CN108242540A - A kind of carbon coating vanadium phosphate sodium microballoon and preparation method thereof and the application as sodium-ion battery positive material - Google Patents
A kind of carbon coating vanadium phosphate sodium microballoon and preparation method thereof and the application as sodium-ion battery positive material Download PDFInfo
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- CN108242540A CN108242540A CN201810008803.XA CN201810008803A CN108242540A CN 108242540 A CN108242540 A CN 108242540A CN 201810008803 A CN201810008803 A CN 201810008803A CN 108242540 A CN108242540 A CN 108242540A
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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
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Application the invention discloses a kind of carbon coating vanadium phosphate sodium microballoon and preparation method thereof and as sodium-ion battery positive material.The vanadium phosphate sodium nanometer sheet assembling that carbon coating vanadium phosphate sodium microballoon is coated with conductive carbon layer by surface is formed；Preparation method is will to be slowly added to dissolved with the hydrogen peroxide solution of vanadic anhydride into the aqueous solution containing Organic Sodium Salt, phosphorus source and itrogenous organic substance, stir evenly, obtain mixed liquor；The mixed liquor, which is transferred in hydrothermal reaction kettle, carries out hydro-thermal reaction, obtains vanadium phosphate sodium hydrogel；The vanadium phosphate sodium hydrogel after drying, be placed in protective atmosphere calcine to get well-crystallized, stable appearance, size uniformity, electrochemical performance carbon coating vanadium phosphate sodium microballoon；It uses it for preparing sodium-ion battery, cyclical stability and the excellent sodium-ion battery of high rate performance can be obtained；And the preparation process of carbon coating vanadium phosphate sodium microballoon is simple, repeatability is high, has good application prospect.
Description
Technical field
The present invention relates to a kind of sodium-ion battery positive materials, and in particular to a kind of carbon coating vanadium phosphate sodium microballoon and its system
Preparation Method and the application as sodium-ion battery positive material；Belong to sodium-ion battery preparing technical field.
Background technology
The world today, fossil fuel are still our main electric power energy provisioning resources.However, with fossil fuel
It is widely used along with a large amount of greenhouse gas emission and problem of environmental pollution, causes global environment crisis.Therefore, the sun
The development and utilization of the regenerative resources such as energy, wind energy, tide energy, nuclear energy, biological energy source is extremely urgent.But because power grid is powered
It needs to stablize and continual supply of electric power, the supply climate of part regenerative resource, season and the influence of region are very tight
Weight, be connected to the grid also many technical barrier urgent need to resolve at present.In order to overcome this problem, based on rechargeable secondary cell
Extensive electrochemical energy storage technology with the advantages such as its cycle efficieny is high, energy supply is flexible, service life is long, maintenance cost is low and
By countries in the world, government is paid much attention to.
Current power grid energy storage technology is concentrated mainly on lithium ion battery, flow battery and high-temperature battery field.Wherein, lithium
The ion battery extensive use in hybrid-power battery and plug-in electric vehicle, and as potential next-generation extensive storage
It can technology.Since the Regional Distribution of the ever-increasing market demand and lithium resource is seriously uneven, the price rising all the way of lithium resource,
Gradually it is difficult to the requirement for meeting extensive, inexpensive stored energy application field.In recent years, since sodium and lithium have similar electrification
Learn deintercalation mechanism, and rich reserves of the sodium in the earth's crust, cheap, researchers have focused on room temperature sodium ion electricity
Chi Shang.But since the ionic radius of sodium oxidation-reduction potential bigger than lithium and higher causes the energy density of sodium-ion battery
It is difficult to meet application demand with power density.The crucial of restricting current sodium-ion battery practical application just can stablize deintercalation in shortage
The electrode material of sodium ion.The electrode material for seeking can to stablize deintercalation sodium ion is the pass of current sodium-ion battery technology development
Where key.
Typical sodium-ion battery positive material includes layered oxide, polyanionic compound, Prussian blue at present
And its derivative and organic compound etc..Polyanionic compound is considered as in numerous sodium ion battery electrode materials
Has one kind of potentiality.By taking phosphate as an example, it contains the special PO with strong covalent bond4Tetrahedron element, valence electron is with gathering
Anion relative separation.This special three-dimensional frame structure is very beneficial for the insertion and abjection of sodium ion.The phosphoric acid having
Salt electrode material has superior ionic conductivity and structural stability, and wherein vanadium base and iron-based NASICON structural materials is recognized
To be most promising sodium ion battery electrode material.In addition, the material of NASICON structures also represents one kind for all solid state
The solid electrolyte of the hybrid batteries such as ion battery, all solid state air cell.
Nevertheless, electron conduction is poor, ion diffusion rates are slow, high temperature sintering structure is difficult to control and remains Na3V2
(PO4)3、NaTi2(PO4)3、Li3V2(PO4)3And LiFePO4Wait the common difficulty of phosphate systems electrode material.
Invention content
For existing vanadium phosphate sodium material, there are electron conduction is poor, ion diffusion rates are slow, high temperature sintering structure is difficult
With technological deficiencies such as controls, of the invention first purpose be to provide a kind of well-crystallized, stable appearance, size uniformity,
The carbon coating vanadium phosphate sodium microballoon of electrochemical performance.
Second object of the present invention be to provide it is a kind of it is simple for process, raw material is inexpensive, is easy to amplify mass production
Preparation carbon coating vanadium phosphate sodium microballoon method.
Third object of the present invention is to be to provide a kind of carbon coating vanadium phosphate sodium microballoon as sodium-ion battery anode
The application of material, the sodium-ion battery prepared as positive electrode show high circulation stability and high rate capability.
In order to realize above-mentioned technical purpose, the present invention provides a kind of carbon coating vanadium phosphate sodium microballoons, are coated by surface
The vanadium phosphate sodium nanometer sheet assembling for having conductive carbon layer is formed.
The present invention carbon coating vanadium phosphate sodium microballoon in vanadium phosphate sodium crystal have two-dimensional nanostructure, can effectively be promoted from
Sub- diffusion rate, and sheet vanadium phosphate sodium is assembled into micro-sphere structure, is oozed with larger specific surface area and sufficient electrolyte
Transmission gap, while it is beneficial to be promoted the tap density of electrode material, and the conductive carbon layer that vanadium phosphate sodium grain surface is evenly coated,
The electron conduction of material is effectively promoted, while improves the stability of material.
Preferred scheme, it at 1 μm~20 μm centers is solid sphere structure that carbon coating vanadium phosphate sodium microballoon, which is grain size,.
The present invention also provides a kind of preparation method of carbon coating vanadium phosphate sodium microballoon, this method is will be dissolved with five oxidations two
The hydrogen peroxide solution of vanadium is slowly added into the aqueous solution containing Organic Sodium Salt, phosphorus source and itrogenous organic substance, is stirred evenly, and is mixed
Close liquid；The mixed liquor, which is transferred in hydrothermal reaction kettle, carries out hydro-thermal reaction, obtains vanadium phosphate sodium hydrogel；The vanadium phosphate sodium
Hydrogel after drying, be placed in protective atmosphere calcine to get.
Preferred scheme, the Organic Sodium Salt include odium stearate, enuatrol, sodium tartrate, sodium citrate, alginic acid
Sodium, lauryl sodium sulfate, neopelex, dodecyl sodium sulfate, sodium benzoate, benzene sulfonic acid sodium salt, ethylenediamine tetraacetic
Acetic acid disodium, dioctyl sodium sulfosuccinate, sodium carboxymethylcellulose, sodium lactate, sodium humate, maltonic acid sodium, hexichol
Amine sodium sulfonate, sodium xylene sulfonate, sodium pentanesulfonate, hexane sodium sulfonate, sodium heptanesulfonate, perfluorooctane sulfonate, natrii tauroglycocholas, sugar
At least one of smart sodium.
Preferred scheme, phosphorus source include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, phosphoric acid, biphosphate
At least one of sodium, disodium hydrogen phosphate, phosphorus pentoxide, microcosmic salt, vanadium phosphate, ortho phosphorous acid.
Preferred scheme, the itrogenous organic substance include urea, thiocarbamide, pyrroles, ethylenediamine, diethylenetriamine, citric acid
Ammonium, dicyanodiamine, polypyrrole, polyvinylpyrrolidone, diallyl dimethyl ammoniumchloride, ammonium chloride, gathers 2-methylimidazole
At least one of acrylonitrile.
Preferred scheme, the mass percent concentration of hydrogen peroxide is in the hydrogen peroxide solution dissolved with vanadic anhydride
1~30%, a concentration of 0.0025mol/L~0.1mol/L of vanadic anhydride.
The molar ratio of preferred scheme, Organic Sodium Salt and phosphorus source using the molar ratio of sodium ion and phosphate anion as 1~
1.1:1 metering.
The mass ratio of preferred scheme, Organic Sodium Salt and itrogenous organic substance is 1:0.1~0.5.
The molar ratio of preferred scheme, Organic Sodium Salt and vanadic anhydride using the molar ratio of sodium ion and vanadium ion as 3~
3.3:2 meterings.
Preferred scheme, the drying process temperature are -40 DEG C~100 DEG C, and pressure condition is -0.1MPa~0.1MPa.
It can effectively prevent the reunion of vanadium phosphate sodium hydrogel under preferred drying condition.
Preferred scheme, the temperature of the hydro-thermal reaction is 100 DEG C~250 DEG C, and the time is 2 hours~96 hours.
Preferred scheme, the calcination process are under protective atmosphere, with the heating rate liter of 1 DEG C/min~10 DEG C/min
6 hours~12 hours are kept the temperature to 600 DEG C~900 DEG C.
More preferably scheme, the protective atmosphere is nitrogen atmosphere, inert atmosphere, nitrogen/reducibility gas mixed atmosphere
Or inert gas/reducibility gas mixed atmosphere.Further preferred nitrogen/reducibility gas mixed atmosphere or inert gas/also
The percent by volume of reducibility gas is 3~15% in originality gas mixing atmosphere；The reducibility gas include hydrogen and/or
Carbon monoxide.
The present invention also provides a kind of applications of carbon coating vanadium phosphate sodium microballoon, should as sodium-ion battery positive material
With.
The present invention synthesizes vanadium phosphate sodium hydrogel precursor, drying, in protective atmosphere using hydro-thermal method first
Target product is obtained after calcining --- carbon coating vanadium phosphate sodium microballoon.The preparation method of specific cladding vanadium phosphate sodium microballoon, packet
Include following steps：
(1) it after vanadium pentoxide powder being dissolved in the hydrogen peroxide that mass concentration is 1%~30%, is stirred at room temperature
0.5 hour~24 hours, obtain transparent salmon solution A；
(2) sodium organic matter, phosphorus source, itrogenous organic substance will be contained to add in deionized water, at a temperature of 40 DEG C~120 DEG C, stirred
It is 1 hour~24 hours to mix the time, obtains turbid solution B；
(3) transparent salmon solution A is slowly added into turbid solution B, at a temperature of 40 DEG C~120 DEG C, during stirring
Between for 1 hour~24 hours, be sufficiently mixed it；
(4) mixed solution in step (3) is moved into hydrothermal reaction kettle, mixed solution total volume accounts for water heating kettle volume
50%~90%, at a temperature of 100 DEG C~250 DEG C, react 2 hours~96 hours, furnace cooling after reaction；
(5) by the vanadium phosphate sodium hydrogel precursor obtained after hydro-thermal reaction in step (4) at -40 DEG C~100 DEG C, pressure
Condition is dry under the conditions of being -0.1MPa~0.1MPa, obtains xerogel presoma.
(6) the xerogel presoma obtained in step (5) is calcined in protective atmosphere, furnace cooling, products therefrom is
For carbon coating vanadium phosphate sodium microsphere powder；Protective atmosphere for nitrogen and/or inert gas or nitrogen and/or inert gas with
The gaseous mixture of reducibility gas；Inert gas is argon gas；Reducibility gas is mixed for hydrogen, carbon monoxide or hydrogen and carbon monoxide
Gas is closed, wherein percent by volume of the reducibility gas in gaseous mixture is 3~15%.
Compared with the prior art, technical scheme of the present invention has the following advantages that：
1. the carbon coating vanadium phosphate sodium microballoon of the present invention has special construction；It is by two-dimensional nano sheet vanadium phosphate sodium crystal
Micro-sphere structure is assembled into, two-dimensional nano sheet vanadium phosphate sodium crystal can effectively promote ion diffusion rates, and with abundant piece
Between gap, make it have larger specific surface area and sufficient electrolyte permeability, while be beneficial to be promoted the jolt ramming of electrode material
Density, and the conductive carbon layer that vanadium phosphate sodium grain surface is evenly coated, effectively promote the electron conduction of material, while improve material
The stability of material.
2. the carbon coating vanadium phosphate sodium microballoon preparation process of the present invention is lived using Organic Sodium Salt as sodium source, carbon source and surface
Property agent, improves the utilization ratio of raw material, reduces manufacturing cost.It can also be by adding in itrogenous organic substance leading in cladding
The defects of realizing N doping in electrical carbon, increasing carbon coated site, promote sodium ion diffusion rate.
It is micro- that 3. the carbon coating vanadium phosphate sodium microballoon preparation process of the present invention by hydro-thermal method prepares water-setting glue vanadium phosphate sodium
Ball presoma, then by controlling dry technology, the reunion scene of material is effectively prevent, and easily Organic Sodium Salt is what template was prepared
Vanadium phosphate sodium microballoon is assembled by a nano level constituent element, has larger specific surface area and sufficient electrolyte permeability
Gap, while it is beneficial to be promoted the tap density of electrode material.
4. the carbon coating vanadium phosphate sodium microballoon of the present invention is as sodium-ion battery positive material application, the sodium ion electricity of preparation
Pond has excellent cyclical stability and high rate performance, and 115mA h g can be discharged under the current density of 1C-1Electric discharge specific volume
Amount, specific discharge capacity still can keep 96% after charge and discharge 500 times, be the ideal electrode material of sodium-ion battery.
5. the method for preparing vanadium phosphate sodium microballoon of the present invention is simple for process, repeatability is high, before having application well
Scape.
Description of the drawings
【Fig. 1】XRD spectrum for carbon coating vanadium phosphate sodium microsphere powder prepared by embodiment 1；
【Fig. 2】XRD spectrum for carbon coating vanadium phosphate sodium microsphere powder prepared by embodiment 2；
【Fig. 3】XRD spectrum for carbon coating vanadium phosphate sodium microsphere powder prepared by embodiment 3；
【Fig. 4】XRD spectrum for carbon coating vanadium phosphate sodium microsphere powder prepared by embodiment 4；
【Fig. 5】Raman collection of illustrative plates for carbon coating vanadium phosphate sodium microsphere powder prepared by embodiment 4；
【Fig. 6】SEM spectrum for carbon coating vanadium phosphate sodium micro-sphere material prepared by embodiment 1；
【Fig. 7】SEM spectrum for carbon coating vanadium phosphate sodium micro-sphere material prepared by embodiment 2；
【Fig. 8】SEM spectrum for carbon coating vanadium phosphate sodium micro-sphere material prepared by embodiment 3；
【Fig. 9】SEM spectrum for carbon coating vanadium phosphate sodium micro-sphere material prepared by embodiment 4；
【Figure 10】SEM spectrum for carbon coating vanadium phosphate sodium micro-sphere material prepared by embodiment 5；
【Figure 11】SEM spectrum for carbon coating vanadium phosphate sodium micro-sphere material prepared by embodiment 6；
【Figure 12】SEM spectrum for carbon coating vanadium phosphate sodium micro-sphere material prepared by embodiment 7；
【Figure 13】SEM spectrum for carbon coating vanadium phosphate sodium micro-sphere material prepared by embodiment 8；
【Figure 14】The sodium ion half-cell that carbon coating vanadium phosphate sodium micro-sphere material for the preparation of embodiment 4 is assembled into is 1C's
Under current density, the cycle performance figure in the voltage window of 2.5V~4V, wherein 1C=117.6mA g-1；
【Figure 15】The sodium ion half-cell that carbon coating vanadium phosphate sodium micro-sphere material for the preparation of embodiment 8 is assembled into is 1C's
Under current density, the cycle performance figure in the voltage window of 2.5V~4V, wherein 1C=117.6mA g-1。
Specific embodiment
It is intended to further illustrate the content of present invention with reference to embodiments, the claim that is not intended to limit the present invention protection model
It encloses.
Embodiment 1
0.1102g vanadium pentoxide powders are poured into 18mL deionized waters, then add in the dioxygen of 2mL a concentration of 30%
Water stirs 1 hour, obtains transparent salmon solution A at room temperature.By 0.5872g enuatrols, 0.2091g ammonium dihydrogen phosphates,
0.2796g urea is added to 20mL deionized waters, is stirred 1 hour at a temperature of 80 DEG C, obtains turbid solution B.It will be orange red
Clear solution A is slowly added into turbid solution B, was stirred for 10 times at a temperature of 80 DEG C, is sufficiently mixed it.It will mix molten
Liquid pours into the polytetrafluoroethylliner liner of 50mL, is put into hydrothermal reaction kettle, and hydro-thermal reaction 12 hours, obtain under conditions of 200 DEG C
To vanadium phosphate sodium hydrogel precursor.By vanadium phosphate sodium hydrogel precursor in -30 DEG C of temperature and the pressure condition of -0.1MPa
Lower freeze-drying, obtains xerogel presoma.Vanadium phosphate sodium xerogel presoma is gone to and is connected with H2/ Ar (Ar and H2Volume ratio is
95:5) in the quartz tube furnace of mixed gas, 800 DEG C of calcining at constant temperature 8h are risen to 2 DEG C/min heating rates, natural cooling obtains
Carbon coating vanadium phosphate sodium microsphere powder material.Gained sample is analyzed using Rigaku D/max-2500 type X-ray diffraction analysis instrument
The crystal structure of product, acquired results are as shown in Figure 1.Use 230 scanning electron microscopic observation samples of FEI Co. of U.S. Nova NanoSEM
The pattern of product finds that sample is the ellipsoid being assembled by nanometer sheet, as shown in Figure 6.
Embodiment 2
0.1102g vanadium pentoxide powders are poured into 18mL deionized waters, then add in the dioxygen of 2mL a concentration of 30%
Water stirs 1 hour, obtains transparent salmon solution A at room temperature.By 0.5872g enuatrols, 0.2091g ammonium dihydrogen phosphates,
0.2796g urea is added to 20mL deionized waters, is stirred 1 hour at a temperature of 80 DEG C, obtains turbid solution B.It will be orange red
Clear solution A is slowly added into turbid solution B, was stirred for 10 times at a temperature of 80 DEG C, is sufficiently mixed it.It will mix molten
Liquid pours into the polytetrafluoroethylliner liner of 50mL, is put into hydrothermal reaction kettle, and hydro-thermal reaction 24 hours, obtain under conditions of 200 DEG C
To vanadium phosphate sodium hydrogel precursor.By vanadium phosphate sodium hydrogel precursor in -30 DEG C of temperature and the pressure condition of -0.1MPa
Lower freeze-drying, obtains xerogel presoma.Vanadium phosphate sodium xerogel presoma is gone to and is connected with H2/ Ar (Ar and H2Volume ratio is
95:5) in the quartz tube furnace of mixed gas, 800 DEG C of calcining at constant temperature 8h are risen to 2 DEG C/min heating rates, natural cooling obtains
Carbon coating vanadium phosphate sodium microsphere powder material.Gained sample is analyzed using Rigaku D/max-2500 type X-ray diffraction analysis instrument
The crystal structure of product, acquired results are as shown in Figure 2.Use 230 scanning electron microscopic observation samples of FEI Co. of U.S. Nova NanoSEM
The pattern of product finds that sample is the microballoon being assembled by nanometer sheet, as shown in Figure 7.
Embodiment 3
0.1102g vanadium pentoxide powders are poured into 18mL deionized waters, then add in the dioxygen of 2mL a concentration of 30%
Water stirs 1 hour, obtains transparent salmon solution A at room temperature.By 0.5872g enuatrols, 0.2091g ammonium dihydrogen phosphates,
0.2796g urea is added to 20mL deionized waters, is stirred 1 hour at a temperature of 80 DEG C, obtains turbid solution B.It will be orange red
Clear solution A is slowly added into turbid solution B, was stirred for 10 times at a temperature of 80 DEG C, is sufficiently mixed it.It will mix molten
Liquid pours into the polytetrafluoroethylliner liner of 50mL, is put into hydrothermal reaction kettle, and hydro-thermal reaction 36 hours, obtain under conditions of 200 DEG C
To vanadium phosphate sodium hydrogel precursor.By vanadium phosphate sodium hydrogel precursor in -30 DEG C of temperature and the pressure condition of -0.1MPa
Lower freeze-drying, obtains xerogel presoma.Vanadium phosphate sodium xerogel presoma is gone to and is connected with H2/ Ar (Ar and H2Volume ratio is
95:5) in the quartz tube furnace of mixed gas, 800 DEG C of calcining at constant temperature 8h are risen to 2 DEG C/min heating rates, natural cooling obtains
Carbon coating vanadium phosphate sodium microsphere powder material.Gained sample is analyzed using Rigaku D/max-2500 type X-ray diffraction analysis instrument
The crystal structure of product, acquired results are as shown in Figure 3.Use 230 scanning electron microscopic observation samples of FEI Co. of U.S. Nova NanoSEM
The pattern of product finds that sample is the microballoon being assembled by nanometer sheet, as shown in Figure 8.
Embodiment 4
0.1102g vanadium pentoxide powders are poured into 18mL deionized waters, then add in the dioxygen of 2mL a concentration of 30%
Water stirs 1 hour, obtains transparent salmon solution A at room temperature.By 0.5872g enuatrols, 0.2091g ammonium dihydrogen phosphates,
0.2796g urea is added to 20mL deionized waters, is stirred 1 hour at a temperature of 80 DEG C, obtains turbid solution B.It will be orange red
Clear solution A is slowly added into turbid solution B, was stirred for 10 times at a temperature of 80 DEG C, is sufficiently mixed it.It will mix molten
Liquid pours into the polytetrafluoroethylliner liner of 50mL, is put into hydrothermal reaction kettle, and hydro-thermal reaction 48 hours, obtain under conditions of 200 DEG C
To vanadium phosphate sodium hydrogel precursor.By vanadium phosphate sodium hydrogel precursor in -30 DEG C of temperature and the pressure condition of -0.1MPa
Lower freeze-drying, obtains xerogel presoma.Vanadium phosphate sodium xerogel presoma is gone to and is connected with H2/ Ar (Ar and H2Volume ratio is
95:5) in the quartz tube furnace of mixed gas, 800 DEG C of calcining at constant temperature 8h are risen to 2 DEG C/min heating rates, natural cooling obtains
Carbon coating vanadium phosphate sodium microsphere powder material.Gained sample is analyzed using Rigaku D/max-2500 type X-ray diffraction analysis instrument
The crystal structure of product, acquired results are as shown in Figure 4.Using the packet in Raman spectrometer (LabRAM HR800) analysed for powder sample
The existence form for covering carbon is the graphited pyrolytic carbon in part, and acquired results are as shown in Figure 5.Use FEI Co. of U.S. Nova
The pattern of 230 scanning electron microscopic observation samples of NanoSEM finds that sample is the microballoon being assembled by nanometer sheet, as shown in Figure 9.It follows
Ring performance test voltage range is 2.5V~4V, current density 1C, its specific capacity is still up to 110.4mA h after recycling 500 times
g-1.Its cycle performance result is as shown in figure 14.
Embodiment 5
0.0367g vanadium pentoxide powders are poured into 18mL deionized waters, then add in the dioxygen of 2mL a concentration of 30%
Water stirs 1 hour, obtains transparent salmon solution A at room temperature.0.1957g enuatrols and 0.0697g ammonium dihydrogen phosphates are added in
To 20mL deionized waters, stirred 1 hour at a temperature of 80 DEG C, obtain turbid solution B.Transparent salmon solution A is slowly added
Enter into turbid solution B, stirred for 10 times at a temperature of 80 DEG C, be sufficiently mixed it.Mixed solution is poured into the poly- of 50mL
Tetrafluoroethene liner, is put into hydrothermal reaction kettle, and hydro-thermal reaction 48 hours under conditions of 200 DEG C obtain vanadium phosphate sodium water-setting
Glue presoma.Vanadium phosphate sodium hydrogel precursor at -30 DEG C of temperature and the pressure condition of -0.1MPa is freeze-dried, is obtained
To xerogel presoma.Vanadium phosphate sodium xerogel presoma is gone to and is connected with H2/ Ar (Ar and H2Volume ratio is 95:5) mixed gas
Quartz tube furnace in, 800 DEG C of calcining at constant temperature 8h are risen to 5 DEG C/min heating rates, natural cooling obtains carbon coating vanadium phosphate
Sodium microsphere powder material.Using the pattern of FEI Co. of U.S. Nova NanoSEM230 scanning electron microscopic observation samples, sample is found
It is the microballoon being assembled by nanometer sheet, as shown in Figure 10.
Embodiment 6
0.0735g vanadium pentoxide powders are poured into 18mL deionized waters, then add in the dioxygen of 2mL a concentration of 30%
Water stirs 1 hour, obtains transparent salmon solution A at room temperature.0.3915g enuatrols and 0.1394g ammonium dihydrogen phosphates are added in
To 20mL deionized waters, stirred 1 hour at a temperature of 80 DEG C, obtain turbid solution B.Transparent salmon solution A is slowly added
Enter into turbid solution B, stirred for 10 times at a temperature of 80 DEG C, be sufficiently mixed it.Mixed solution is poured into the poly- of 50mL
Tetrafluoroethene liner, is put into hydrothermal reaction kettle, and hydro-thermal reaction 48 hours under conditions of 200 DEG C obtain vanadium phosphate sodium water-setting
Glue presoma.Vanadium phosphate sodium hydrogel precursor at -30 DEG C of temperature and the pressure condition of -0.1MPa is freeze-dried, is obtained
To xerogel presoma.Vanadium phosphate sodium xerogel presoma is gone to and is connected with H2/ Ar (Ar and H2Volume ratio is 95:5) mixed gas
Quartz tube furnace in, 800 DEG C of calcining at constant temperature 8h are risen to 5 DEG C/min heating rates, natural cooling obtains carbon coating vanadium phosphate
Sodium microsphere powder material.Using the pattern of FEI Co. of U.S. Nova NanoSEM230 scanning electron microscopic observation samples, sample is found
It is the microballoon being assembled by nanometer sheet, as shown in figure 11.
Embodiment 7
0.1469g vanadium pentoxide powders are poured into 18mL deionized waters, then add in the dioxygen of 2mL a concentration of 30%
Water stirs 1 hour, obtains transparent salmon solution A at room temperature.0.7829g enuatrols and 0.2788g ammonium dihydrogen phosphates are added in
To 20mL deionized waters, stirred 1 hour at a temperature of 80 DEG C, obtain turbid solution B.Transparent salmon solution A is slowly added
Enter into turbid solution B, stirred for 10 times at a temperature of 80 DEG C, be sufficiently mixed it.Mixed solution is poured into the poly- of 50mL
Tetrafluoroethene liner, is put into hydrothermal reaction kettle, and hydro-thermal reaction 48 hours under conditions of 200 DEG C obtain vanadium phosphate sodium water-setting
Glue presoma.Vanadium phosphate sodium hydrogel precursor at -30 DEG C of temperature and the pressure condition of -0.1MPa is freeze-dried, is obtained
To xerogel presoma.Vanadium phosphate sodium xerogel presoma is gone to and is connected with H2/ Ar (Ar and H2Volume ratio is 95:5) mixed gas
Quartz tube furnace in, 800 DEG C of calcining at constant temperature 8h are risen to 5 DEG C/min heating rates, natural cooling obtains carbon coating vanadium phosphate
Sodium microsphere powder material.Using the pattern of FEI Co. of U.S. Nova NanoSEM230 scanning electron microscopic observation samples, sample is found
It is the microballoon being assembled by nanometer sheet, as shown in figure 12.
Embodiment 8
0.1837g vanadium pentoxide powders are poured into 18mL deionized waters, then add in the dioxygen of 2mL a concentration of 30%
Water stirs 1 hour, obtains transparent salmon solution A at room temperature.0.9787g enuatrols and 0.3485g ammonium dihydrogen phosphates are added in
To 20mL deionized waters, stirred 1 hour at a temperature of 80 DEG C, obtain turbid solution B.Transparent salmon solution A is slowly added
Enter into turbid solution B, stirred for 10 times at a temperature of 80 DEG C, be sufficiently mixed it.Mixed solution is poured into the poly- of 50mL
Tetrafluoroethene liner, is put into hydrothermal reaction kettle, and hydro-thermal reaction 48 hours under conditions of 200 DEG C obtain vanadium phosphate sodium water-setting
Glue presoma.Vanadium phosphate sodium hydrogel precursor at -30 DEG C of temperature and the pressure condition of -0.1MPa is freeze-dried, is obtained
To xerogel presoma.Vanadium phosphate sodium xerogel presoma is gone to and is connected with H2/ Ar (Ar and H2Volume ratio is 95:5) mixed gas
Quartz tube furnace in, 800 DEG C of calcining at constant temperature 8h are risen to 5 DEG C/min heating rates, natural cooling obtains carbon coating vanadium phosphate
Sodium microsphere powder material.Using the pattern of FEI Co. of U.S. Nova NanoSEM230 scanning electron microscopic observation samples, sample is found
It is the microballoon being assembled by nano particle, as shown in figure 13.Cycle performance test voltage ranging from 2.5V~4V, current density are
1C, its specific capacity is still up to 101.5mA h g after recycling 500 times-1.Its cycle performance result is as shown in figure 15.
Embodiment 9
Carbon coating vanadium phosphate sodium microsphere powder material prepared by embodiment 4 and embodiment 8, conductive carbon Super P and poly- inclined
Difluoroethylene (PVDF) binding agent is according to 8:1:1 mass ratio after mixing, be dispersed in N- methyl pyrroles alkanone (NMP) solution
In obtain starchy mixture.The paste mixture of acquisition is uniformly coated on aluminium foil, and is dried in vacuo 12 at 100 DEG C
Hour.The assembling of vanadium phosphate sodium/sodium button cell (2016 model) is in the glove box (German Braun) full of high-purity argon gas
Middle progress.Using metallic sodium piece as cathode, using glass fibre as diaphragm, 1M NaClO4It is dissolved in propene carbonate/fluoro carbonic acid
Vinyl acetate (PC/FEC) (1:1, volume ratio) as electrolyte, the carbon coating vanadium phosphate sodium microsphere powder of synthesis as battery just
Pole material.The charging and discharging test of sodium-ion battery carries out on blue electric battery test system at room temperature, the voltage of test
Ranging from 2.5V~4V references are in Na/Na+。
Claims (10)
1. a kind of carbon coating vanadium phosphate sodium microballoon, it is characterised in that：The vanadium phosphate sodium nanometer sheet of conductive carbon layer is coated with by surface
Assembling is formed.
2. a kind of preparation method of carbon coating vanadium phosphate sodium microballoon described in claim 1, it is characterised in that：It will be dissolved with five oxidations
The hydrogen peroxide solution of two vanadium is slowly added into the aqueous solution containing Organic Sodium Salt, phosphorus source and itrogenous organic substance, is stirred evenly, and is obtained
Mixed liquor；The mixed liquor, which is transferred in hydrothermal reaction kettle, carries out hydro-thermal reaction, obtains vanadium phosphate sodium hydrogel；The vanadium phosphate
Sodium hydrogel after drying, be placed in protective atmosphere calcine to get.
3. a kind of preparation method of carbon coating vanadium phosphate sodium microballoon according to claim 1, it is characterised in that：It is described organic
Sodium salt includes odium stearate, enuatrol, sodium tartrate, sodium citrate, sodium alginate, lauryl sodium sulfate, detergent alkylate
Sodium sulfonate, dodecyl sodium sulfate, sodium benzoate, benzene sulfonic acid sodium salt, disodium ethylene diamine tetraacetate, dioctyl sodium sulfosuccinate,
Sodium carboxymethylcellulose, sodium lactate, sodium humate, maltonic acid sodium, diphenylamine sulfonic acid sodium salt, sodium xylene sulfonate, pentane sulphur
At least one of sour sodium, hexane sodium sulfonate, sodium heptanesulfonate, perfluorooctane sulfonate, natrii tauroglycocholas, saccharin sodium；
Phosphorus source includes ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, five
Aoxidize at least one of two phosphorus, microcosmic salt, vanadium phosphate, ortho phosphorous acid.
4. a kind of preparation method of carbon coating vanadium phosphate sodium microballoon according to claim 1, it is characterised in that：It is described nitrogenous
Organic matter includes urea, thiocarbamide, pyrroles, ethylenediamine, diethylenetriamine, ammonium citrate, 2-methylimidazole, dicyanodiamine, poly- pyrrole
It coughs up, at least one of polyvinylpyrrolidone, diallyl dimethyl ammoniumchloride, ammonium chloride, polyacrylonitrile.
5. a kind of preparation method of carbon coating vanadium phosphate sodium microballoon according to claim 1, it is characterised in that：It is described dissolved with
In the hydrogen peroxide solution of vanadic anhydride the mass percent concentration of hydrogen peroxide be 1~30%, vanadic anhydride it is a concentration of
0.0025mol/L~0.1mol/L.
6. according to a kind of preparation method of carbon coating vanadium phosphate sodium microballoon of Claims 1 to 5 any one of them, feature exists
In：The molar ratio of Organic Sodium Salt and phosphorus source is using the molar ratio of sodium ion and phosphate anion as 1~1.1:1 metering；
The mass ratio of Organic Sodium Salt and itrogenous organic substance is 1:0.1~0.5；
The molar ratio of Organic Sodium Salt and vanadic anhydride is using the molar ratio of sodium ion and vanadium ion as 3~3.3:2 meterings.
7. according to a kind of preparation method of carbon coating vanadium phosphate sodium microballoon of Claims 1 to 5 any one of them, feature exists
In：The drying process temperature is -40 DEG C~100 DEG C, and pressure condition is -0.1MPa~0.1MPa.
8. according to a kind of preparation method of carbon coating vanadium phosphate sodium microballoon of Claims 1 to 5 any one of them, feature exists
In：
The temperature of the hydro-thermal reaction is 100 DEG C~250 DEG C, and the time is 2 hours~96 hours.
9. according to a kind of preparation method of carbon coating vanadium phosphate sodium microballoon of Claims 1 to 5 any one of them, feature exists
In：The calcination process is under protective atmosphere, and 600 DEG C~900 DEG C guarantors are risen to the heating rate of 1 DEG C/min~10 DEG C/min
Temperature 6 hours~12 hours.
10. a kind of application of carbon coating vanadium phosphate sodium microballoon described in claim 1, it is characterised in that：As sodium-ion battery
Positive electrode application.
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| CN109775680A (en) * | 2018-08-07 | 2019-05-21 | 上海紫剑化工科技有限公司 | A kind of vanadium phosphate sodium nanometer sheet and its preparation method and application |
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| CN109775680A (en) * | 2018-08-07 | 2019-05-21 | 上海紫剑化工科技有限公司 | A kind of vanadium phosphate sodium nanometer sheet and its preparation method and application |
| CN109775680B (en) * | 2018-08-07 | 2022-06-10 | 上海紫剑化工科技有限公司 | Sodium vanadium phosphate nanosheet and preparation method and application thereof |
| CN110970612A (en) * | 2018-09-29 | 2020-04-07 | 中国科学院大连化学物理研究所 | Preparation of transition metal oxide positive electrode material and application of transition metal oxide positive electrode material in sodium ion battery |
| CN110970612B (en) * | 2018-09-29 | 2022-05-06 | 中国科学院大连化学物理研究所 | Preparation of transition metal oxide positive electrode material and application of transition metal oxide positive electrode material in sodium ion battery |
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| CN114335529B (en) * | 2021-11-05 | 2024-01-26 | 四川龙蟒磷化工有限公司 | Preparation method of vanadium sodium phosphate type sodium battery positive electrode material |
| CN114335529A (en) * | 2021-11-05 | 2022-04-12 | 四川龙蟒磷化工有限公司 | Preparation method of vanadium sodium phosphate type sodium battery positive electrode material |
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| CN114400309B (en) * | 2022-01-13 | 2023-08-04 | 蜂巢能源科技股份有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN114824250A (en) * | 2022-01-17 | 2022-07-29 | 常州大学 | Multifunctional additive synchronously modified carbon-coated sodium vanadium fluorophosphate composite material, and preparation method and application thereof |
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