CN105375008A - Laminated Na3V2(PO4)3@rGo nanocomposite and preparation method and application therefor - Google Patents

Laminated Na3V2(PO4)3@rGo nanocomposite and preparation method and application therefor Download PDF

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CN105375008A
CN105375008A CN201510772387.7A CN201510772387A CN105375008A CN 105375008 A CN105375008 A CN 105375008A CN 201510772387 A CN201510772387 A CN 201510772387A CN 105375008 A CN105375008 A CN 105375008A
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stratiform
nano composite
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rgo nano
rgo
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CN105375008B (en
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安琴友
徐亚楠
麦立强
魏湫龙
盛进之
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Wuhan University of Technology WUT
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    • 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
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Abstract

The invention relates to a laminated Na3V2(PO4)3@rGo nanocomposite and an preparation method and an application therefor. The nanocomposite can be used as a sodium ion battery positive electrode active material with high rate capability and long service life; and the nanocomposite is formed by a sheet structure and rGO nano-sheets in a layer-to-layer overlapping manner, wherein the sheet structure is formed by nanoscale sub-unit Na3V2(PO4)3 particles. When the laminated Na3V2(PO4)3@rGo nanocomposite is used as the sodium ion battery positive electrode active material, the material is excellent in cycling stability and high in rate capability, so that the laminated Na3V2(PO4)3@rGo nanocomposite is the potential application material for the sodium ion batteries with high rate capability and long service life; and in addition, the preparation method is simple in process, capable of meeting the green chemistry demand, low in equipment requirement and good for the marketization promotion.

Description

Stratiform Na 3v 2(PO 4) 3@rGO nano composite material and its preparation method and application
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to a kind of stratiform Na 3v 2(PO 4) 3@rGO nano composite material and preparation method thereof, this material can be used as high magnification, long-life sodium-ion battery positive electrode active materials.
Background technology
The society that is stored in of the energy occupies very consequence.As electric automobile, mobile phone, notebook computer, electric device and electronic product constantly update, and this has had urgent requirement to the energy storage device possessing high power and high-energy-density.In order to meet these demands, lithium battery, as a kind of energy storage and function element, is a kind of to select preferably, because it has high-energy-density, long circulation life and the relatively advantage such as environmental protection.But limited lithium resource will face shortage problem, elemental lithium expensive and in the earth's crust content few, this, for the long-life energy-storage battery of the extensive energy storage of development, may become a major issue, also result in the generally worry of people.The research and development of sodium-ion battery can relax the battery development limitation problem because lithium resource shortage causes to a certain extent.If develop the material of function admirable, safety and stability on this basis, sodium-ion battery will have the market competition advantage larger than lithium battery.
As the potential positive electrode of one, there is the Na of sodium superionic conductors (NASICON) structure 3v 2(PO 4) 3have raw material cheap, rich reserves, energy density advantages of higher, is thus extensively studied.But lower electronic conductivity limits its more long-range development, in order to obtain significant chemical property, multiplying power and the circulatory problems of difference are in the urgent need to address.In the last few years, the Na that carbon is coated 3v 2(PO 4) 3be embedded in porous carbon substrate, show super good multiplying power and cyclical stability.
Graphene has high conductivity because of it, and the Graphene of various nanotopography and the compound of active material are repeatedly reported in recent years, confirm that Graphene has extremely important effect for the chemical property improving material.But change Na by hydro thermal method 3v 2(PO 4) 3the surface charge of presoma is electrical, with graphene oxide hydrogel interface Interaction of substituents, formation is uniformly dispersed, mixed gel disperse system steady in a long-term, is then kept the internal structure of presoma by Freeze Drying Technique, synthesizes a kind of stratiform Na finally by Post isothermal treatment 3v 2(PO 4) 3@rGO nano composite material has not yet to see report.
Summary of the invention
Technical problem to be solved by this invention provides a kind of stratiform Na for above-mentioned prior art 3v 2(PO 4) 3@rGO nano composite material and preparation method thereof, its technique is simple, the requirement that meets Green Chemistry, stratiform Na 3v 2(PO 4) 3@rGO nano composite material has excellent chemical property.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of stratiform Na 3v 2(PO 4) 3@rGO nano composite material, by nanoscale subunit Na 3v 2(PO 4) 3the laminated structure of particle composition and and rGO nanometer sheet overlap layer by layer and form, adopt following method to obtain, include following steps:
1) by Na 2cO 3, V (C 5h 7o 2) 3, NH 4h 2pO 4dissolve in deionized water according to stoichiometric proportion 1.5:2:3; Described Na 2cO 3be 0.75 ~ 3mmol; V (C 5h 7o 2) 3be 1 ~ 4mmol; NH 4h 2pO 4be 1.5 ~ 6mmol;
2) by step 1) after the ultrasonic process of gained solution, then stir under water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in reactor, and hydro-thermal reaction, naturally cools to room temperature;
4) to step 3) add 10 ~ 30mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid;
6) by step 5) after the grinding of the desciccate of gained, calcination, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
By such scheme, step 1) described in deionized water be 40 ~ 80mL; Step 2) described in ultrasonic power be 60 ~ 90kHz, the time is 30 ~ 60 minutes; Bath temperature is 70 ~ 90 DEG C, and the time is 60 ~ 120 minutes.
By such scheme, step 3) described in hydrothermal temperature be 180 DEG C; Reaction time is 6 ~ 24 hours.
By such scheme, step 5) described in drying be adopt Freeze Drying Technique.
By such scheme, step 6) described in calcining heat be 650 ~ 750 DEG C; Calcination atmosphere is Ar/H 2; Heating rate is 2 DEG C/min; Calcination time is 6 ~ 10 hours.
Described stratiform Na 3v 2(PO 4) 3the preparation method of@rGO nano composite material, includes following steps:
1) by Na 2cO 3, V (C 5h 7o 2) 3, NH 4h 2pO 4dissolve in deionized water according to stoichiometric proportion 1.5:2:3; Described Na 2cO 3be 0.75 ~ 3mmol; V (C 5h 7o 2) 3be 1 ~ 4mmol; NH 4h 2pO 4be 1.5 ~ 6mmol;
2) by step 1) after the ultrasonic process of gained solution, then stir under water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in reactor, and hydro-thermal reaction, naturally cools to room temperature;
4) to step 3) add 10 ~ 30mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid;
6) by step 5) after the grinding of the desciccate of gained, calcination, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
Described stratiform Na 3v 2(PO 4) 3@rGO nano composite material is as the application of high magnification, long-life sodium-ion battery positive electrode active materials.
The present invention changes Na by hydro thermal method 3v 2(PO 4) 3the surface charge of presoma is electrical, by with graphene oxide hydrogel interface Interaction of substituents, formation is uniformly dispersed, mixed gel disperse system steady in a long-term, is then kept the internal structure of presoma by Freeze Drying Technique, synthesizes a kind of stratiform Na finally by Post isothermal treatment 3v 2(PO 4) 3@rGO nano composite material, by nanoscale subunit Na 3v 2(PO 4) 3the laminated structure of particle composition and and rGO nanometer sheet overlap layer by layer and form,
Present invention dramatically increases Na 3v 2(PO 4) 3the conductivity of material, shorten sodium ion diffusion length, in sodium ion deintercalation process, padded coaming volume sharply changes and ensures its structure and electrochemical stability, and then substantially increases the chemical property of material.When this material is as sode cell positive electrode active materials, the constant current charge-discharge test result of carrying out under 2.2A/g high current density shows, its first discharge specific capacity can reach 101mAh/g, and be 79mAh/g after 7000 circulations, capability retention reaches 79%.Even under the superhigh-current-density of 11A/g and 22A/g, this material still can provide the specific capacity of 73mAh/g and 41mAh/g.This result shows this stratiform Na 3v 2(PO 4) 3@rGO nano composite material has excellent cyclical stability and high-rate characteristics, is the potential application material of high power, long-life sode cell.
In addition, stratiform Na 3v 2(PO 4) 3@rGO nano composite material synthesis technique is simple, and reaction condition is gentle, and its layer structure can control by changing reactant concentration, reaction temperature and time, has made effort for exploring extensive synthesis laminated nano composition.
The invention has the beneficial effects as follows: based on the synthesis mechanism of mixing presoma colloidal interface Interaction of substituents, in conjunction with Na 3v 2(PO 4) 3the unique advantage of two-dimensional sheet structure and three-dimensional rGO network configuration, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite material.During as sodium-ion battery positive electrode active materials, this material list reveals excellent cyclical stability and high-rate characteristics, is the potential application material of high magnification, long-life sodium-ion battery.Present invention process is simple, meets the requirement of Green Chemistry, low for equipment requirements, is conducive to the marketization and promotes.
Accompanying drawing explanation
Fig. 1 is the stratiform Na of the embodiment of the present invention 1 3v 2(PO 4) 3the XRD figure of@rGO nano composite material;
Fig. 2 is the stratiform Na of the embodiment of the present invention 1 3v 2(PO 4) 3the SEM figure of@rGO nano composite material;
Fig. 3 is the stratiform Na of the embodiment of the present invention 1 3v 2(PO 4) 3the TEM figure of@rGO nano composite material;
Fig. 4 is the stratiform Na of the embodiment of the present invention 1 3v 2(PO 4) 3the synthesis mechanism figure of@rGO nano composite material;
Fig. 5 is the stratiform Na of the embodiment of the present invention 1 3v 2(PO 4) 3the Raman spectrogram of@rGO nano composite material;
Fig. 6 is the stratiform Na of the embodiment of the present invention 1 3v 2(PO 4) 3the multiplying power figure of@rGO nano composite material;
Fig. 7 is the stratiform Na of the embodiment of the present invention 1 3v 2(PO 4) 3the high current density cycle graph of@rGO nano composite material.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
Stratiform Na 3v 2(PO 4) 3the preparation method of@rGO nano composite material, it comprises the steps:
1) by 0.75mmolNa 2cO 3, 1mmolV (C 5h 7o 2) 3, 1.5mmolNH 4h 2pO 4be dissolved in 40mL deionized water;
2) by step 1) the ultrasonic process of gained solution is after 60 minutes, stirs 120 minutes under 80 DEG C of water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in 50mL reactor, and at 180 DEG C, hydro-thermal 8 hours, naturally cools to room temperature;
4) to step 3) add 10mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid employing Freeze Drying Technique;
6) by step 5) after the grinding of the desciccate of gained, at 750 DEG C of Ar/H 2calcination 6 hours under atmosphere, heating rate is 2 DEG C/min, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
As shown in Figure 4, synthesis mechanism of the present invention is: change Na by hydro thermal method 3v 2(PO 4) 3the surface charge of presoma is electrical, by with graphene oxide hydrogel interface Interaction of substituents, formation is uniformly dispersed, mixed gel disperse system steady in a long-term, then kept the internal structure of presoma stacked in layers by Freeze Drying Technique, synthesize a kind of stratiform Na finally by Post isothermal treatment 3v 2(PO 4) 3@rGO nano composite material; This kind of structure can effectively in conjunction with Na 3v 2(PO 4) 3the unique advantage of two-dimensional sheet structure and three-dimensional rGO network configuration, the electronic conductance of collaborative raising electrode material and ionic conductance, the dilation of buffer electrode material charge and discharge process, thus obtain long-life, powerful chemical property.
With this example product stratiform Na 3v 2(PO 4) 3@rGO nano composite material is example, and its structure is determined by x-ray diffractometer.As shown in Figure 1, X-ray diffracting spectrum (XRD) shows, the stratiform Na of sodium superionic conductors structure 3v 2(PO 4) 3(JCPDS card number is@rGO nano composite material: 53-0018), without other dephasign.As shown in Figure 2, field emission scanning electron microscope (FESEM) test shows, this stratiform Na 3v 2(PO 4) 3@rGO nano composite material is by nanoscale subunit Na 3v 2(PO 4) 3the laminated structure of particle composition and and rGO nanometer sheet overlap layer by layer and form.As shown in Figure 3, transmission electron microscope (TEM) and high-resolution transmission electrode (HRTEM) test demonstrate this layer structure and have good crystal structure.As shown in Figure 4, this stratiform Na 3v 2(PO 4) 3the forming process of@rGO nano composite material changes Na by hydro thermal method 3v 2(PO 4) 3the surface charge of presoma is electrical, by with graphene oxide hydrogel interface Interaction of substituents, formation is uniformly dispersed, mixed gel disperse system steady in a long-term, then kept the internal structure of presoma stacked in layers by Freeze Drying Technique, synthesize a kind of stratiform Na finally by Post isothermal treatment 3v 2(PO 4) 3@rGO nano composite material.As shown in Figure 5, Raman spectrum (Ramanspectrum) shows the characteristic peak of all D and G of Graphene, describes the existence of Graphene.
Stratiform Na prepared by the present invention 3v 2(PO 4) 3@rGO nano composite material is as sodium-ion battery positive electrode active materials, and all the other steps of the preparation method of sodium-ion battery are identical with common preparation method.The preparation method of positive plate is as follows, adopts stratiform Na 3v 2(PO 4) 3@rGO nano composite material is as active material, and acetylene black is as conductive agent, and polyvinylidene fluoride is as binding agent, and the mass ratio of active material, acetylene black, polyvinylidene fluoride is 70:20:10; Be solvent with 1-METHYLPYRROLIDONE by them, after fully mixing in proportion, ultrasonic 60 minutes, then be uniformly coated on aluminium foil, the load capacity of its active material is 1.5-2.0gcm -1; It is for subsequent use after 24 hours that the positive plate pressed is placed in the oven drying of 80 DEG C.With the NaClO of 1M 4be dissolved in as electrolyte in vinyl carbonate (EC) and dimethyl carbonate (DMC), sodium sheet is negative pole, and glass fibre is barrier film, and CR2016 type stainless steel is that battery case is assembled into button sodium-ion battery.
With stratiform Na 3v 2(PO 4) 3@rGO is example, as shown in Figure 6, when this material is as sode cell positive electrode active materials, the constant current charge-discharge test result of carrying out under 2.2A/g high current density shows, its first discharge specific capacity can reach 101mAh/g respectively, and be 79mAh/g after 7000 circulations, capability retention reaches 79%.As shown in Figure 7, under the superhigh-current-density of 11A/g and 22A/g, this material still can provide the specific capacity of 73mAh/g and 41mAh/g.This result shows stratiform Na 3v 2(PO 4) 3@rGO nano composite material has excellent high magnification and long-life characteristics, is the potential application material of high-performance sodium-ion battery.
Embodiment 2:
Stratiform Na 3v 2(PO 4) 3@rGO Nano-composite materials method, it comprises the steps:
1) by 0.75mmolNa 2cO 3, 1mmolV (C 5h 7o 2) 3, 1.5mmolNH 4h 2pO 4be dissolved in 40mL deionized water;
2) by step 1) the ultrasonic process of gained solution is after 30 minutes, stirs 60 minutes under 90 DEG C of water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in 50mL reactor, and at 180 DEG C, hydro-thermal 10 hours, naturally cools to room temperature;
4) to step 3) add 20mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid employing Freeze Drying Technique;
6) by step 5) after the grinding of the desciccate of gained, at 750 DEG C of Ar/H 2calcination 6 hours under atmosphere, heating rate is 2 DEG C/min, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
This stratiform Na 3v 2(PO 4) 3@rGO nano composite material is by nanoscale subunit Na 3v 2(PO 4) 3the laminated structure of particle composition and and rGO nanometer sheet overlap layer by layer and form.
With the three-dimensional porous V of the present embodiment gained 2o 5classifying nano dish is example, and the constant current charge-discharge test result of carrying out under 2.2A/g shows, its first discharge specific capacity can reach 96mAh/g respectively, for 80mAh/g capability retention reaches 83.3% after 1000 circulations.Embodiment 3:
Stratiform Na 3v 2(PO 4) 3@rGO Nano-composite materials method, it comprises the steps:
1) by 1.5mmolNa 2cO 3, 2mmolV (C 5h 7o 2) 3, 3mmolNH 4h 2pO 4be dissolved in 70mL deionized water;
2) by step 1) the ultrasonic process of gained solution is after 60 minutes, stirs 60 minutes under 80 DEG C of water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in 100mL reactor, and at 180 DEG C, hydro-thermal 8 hours, naturally cools to room temperature;
4) to step 3) add 30mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid employing Freeze Drying Technique;
6) by step 5) after the grinding of the desciccate of gained, at 700 DEG C of Ar/H 2calcination 8 hours under atmosphere, heating rate is 2 DEG C/min, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
This stratiform Na of product of the present invention 3v 2(PO 4) 3@rGO nano composite material is by nanoscale subunit Na 3v 2(PO 4) 3the laminated structure of particle composition and and rGO nanometer sheet overlap layer by layer and form.
With the stratiform Na of the present embodiment gained 3v 2(PO 4) 3@rGO nano composite material is example, and the constant current charge-discharge test result of carrying out under 2.2A/g high current density shows, its first discharge specific capacity can reach 99mAh/g respectively, and be 82mAh/g after 1000 circulations, capability retention reaches 82.8%.
Embodiment 4:
Stratiform Na 3v 2(PO 4) 3@rGO Nano-composite materials method, it comprises the steps:
1) by 1.5mmolNa 2cO 3, 2mmolV (C 5h 7o 2) 3, 3mmolNH 4h 2pO 4be dissolved in 80mL deionized water;
2) by step 1) the ultrasonic process of gained solution is after 30 minutes, stirs 60 minutes under 90 DEG C of water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in 100mL reactor, and at 180 DEG C, hydro-thermal 8 hours, naturally cools to room temperature;
4) to step 3) add 20mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid employing Freeze Drying Technique;
6) by step 5) after the grinding of the desciccate of gained, at 650 DEG C of Ar/H 2calcination 10 hours under atmosphere, heating rate is 2 DEG C/min, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
This stratiform Na of product of the present invention 3v 2(PO 4) 3@rGO nano composite material is by nanoscale subunit Na 3v 2(PO 4) 3the laminated structure of particle composition and and rGO nanometer sheet overlap layer by layer and form.
With the stratiform Na of the present embodiment gained 3v 2(PO 4) 3@rGO nano composite material is example, and the constant current charge-discharge test result of carrying out under 2.2A/g shows, its first discharge specific capacity can reach 97mAh/g respectively, and be 80mAh/g after 1000 circulations, capability retention reaches 82.5%.
Embodiment 5:
Stratiform Na 3v 2(PO 4) 3@rGO Nano-composite materials method, it comprises the steps:
1) by 0.75mmolNa 2cO 3, 1mmolV (C 5h 7o 2) 3, 1.5mmolNH 4h 2pO 4be dissolved in 30mL deionized water;
2) by step 1) the ultrasonic process of gained solution is after 30 minutes, stirs 120 minutes under 70 DEG C of water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in 50mL reactor, and at 180 DEG C, hydro-thermal 10 hours, naturally cools to room temperature;
4) to step 3) add 10mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid employing Freeze Drying Technique;
6) by step 5) after the grinding of the desciccate of gained, at 750 DEG C of Ar/H 2calcination 6 hours under atmosphere, heating rate is 2 DEG C/min, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
This stratiform Na of product of the present invention 3v 2(PO 4) 3@rGO nano composite material is by nanoscale subunit Na 3v 2(PO 4) 3the laminated structure of particle composition and and rGO nanometer sheet overlap layer by layer and form.
With the stratiform Na of the present embodiment gained 3v 2(PO 4) 3@rGO nano composite material is example, and the constant current charge-discharge test result of carrying out under 2.2A/g shows, its first discharge specific capacity can reach 99mAh/g respectively, and be 86mAh/g after 1000 circulations, capability retention reaches 6.8%.
Embodiment 6:
Stratiform Na 3v 2(PO 4) 3@rGO Nano-composite materials method, it comprises the steps:
1) by 1.5mmolNa 2cO 3, 2mmolV (C 5h 7o 2) 3, 3mmolNH 4h 2pO 4be dissolved in 60mL deionized water;
2) by step 1) the ultrasonic process of gained solution is after 60 minutes, stirs 60 minutes under 90 DEG C of water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in 100mL reactor, and at 180 DEG C, hydro-thermal 6 hours, naturally cools to room temperature;
4) to step 3) add 20mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid employing Freeze Drying Technique;
6) by step 5) after the grinding of the desciccate of gained, at 750 DEG C of Ar/H 2calcination 8 hours under atmosphere, heating rate is 2 DEG C/min, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
This stratiform Na of product of the present invention 3v 2(PO 4) 3@rGO nano composite material is by nanoscale subunit Na 3v 2(PO 4) 3the laminated structure of particle composition and and rGO nanometer sheet overlap layer by layer and form.
With the stratiform Na of the present embodiment gained 3v 2(PO 4) 3@rGO nano composite material is example, and the constant current charge-discharge test result of carrying out under 2.2A/g shows, its first discharge specific capacity can reach 100mAh/g respectively, and be 91mAh/g after 1000 circulations, capability retention reaches 91.0%.

Claims (11)

1. a stratiform Na 3v 2(PO 4) 3@rGO nano composite material, by nanoscale subunit Na 3v 2(PO 4) 3the laminated structure of particle composition and and rGO nanometer sheet overlap layer by layer and form, adopt following method to obtain, include following steps:
1) by Na 2cO 3, V (C 5h 7o 2) 3, NH 4h 2pO 4dissolve in deionized water according to stoichiometric proportion 1.5:2:3; Described Na 2cO 3be 0.75 ~ 3mmol; V (C 5h 7o 2) 3be 1 ~ 4mmol; NH 4h 2pO 4be 1.5 ~ 6mmol;
2) by step 1) after the ultrasonic process of gained solution, then stir under water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in reactor, and hydro-thermal reaction, naturally cools to room temperature;
4) to step 3) add 10 ~ 30mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid;
6) by step 5) after the grinding of the desciccate of gained, calcination, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
2. stratiform Na according to claim 1 3v 2(PO 4) 3@rGO nano composite material, is characterized in that step 1) described in deionized water be 40 ~ 80mL; Step 2) described in ultrasonic power be 60 ~ 90kHz, the time is 30 ~ 60 minutes; Bath temperature is 70 ~ 90 DEG C, and the time is 60 ~ 120 minutes.
3. stratiform Na according to claim 1 and 2 3v 2(PO 4) 3@rGO nano composite material, is characterized in that step 3) described in hydrothermal temperature be 180 DEG C; Reaction time is 6 ~ 24 hours.
4. stratiform Na according to claim 1 and 2 3v 2(PO 4) 3@rGO nano composite material, is characterized in that step 5) described in drying be adopt Freeze Drying Technique.
5. stratiform Na according to claim 1 and 2 3v 2(PO 4) 3@rGO nano composite material, is characterized in that step 6) described in calcining heat be 650 ~ 750 DEG C; Calcination atmosphere is Ar/H 2; Heating rate is 2 DEG C/min; Calcination time is 6 ~ 10 hours.
6. stratiform Na according to claim 1 3v 2(PO 4) 3the preparation method of@rGO nano composite material, includes following steps:
1) by Na 2cO 3, V (C 5h 7o 2) 3, NH 4h 2pO 4dissolve in deionized water according to stoichiometric proportion 1.5:2:3; Described Na 2cO 3be 0.75 ~ 3mmol; V (C 5h 7o 2) 3be 1 ~ 4mmol; NH 4h 2pO 4be 1.5 ~ 6mmol;
2) by step 1) after the ultrasonic process of gained solution, then stir under water bath condition;
3) by step 2) the light blue precursor mixture that obtains transfers in reactor, and hydro-thermal reaction, naturally cools to room temperature;
4) to step 3) add 10 ~ 30mg graphene oxide in the green g., jelly-like gel that obtains and be stirred to dispersed;
5) by step 4) drying of gained Homogeneous phase mixing gel dispersion liquid;
6) by step 5) after the grinding of the desciccate of gained, calcination, obtains stratiform Na 3v 2(PO 4) 3@rGO nano composite powder.
7. stratiform Na according to claim 6 3v 2(PO 4) 3the preparation method of@rGO nano composite material, is characterized in that step 1) described in deionized water be 40 ~ 80mL; Step 2) described in ultrasonic power be 60 ~ 90kHz, the time is 30 ~ 60 minutes; Bath temperature is 70 ~ 90 DEG C, and the time is 60 ~ 120 minutes.
8. the stratiform Na according to claim 6 or 7 3v 2(PO 4) 3the preparation method of@rGO nano composite material, is characterized in that step 3) described in hydrothermal temperature be 180 DEG C; Reaction time is 6 ~ 24 hours.
9. the stratiform Na according to claim 6 or 7 3v 2(PO 4) 3the preparation method of@rGO nano composite material, is characterized in that step 5) described in drying be adopt Freeze Drying Technique.
10. the stratiform Na according to claim 6 or 7 3v 2(PO 4) 3the preparation method of@rGO nano composite material, is characterized in that step 6) described in calcining heat be 650 ~ 750 DEG C; Calcination atmosphere is Ar/H 2; Heating rate is 2 DEG C/min; Calcination time is 6 ~ 10 hours.
11. stratiform Na according to claim 1 3v 2(PO 4) 3@rGO nano composite material is as the application of high magnification, long-life sodium-ion battery positive electrode active materials.
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CN106058202A (en) * 2016-07-29 2016-10-26 华南理工大学 Carbon-coated metal ion-doped sodium vanadium phosphate composite cathode material prepared by freeze drying method, as well as preparation method and application thereof
WO2018032980A1 (en) * 2016-08-15 2018-02-22 福建新峰二维材料科技有限公司 Manufacturing method of positive-electrode material for sodium-ion battery
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CN106328990A (en) * 2016-11-07 2017-01-11 上海碳源汇谷新材料科技有限公司 Lithium ion battery anode material based on redox graphene/layered metal phosphate composite material
CN106783193A (en) * 2017-02-21 2017-05-31 上海奥威科技开发有限公司 Graphene-based sodium ion ultracapacitor and preparation method thereof
CN107359340A (en) * 2017-07-19 2017-11-17 广东迈纳科技有限公司 A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support
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CN109616651A (en) * 2018-12-11 2019-04-12 南京工业大学 A kind of graphene-based vanadium phosphate sodium composite nano materials of sodium ion positive electrode Heteroatom doping
CN109616651B (en) * 2018-12-11 2022-03-11 南京工业大学 Heteroatom-doped graphene-based vanadium sodium phosphate composite nano material for sodium ion anode material
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