.1～1.5mmol 2O 5Colloidal sol also is diluted in and obtains 40ml V in the deionized water 2O 5Solution is pressed and V 2O 5Amount of substance splashes into V than measuring aniline solution for 0.03:1 2O 5In the solution, stir;
2) in step 1) gained solution, add the Graphene dispersion liquid in proportion, and to add deionized water to overall solution volume be 60ml, at room temperature stir;
3) with step 2) uniform solution of gained is transferred in the thermostat water bath, carries out the water bath with thermostatic control heat treated;
4) solution after the step 3) processing is changed in the 100ml reactor, carry out hydro-thermal reaction, from reactor, take out then, naturally cool to room temperature;
5) with absolute ethyl alcohol cyclic washing step 4) products therefrom, oven dry promptly obtains V 2O 5Quantum dot/graphene composite material.
7. V as claimed in claim 6 2O 5The preparation method of quantum dot/graphene composite material is characterized in that step 2) preparation method of described Graphene dispersion liquid includes following steps:
A) in the 250ml conical flask, add the 1g graphite powder and the 23ml concentrated sulfuric acid, at room temperature mix and stirred 24 hours;
B) conical flask is put into thermostat water bath, 40 ℃ of reaction temperatures add 100mgNaNO in step a) gained dispersion liquid 3, stirred 5 minutes, slowly add 500mg KMnO subsequently 4, and keep solution temperature below 45 ℃, stirred 30 minutes;
C) in step b) gained dispersion liquid, add the 3ml deionized water, stir after 5 minutes, add the 3ml deionized water again, stirred subsequently 5 minutes, add the 40ml deionized water again, stirred 15 minutes;
D) conical flask is shifted out water-bath, add 140ml deionized water and 10ml mass percent concentration 30%H 2O 2To stop oxidation reaction;
E) with step d) gained suspension service quality percent concentration 5%HCl solution washing twice, extremely neutral with deionized water wash subsequently, be dispersed in the 100ml deionized water ultrasonic 60 minutes;
F) 5000 rev/mins of step e) gained suspension is centrifugal, the time is 5 minutes, gets supernatant liquor repeatedly, and until isolating uniform Graphene dispersion liquid, concentration is 1mg/ml.
8. as claim 6 or 7 described V 2O 5The preparation method of quantum dot/graphene composite material is characterized in that the described water bath with thermostatic control temperature of step 3) is 70-90 ℃, and the reaction time is 22-26 hour.
9. as claim 6 or 7 described V 2O 5The preparation method of quantum dot/graphene composite material is characterized in that step 2) amount of described Graphene is 10-16mg.
10. as claim 6 or 7 described V 2O 5The preparation method of quantum dot/graphene composite material is characterized in that the described hydrothermal temperature of step 4) is 160-200 ℃, and the time is 36-60 hour.
11. the described V of claim 1 2O 5Quantum dot/graphene composite material is as the application of anode active material of lithium ion battery.
CN2013100993772A 2013-03-26 2013-03-26 V205 quantum dot/graphene composite materials and preparation method thereof and application thereof Pending CN103227317A (en)

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