CN107359340A - A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support - Google Patents
A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support Download PDFInfo
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- CN107359340A CN107359340A CN201710589937.0A CN201710589937A CN107359340A CN 107359340 A CN107359340 A CN 107359340A CN 201710589937 A CN201710589937 A CN 201710589937A CN 107359340 A CN107359340 A CN 107359340A
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support, about 1 ~ 5 micron of the micron bulb diameter of gained, wherein about 200 ~ 500 nanometers embedded of nano particle, specific steps：Ammonium metavanadate is dissolved in deionized water, is completely dissolved it, after taking-up in the state of lasting stirring, is down to room temperature；Sodium fluoride is slowly added in resulting solution, is stirred well to dissolving at room temperature；Ammonium dihydrogen phosphate is slowly added in resulting solution, is stirred well to dissolving at room temperature；Under continuous stirring, by graphene oxide dispersion, it is added dropwise in step resulting solution；Resulting solution is transferred in spray-drying installation, obtains spherical precursor powder sample；It is placed in tube furnace and obtains the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support by high-temperature calcination.The present invention has the characteristics of technique is simple, yield is big, reaction condition is gentle, material electrochemical performance is excellent.
Description
Technical field
The present invention relates to nanometer material and electrochemical technology field, particularly a kind of three-dimensional grapheme network skeleton support
The preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium.
Background technology
With energy shortage and being on the rise the problems such as environmental pollution, sustainable novel energy is cleaned in exploitation to be become
Urgent problem to be solved.At present, lithium ion battery is had extended cycle life due to energy density height, is had been widely used for mobile phone, pen
Remember this grade mancarried electronic aid, and by the optimal selection as power mobile power supply.However, the reserves of lithium are limited and skewness
It is even, limit the development of extensive energy storage.
Sodium-ion battery has the advantage such as aboundresources, cheap, be the most potential substitute of lithium ion battery it
One, it is that extensive energy storage system very suitably selects.Positive electrode is the pass for determining sodium-ion battery chemical property
One of key factor, therefore it is significant to develop further development of the high performance positive electrode for sodium-ion battery.
Fluorophosphoric acid vanadyl sodium has aboundresources, theoretical capacity high（~130 mA h/g）And discharge potential is high（~3.8 V）
It is a kind of potential sodium-ion battery positive material of tool etc. advantage.However, itself existing low ionic conductance（1.8
×10-7 s/cm）Poor circulation is result in, capacity is low, limits its practical application.
In recent years, people are mainly modified using nanosizing, carbon coating and doping techniques to the material, but in multiplying power
Still have much room for improvement in terms of performance and cycle life.The contact area for improving graphene and nano material is to improve electron conduction
With the most important thing of ionic conductance, and the previous technical barrier urgently to be resolved hurrily of mesh.
The content of the invention
In order to overcome the disadvantages mentioned above of prior art, it is an object of the invention to provide a kind of three-dimensional grapheme network skeleton branch
Compound micron ball of fluorophosphoric acid vanadyl sodium of support and preparation method thereof, its technique is simple, yield is high and production cost is low；Prepare
The electronic conductivity of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support is high, as sodium-ion battery just
During the material of pole, excellent chemical property is obtained.
The technical solution adopted for the present invention to solve the technical problems is：A kind of fluorine of three-dimensional grapheme network skeleton support
The preparation method of the compound micron ball of vanadyl phosphate sodium, wherein：Comprise the following steps：
1）0.9358g ammonium metavanadates are dissolved in 100mL deionized waters, water-bath 10min in 70 DEG C of water-bath is placed in, makes its complete
Fully dissolved, after taking-up in the state of lasting stirring, it is down to room temperature；
2）In step 1）0.5039g sodium fluorides are slowly added in resulting solution, are stirred well to dissolving at room temperature；
3）In step 2）0.9202g ammonium dihydrogen phosphates are slowly added in resulting solution, are stirred well to dissolving at room temperature；
4）Under continuous stirring, by 80mL graphene oxide dispersions, it is added dropwise to step 3）In resulting solution；
5）By step 4）Resulting solution is transferred in spray-drying installation, is refined by drop, moisture is evaporated and reclaimed with whirlwind
Journey obtains spherical precursor powder sample；
6）By step 5）Obtained precursor powder sample, it is placed in tube furnace and obtains three-dimensional grapheme network bone by high-temperature calcination
The compound micron ball of fluorophosphoric acid vanadyl sodium of frame support.
As a further improvement on the present invention：The step 1）2）3）Described in ammonium metavanadate, sodium fluoride and di(2-ethylhexyl)phosphate
Hydrogen ammonium mol ratio is 2：3：2.
As a further improvement on the present invention：The specification of described graphene oxide dispersion is：2mg/mL, lamella size
＞ 500nm, addition are the 10% of generation product quality.
As a further improvement on the present invention：The step 4）The pH value of resulting solution is 6.55 ~ 7.
As a further improvement on the present invention：In the step 5）In the preparation process of presoma, step 4）Resulting
Solution is in the state being stirred continuously.
As a further improvement on the present invention：The step 5）Spray-drying installation in ambient parameter include：Dry
Cavity temperature is 200 DEG C ~ 220 DEG C, intake（Aspirator）For 85% ~ 95%, sample rate (Pump) is 5%, impact sample
Number（Nozzle）For 3 times/min.
As a further improvement on the present invention：The step 6）Used high-temperature calcination system is:Programming rate is 2 ~ 5
DEG C/min, calcining heat is 500 DEG C, and calcination time is 5 hours；Calcination atmosphere is argon gas, nitrogen or vacuum.
The compound micron ball of fluorophosphoric acid vanadyl sodium supported according to a kind of three-dimensional grapheme network skeleton obtained by above-mentioned preparation method,
About 1 ~ 5 micron of the micron bulb diameter, wherein about 200 ~ 500 nanometers embedded of nano particle.
A kind of compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support is as sodium-ion battery positive pole
The application of active material.
The present invention has developed a kind of spray drying-carbonizatin method prepared suitable for magnanimity, first using the high-flexibility of graphene
Secondary design has constructed the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support, and wherein fluorophosphoric acid vanadyl sodium is received
Rice grain is uniformly embedded between the graphene network to fold.In the three-dimensional grapheme conductive network available buffer charge and discharge process
Volumetric expansion, improve the cyclical stability and high rate capability of material.
The beneficial effects of the invention are as follows：Based on from simulated acid rain, using spray drying technology, it is ingenious construct high-flexibility with
The three-dimensional grapheme network skeleton of high conductivity.By high-temperature calcination, the fluorophosphoric acid that three-dimensional grapheme network skeleton supports is obtained
The compound micron ball of vanadyl sodium.When the present invention is used as sodium-ion battery positive electrode active materials, the compound micron ball shows excellent
Cyclical stability and high-rate characteristics, it is the potential application material of high power, long-life sodium-ion battery.As sodium-ion battery
Positive electrode active materials, under 65mA/g high current density, capacity is up to 120.4mAh/g first, and capacity is still after circulation 200 times
Up to 107.9mAh/g, capability retention 89.7%；Under 3900mA/g high current density, capacity is reachable first
87.2mAh/g, capacity is still up to 72.7mAh/g, capability retention 83.4% after circulating 2000 times.Present invention process is simple, institute
Spray drying-carbonizatin method of use has universality, and equipment requirement is low, and obtained material purity is high, good dispersion, is easy to advise
Modelling magnanimity produces, and is very beneficial for market-oriented popularization.
Brief description of the drawings
Fig. 1 is the compound micron ball of fluorophosphoric acid vanadyl sodium of the three-dimensional grapheme network skeleton support of the embodiment of the present invention 1
XRD；
Fig. 2 is the scanning of the compound micron ball of fluorophosphoric acid vanadyl sodium of the three-dimensional grapheme network skeleton support of the embodiment of the present invention 1
Electron microscope；
Fig. 3 is the transmission of the compound micron ball of fluorophosphoric acid vanadyl sodium of the three-dimensional grapheme network skeleton support of the embodiment of the present invention 1
Electron microscope；
Fig. 4 is the compound micron ball of fluorophosphoric acid vanadyl sodium of the three-dimensional grapheme network skeleton support of the embodiment of the present invention 1 in 65mA/
Cycle performance of battery curve map under g current densities；
Fig. 5 is that the compound micron ball of fluorophosphoric acid vanadyl sodium of the three-dimensional grapheme network skeleton support of the embodiment of the present invention 1 exists
Cycle performance of battery curve map under 3900mA/g current densities.
Embodiment
In conjunction with brief description of the drawings, the present invention is further described with embodiment：
Embodiment 1：
A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support, including following step
Suddenly：
1）0.9358g ammonium metavanadates are dissolved in 100mL deionized waters, water-bath 10min in 70 DEG C of water-bath is placed in, makes its complete
Fully dissolved, after taking-up in the state of lasting stirring, it is down to room temperature；
2）In step 1）0.5039g sodium fluorides are slowly added in resulting solution, are stirred well to dissolving at room temperature；
3）In step 2）0.9202g ammonium dihydrogen phosphates are slowly added in resulting solution, are stirred well to dissolving at room temperature；
4）Under continuous stirring, by 80mL graphene oxide dispersions, it is added dropwise to step 3）In resulting solution；Described oxygen
The specification of graphite alkene dispersion liquid is：2mg/mL, lamella size ＞ 500nm, addition are the 10% of generation product quality.
5）By step 4）Resulting solution is transferred in spray-drying installation, is refined by drop, moisture is evaporated and returned with whirlwind
The processes such as receipts obtain spherical precursor powder sample；Spray drying panel parameter is arranged to：It is 220 DEG C to dry cavity temperature, air intake
Amount（Aspirator）For 90%, sample rate (Pump) is 5%, impacts sample number（Nozzle）For 3 times/min.
6）By step 5）Obtained precursor powder sample, is placed in tube furnace and obtains three-dimensional grapheme net by high-temperature calcination
The compound micron ball of fluorophosphoric acid vanadyl sodium of network skeletal support；Programming rate is 2 DEG C/min, and calcining heat is 500 DEG C, during calcining
Between be 5 hours；Calcination atmosphere is argon gas.
By taking the compound micron ball of fluorophosphoric acid vanadyl sodium of this example product three-dimensional grapheme network skeleton support as an example, its structure
Determined by x-ray diffractometer.As shown in figure 1, X-ray diffracting spectrum (XRD) shows, three-dimensional grapheme network skeleton support
The compound micron ball of fluorophosphoric acid vanadyl sodium be Na3V2O2(PO4)2F phases（PDF card numbers are 97-041-1950）, space group I4/
Mmm, without other dephasigns.As shown in Fig. 2 ESEM (SEM) test shows that the compound micron spherical structure is led by three-dimensional grapheme
Electric network and fluorophosphoric acid vanadyl sodium nano particle are formed, wherein a diameter of 1 ~ 5 micron of the compound micron ball, the chi of nano particle
Very little is 200 ~ 500 nanometers.As shown in figure 3, transmission electron microscope (TEM) and high-resolution-ration transmission electric-lens (HRTEM) test show that this is compound
Micron ball has good crystal structure, and nano particle is evenly embedded into three-dimensional grapheme network.
The compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support prepared by the present invention is as sodium ion
Battery anode active material, remaining step of the preparation method of sodium-ion battery are identical with common preparation method.The system of positive plate
Preparation Method is as follows, using the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support as active material, second
Acetylene black is as conductive agent, and for Kynoar as binding agent, active material, acetylene black, the mass ratio of Kynoar are 60:
30:10；Grind 30min after active material and acetylene black are weighed in proportion, add the Kynoar of corresponding proportion with it is a small amount of
1-METHYLPYRROLIDONE, ultrasonic 1h are equably coated on aluminium foil to well mixed, then by it；After to be dried, inscribed with perforating press
A diameter of 1 centimetre of positive plate, it is standby after 12 hours of oven drying for being placed in 70 DEG C.With 1M NaClO4It is dissolved in carbonic acid
Propylene（PC）With 5% fluorinated ethylene carbonate（FEC）As electrolyte, for metallic sodium as negative pole, glass fibre membrane is barrier film,
The type stainless steels of CR 2016 are that battery case is assembled into button sodium-ion battery.
Using this example prepare three-dimensional grapheme network skeleton support the compound micron ball of fluorophosphoric acid vanadyl sodium as sodium from
Exemplified by sub- battery anode active material, as shown in figure 4, under 65mA/g current density, capacity is up to 120.4mAh/g first,
Capacity is still up to 107.9mAh/g, capability retention 89.7% after circulating 200 times；As shown in figure 5, in 3900mA/g height electricity
Under current density, capacity is up to 87.2mAh/g first, and capacity is still up to 72.7mAh/g, capability retention after circulating 2000 times
83.4%.The result shows that the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support has excellent circulation
Stability and high capacity characteristics, are high powers, high power capacity, the potential application material of long-life sodium-ion battery.
Embodiment 2：
A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support, including following step
Suddenly：
1）0.9358g ammonium metavanadates are dissolved in 100mL deionized waters, water-bath 10min in 70 DEG C of water-bath is placed in, makes its complete
Fully dissolved, after taking-up in the state of lasting stirring, it is down to room temperature；
2）In step 1）0.5039g sodium fluorides are slowly added in resulting solution, are stirred well to dissolving at room temperature；
3）In step 2）0.9202g ammonium dihydrogen phosphates are slowly added in resulting solution, are stirred well to dissolving at room temperature；
4）Under continuous stirring, by 80mL graphene oxide dispersions, it is added dropwise to step 3）In resulting solution；Described oxygen
The specification of graphite alkene dispersion liquid is：2mg/mL, lamella size ＞ 500nm, addition are the 10% of generation product quality.
5）By step 4）Resulting solution is transferred in spray-drying installation, is refined by drop, moisture is evaporated and returned with whirlwind
The processes such as receipts obtain spherical precursor powder sample；Spray drying panel parameter is arranged to：It is 200 DEG C to dry cavity temperature, air intake
Amount（Aspirator）For 95%, sample rate (Pump) is 5%, impacts sample number（Nozzle）For 3 times/min.
6）By step 5）Obtained precursor powder sample, is placed in tube furnace and obtains three-dimensional grapheme net by high-temperature calcination
The compound micron ball of fluorophosphoric acid vanadyl sodium of network skeletal support；Programming rate is 2 DEG C/min, and calcining heat is 500 DEG C, during calcining
Between be 5 hours；Calcination atmosphere is argon gas.
Using this example prepare three-dimensional grapheme network skeleton support the compound micron ball of fluorophosphoric acid vanadyl sodium as sodium from
Exemplified by sub- battery anode active material, under 3900mA/g high current density, capacity is up to 87.5mAh/g, circulation first
Capacity is still up to 71.4mAh/g, capability retention 81.6% after 2000 times.；
Embodiment 3：
A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support, including following step
Suddenly：
1）0.9358g ammonium metavanadates are dissolved in 100mL deionized waters, water-bath 10min in 70 DEG C of water-bath is placed in, makes its complete
Fully dissolved, after taking-up in the state of lasting stirring, it is down to room temperature；
2）In step 1）0.5039g sodium fluorides are slowly added in resulting solution, are stirred well to dissolving at room temperature；
3）In step 2）0.9202g ammonium dihydrogen phosphates are slowly added in resulting solution, are stirred well to dissolving at room temperature；
4）Under continuous stirring, by 80mL graphene oxide dispersions, it is added dropwise to step 3）In resulting solution；Described oxygen
The specification of graphite alkene dispersion liquid is：2mg/mL, lamella size ＞ 500nm, addition are the 10% of generation product quality.
5）By step 4）Resulting solution is transferred in spray-drying installation, is refined by drop, moisture is evaporated and returned with whirlwind
The processes such as receipts obtain spherical precursor powder sample；Spray drying panel parameter is arranged to：It is 210 DEG C to dry cavity temperature, air intake
Amount（Aspirator）For 85%, sample rate (Pump) is 5%, impacts sample number（Nozzle）For 3 times/min.
6）By step 5）Obtained precursor powder sample, is placed in tube furnace and obtains three-dimensional grapheme net by high-temperature calcination
The compound micron ball of fluorophosphoric acid vanadyl sodium of network skeletal support；Programming rate is 3 DEG C/min, and calcining heat is 500 DEG C, during calcining
Between be 5 hours；Calcination atmosphere is nitrogen.
Using this example prepare three-dimensional grapheme network skeleton support the compound micron ball of fluorophosphoric acid vanadyl sodium as sodium from
Exemplified by sub- battery anode active material, under 3900mA/g high current density, capacity is up to 88.6mAh/g, circulation first
Capacity is still up to 73.9mAh/g, capability retention 82.5% after 2000 times.
Embodiment 4：
A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support, including following step
Suddenly：
1）0.9358g ammonium metavanadates are dissolved in 100mL deionized waters, water-bath 10min in 70 DEG C of water-bath is placed in, makes its complete
Fully dissolved, after taking-up in the state of lasting stirring, it is down to room temperature；
2）In step 1）0.5039g sodium fluorides are slowly added in resulting solution, are stirred well to dissolving at room temperature；
3）In step 2）0.9202g ammonium dihydrogen phosphates are slowly added in resulting solution, are stirred well to dissolving at room temperature；
4）Under continuous stirring, by 80mL graphene oxide dispersions, it is added dropwise to step 3）In resulting solution；Described oxygen
The specification of graphite alkene dispersion liquid is：2mg/mL, lamella size ＞ 500nm, addition are the 10% of generation product quality.
5）By step 4）Resulting solution is transferred in spray-drying installation, is refined by drop, moisture is evaporated and returned with whirlwind
The processes such as receipts obtain spherical precursor powder sample；Spray drying panel parameter is arranged to：It is 220 DEG C to dry cavity temperature, air intake
Amount（Aspirator）For 95%, sample rate (Pump) is 5%, impacts sample number（Nozzle）For 3 times/min.
6）By step 5）Obtained precursor powder sample, is placed in tube furnace and obtains three-dimensional grapheme net by high-temperature calcination
The compound micron ball of fluorophosphoric acid vanadyl sodium of network skeletal support；Programming rate is 5 DEG C/min, and calcining heat is 500 DEG C, during calcining
Between be 5 hours；Calcination atmosphere is vacuum.
Using this example prepare three-dimensional grapheme network skeleton support the compound micron ball of fluorophosphoric acid vanadyl sodium as sodium from
Exemplified by sub- battery anode active material, under 3900mA/g high current density, capacity is up to 86.3 mAh/g, circulation first
Capacity is still up to 70.2 mAh/g, capability retention 81.3% after 2000 times.
Embodiment 5：
A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support, including following step
Suddenly：
1）0.9358g ammonium metavanadates are dissolved in 100mL deionized waters, water-bath 10min in 70 DEG C of water-bath is placed in, makes its complete
Fully dissolved, after taking-up in the state of lasting stirring, it is down to room temperature；
2）In step 1）0.5039g sodium fluorides are slowly added in resulting solution, are stirred well to dissolving at room temperature；
3）In step 2）0.9202g ammonium dihydrogen phosphates are slowly added in resulting solution, are stirred well to dissolving at room temperature；
4）Under continuous stirring, by 80mL graphene oxide dispersions, it is added dropwise to step 3）In resulting solution；Described oxygen
The specification of graphite alkene dispersion liquid is：2mg/mL, lamella size ＞ 500nm, addition are the 10% of generation product quality.
5）By step 4）Resulting solution is transferred in spray-drying installation, is refined by drop, moisture is evaporated and returned with whirlwind
The processes such as receipts obtain spherical precursor powder sample；Spray drying panel parameter is arranged to：It is 220 DEG C to dry cavity temperature, air intake
Amount（Aspirator）For 85%, sample rate (Pump) is 5%, impacts sample number（Nozzle）For 3 times/min.
6）By step 5）Obtained precursor powder sample, is placed in tube furnace and obtains three-dimensional grapheme net by high-temperature calcination
The compound micron ball of fluorophosphoric acid vanadyl sodium of network skeletal support；Programming rate is 2 DEG C/min, and calcining heat is 500 DEG C, during calcining
Between be 5 hours；Calcination atmosphere is vacuum.
Using this example prepare three-dimensional grapheme network skeleton support the compound micron ball of fluorophosphoric acid vanadyl sodium as sodium from
Exemplified by sub- battery anode active material, under 3900mA/g high current density, capacity is up to 89.4mAh/g, circulation first
Capacity is still up to 74.5mAh/g, capability retention 83.3% after 2000 times.
In summary, after one of ordinary skill in the art reads file of the present invention, technique according to the invention scheme and
Technical concept makes other various corresponding conversion schemes without creative mental labour, belongs to the model that the present invention is protected
Enclose.
Claims (9)
1. a kind of compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support, it is characterized in that：The micron ball
About 1 ~ 5 micron of diameter, wherein about 200 ~ 500 nanometers embedded of nano particle.
2. a kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support, it is characterized in that：
Comprise the following steps：
1）A certain amount of ammonium metavanadate is dissolved in 100mL deionized waters, water-bath 10min in 70 DEG C of water-bath is placed in, makes its complete
Fully dissolved, after taking-up in the state of lasting stirring, it is down to room temperature；
2）In step 1）A certain amount of sodium fluoride is slowly added in resulting solution, is stirred well to dissolving at room temperature；
3）In step 2）A certain amount of ammonium dihydrogen phosphate is slowly added in resulting solution, is stirred well to dissolving at room temperature；
4）Under continuous stirring, by 80mL graphene oxide dispersions, it is added dropwise to step 3）In resulting solution；
5）By step 4）Resulting solution is transferred in spray-drying installation, is refined by drop, moisture is evaporated and reclaimed with whirlwind
Journey obtains spherical precursor powder sample；
6）By step 5）Obtained precursor powder sample, it is placed in tube furnace and obtains three-dimensional grapheme network bone by high-temperature calcination
The compound micron ball of fluorophosphoric acid vanadyl sodium of frame support.
3. a kind of compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support according to claim 2
Preparation method, it is characterized in that：The step 1）2）3）Described in ammonium metavanadate, sodium fluoride and ammonium dihydrogen phosphate mol ratio be 2：
3：2, preferably ammonium metavanadate 0.9358g, sodium fluoride 0.5039g, ammonium dihydrogen phosphate 0.9202g.
4. a kind of compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support according to claim 2
Preparation method, it is characterized in that：The specification of described graphene oxide dispersion is：2mg/mL, lamella size ＞ 500nm, add
Measure to generate the 10% of product quality.
5. a kind of compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support according to claim 2
Preparation method, it is characterized in that：The step 4）The pH value of resulting solution is 6.55 ~ 7.
6. a kind of compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support according to claim 2
Preparation method, it is characterized in that：In the step 5）In the preparation process of presoma, step 4）Resulting solution is in continuous
The state of stirring.
7. a kind of compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support according to claim 2
Preparation method, it is characterized in that：The step 5）Spray-drying installation in ambient parameter include：It is 200 to dry cavity temperature
DEG C ~ 220 DEG C, intake（Aspirator）For 85% ~ 95%, sample rate (Pump) is 5%, impacts sample number（Nozzle）For 3
Secondary/min.
8. a kind of compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support according to claim 2
Preparation method, it is characterized in that：The step 6）Used high-temperature calcination system is:Programming rate is 2 ~ 5 DEG C/min, calcining
Temperature is 500 DEG C, and calcination time is 5 hours；Calcination atmosphere is argon gas, nitrogen or vacuum.
9. a kind of compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support according to claim 1,
It is characterized in that：Application as sodium-ion battery positive electrode active materials.
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| CN201710589937.0A CN107359340A (en) | 2017-07-19 | 2017-07-19 | 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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| CN201710589937.0A CN107359340A (en) | 2017-07-19 | 2017-07-19 | 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108899520A (en) * | 2018-07-05 | 2018-11-27 | 武汉理工大学 | Globe daisy shape Na3V2O2(PO4)2F-GO nanocomposite and its preparation method and application |
| CN109037630A (en) * | 2018-07-25 | 2018-12-18 | 三峡大学 | A kind of phosphorus doping carbon coating Na3V2(PO4)2O2F positive electrode and preparation method thereof |
| CN110247037A (en) * | 2019-06-11 | 2019-09-17 | 华中科技大学 | A kind of fluorophosphoric acid vanadium oxygen sodium/graphene complex and preparation method and purposes |
| CN111162252A (en) * | 2019-12-23 | 2020-05-15 | 浙江大学 | Preparation method, product and application of RGO modified fluoro-substituted sodium vanadyl phosphate composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104078676A (en) * | 2014-07-29 | 2014-10-01 | 齐鲁工业大学 | Preparation method of sodium vanadyl phosphate/graphene composite material |
| CN105244503A (en) * | 2015-11-13 | 2016-01-13 | 武汉大学 | Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material |
| CN105375008A (en) * | 2015-11-13 | 2016-03-02 | 武汉理工大学 | Laminated Na3V2(PO4)3@rGo nanocomposite and preparation method and application therefor |
| CN106299248A (en) * | 2016-08-24 | 2017-01-04 | 东北师范大学 | A kind of fluorophosphate quadrangular nano material and preparation method thereof |
-
2017
- 2017-07-19 CN CN201710589937.0A patent/CN107359340A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104078676A (en) * | 2014-07-29 | 2014-10-01 | 齐鲁工业大学 | Preparation method of sodium vanadyl phosphate/graphene composite material |
| CN105244503A (en) * | 2015-11-13 | 2016-01-13 | 武汉大学 | Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material |
| CN105375008A (en) * | 2015-11-13 | 2016-03-02 | 武汉理工大学 | Laminated Na3V2(PO4)3@rGo nanocomposite and preparation method and application therefor |
| CN106299248A (en) * | 2016-08-24 | 2017-01-04 | 东北师范大学 | A kind of fluorophosphate quadrangular nano material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MAOWEN XU等: "Na3V2O2(PO4)2F/graphene sandwich structure for high-performance cathode of a sodium-ion battery", 《PHYS. CHEM. CHEM. PHYS.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108899520A (en) * | 2018-07-05 | 2018-11-27 | 武汉理工大学 | Globe daisy shape Na3V2O2(PO4)2F-GO nanocomposite and its preparation method and application |
| CN108899520B (en) * | 2018-07-05 | 2021-07-27 | 武汉理工大学 | Globose Na3V2O2(PO4)2F-GO nano composite material and preparation method and application thereof |
| CN109037630A (en) * | 2018-07-25 | 2018-12-18 | 三峡大学 | A kind of phosphorus doping carbon coating Na3V2(PO4)2O2F positive electrode and preparation method thereof |
| CN109037630B (en) * | 2018-07-25 | 2019-04-30 | 三峡大学 | A kind of phosphorus doping carbon coating Na3V2(PO4)2O2F positive electrode and preparation method thereof |
| CN110247037A (en) * | 2019-06-11 | 2019-09-17 | 华中科技大学 | A kind of fluorophosphoric acid vanadium oxygen sodium/graphene complex and preparation method and purposes |
| CN110247037B (en) * | 2019-06-11 | 2021-01-01 | 华中科技大学 | Preparation method and application of sodium vanadium oxygen fluorophosphate/graphene compound |
| CN111162252A (en) * | 2019-12-23 | 2020-05-15 | 浙江大学 | Preparation method, product and application of RGO modified fluoro-substituted sodium vanadyl phosphate composite material |
| CN111162252B (en) * | 2019-12-23 | 2021-09-03 | 浙江大学 | Preparation method, product and application of RGO modified fluoro-substituted sodium vanadyl phosphate composite material |
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