CN105098179A - Preparation method of sodium-ion battery cathode material Na3V2(PO4)3 - Google Patents

Preparation method of sodium-ion battery cathode material Na3V2(PO4)3 Download PDF

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CN105098179A
CN105098179A CN201410212580.0A CN201410212580A CN105098179A CN 105098179 A CN105098179 A CN 105098179A CN 201410212580 A CN201410212580 A CN 201410212580A CN 105098179 A CN105098179 A CN 105098179A
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sodium
solution
spinning
phosphate
ion battery
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CN105098179B (en
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吴川
李慧
吴锋
白莹
吴伯荣
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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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 preparation method of a sodium-ion battery cathode material Na3V2(PO4)3. The method comprises the following steps: (1) mixing a sodium salt, a vandic salt, phosphate, a complexing agent, a high-molecular compound and a solvent to obtain a Na3V2(PO4)3 spinning solution; (2) carrying out electrostatic spinning on the Na3V2(PO4)3 spinning solution to obtain a Na3V2(PO4)3 spinning precursor; and (3) collecting the Na3V2(PO4)3 spinning precursor, carrying out thermal treatment on the Na3V2(PO4)3 spinning precursor in an inert atmosphere and cooling the Na3V2(PO4)3 spinning precursor to obtain the sodium-ion battery cathode material Na3V2(PO4)3. According to the sodium-ion battery cathode material Na3V2(PO4)3 prepared by the method disclosed by the invention, high-capacity charging and discharging of the battery can be realized; and the cycle stability of the battery can be improved.

Description

A kind of sodium-ion battery positive material Na 3v 2(PO 4) 3preparation method
Technical field
The invention belongs to chemical power source and field of energy source materials, relate to a kind of preparation method of sodium ion battery electrode material, particularly a kind of sodium-ion battery positive material Na 3v 2(PO 4) 3preparation method.
Background technology
The energy is the material base supporting whole human civilization progress.Along with socioeconomic high speed development, the interdependency of human society to the energy improves constantly.At present, traditional fossil energy as coal, oil, natural gas etc. for human society provides the main energy.The consumption of fossil energy not only makes it increasingly exhausted, and remarkable to environmental impact.Therefore change existing irrational energy resource structure and become the matter of utmost importance that human social faces.At present, the wind energy greatly developed, solar energy, tidal energy, geothermal energy etc. all belong to renewable and clean energy resource, due to its feature such as randomness, intermittence, if the electric energy it produced directly inputs electrical network, can produce very large impact to electrical network.Under these circumstances, the efficient energy storage technology easily of development becomes worldwide study hotspot with the energy demand meeting the mankind.
Lithium ion battery as one of energy storage mode, have energy density large, have extended cycle life, the advantage such as operating voltage is high, memory-less effect, self discharge is little, operating temperature range is wide.But it still exists a lot of problem, as cell safety, cycle life and Cost Problems etc.And, along with lithium ion battery is applied to electric automobile gradually, to greatly increase the demand of lithium, and the reserves of lithium are limited, and skewness, the long-life energy-storage battery of the intelligent grid that this is cheap for demand for development, fail safe is high and the extensive energy storage of regenerative resource may be a bottleneck problem.Compare lithium resource, sodium reserves are very abundant, account for 2.64% of earth's crust reserves, and widely distributed, refine simple, meanwhile, sodium and lithium, in the same main group of the periodic table of elements, have similar physicochemical properties, and sodium-ion battery has the operation principle similar with lithium ion battery, both positive and negative polarity is made up of two kinds of different sodium ion inlaid scheme.From discharge and recharge invertibity, sodium-ion battery reaction is a kind of desirable reversible reaction.Therefore, develop the sodium-ion battery technology being directed to extensive stored energy application and there is important strategic importance.
For embedding sodium positive electrode, the cell positive material with sodium superionic conductors (NASICON) structure, owing to having stable structure and good cyclical stability, arouses widespread concern.The main conventional solid-state method that adopts prepares sodium-ion battery positive material Na at present 3v 2(PO 4) 3, and the chemical property such as voltage of sodium-ion battery positive material of preparing of the method has much room for improvement, and therefore, finds a kind of preparation method that can improve the sodium-ion battery positive material of chemical property significant.
Summary of the invention
The object of this invention is to provide a kind of sodium-ion battery positive material Na 3v 2(PO 4) 3preparation method, the sodium-ion battery positive material Na that the method prepares 3v 2(PO 4) 3the high power capacity discharge and recharge of battery can be realized, and the cyclical stability of battery can be improved.
The present inventor surprisingly finds under study for action, by sodium salt, vanadic salts, phosphate, complexing agent, macromolecular compound and solvent, prepares Na 3v 2(PO 4) 3after spinning solution, recycling electrostatic spinning prepares Na 3v 2(PO 4) 3spinning presoma, then under an inert atmosphere by Na 3v 2(PO 4) 3spinning presoma is heat-treated and the sodium-ion battery positive material Na prepared after cooling 3v 2(PO 4) 3there is nano bar-shape form, be conducive to sodium ion deintercalation fast in the material, the polarization phenomena of electrode in electrochemical reaction process and the contact increased between electrode and electrolyte can be reduced simultaneously, be conducive to the transmission of ion, realize the high power capacity discharge and recharge of battery, and improve the cyclical stability of battery.
Therefore, to achieve these goals, the invention provides a kind of sodium-ion battery positive material Na 3v 2(PO 4) 3preparation method, the method comprises the following steps:
(1) by sodium salt, vanadic salts, phosphate, complexing agent, macromolecular compound and solvent, Na is obtained 3v 2(PO 4) 3spinning solution;
(2) by Na 3v 2(PO 4) 3spinning solution carries out electrostatic spinning, obtains Na 3v 2(PO 4) 3spinning presoma;
(3) Na is collected 3v 2(PO 4) 3spinning presoma, under an inert atmosphere to Na 3v 2(PO 4) 3spinning presoma is heat-treated, and obtains sodium-ion battery positive material Na after cooling 3v 2(PO 4) 3.
Method of the present invention has following useful technique effect:
The first, the sodium-ion battery positive material Na that the present invention utilizes electrostatic spinning to prepare 3v 2(PO 4) 3have nano bar-shape form, the fibre diameter of nanofiber is less, and sodium ion insert depth is in the fibre shallow, the evolving path is short, is conducive to sodium ion deintercalation fast in the material.
The second, nanofiber has larger specific area, contributes to reducing the polarization phenomena of electrode in electrochemical reaction process and the contact increased between electrode and electrolyte, is conducive to the transmission of ion.
3rd, the nanofiber utilizing electrostatic spinning to prepare has a lot of blemish or lattice defect on fiber axial direction, can provide more reaction site for ion, and then improves the storage sodium performance of material.
4th, sodium-ion battery positive material Na prepared by the present invention 3v 2(PO 4) 3the high power capacity discharge and recharge of battery can be realized, the cyclical stability of battery can be improved.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the Na that embodiment 1 prepares 3v 2(PO 4) 3spinning presoma (a) and sodium-ion battery positive material Na 3v 2(PO 4) 3the scanning electron microscope (SEM) photograph of (b).
Fig. 2 is the sodium-ion battery positive material Na that embodiment 1 prepares 3v 2(PO 4) 3the transmission electron microscope picture of (b).
Fig. 3 is the sodium-ion battery positive material Na that embodiment 1-3 prepares 3v 2(PO 4) 3x-ray diffractogram.
Fig. 4 is the Na that embodiment 4 prepares 3v 2(PO 4) 3spinning presoma (a) and sodium-ion battery positive material Na 3v 2(PO 4) 3the scanning electron microscope (SEM) photograph of (b).
Fig. 5 is the first charge-discharge curve of the CR2025 experiment button cell that embodiment 1 prepares.
Fig. 6 is that the CR2025 that embodiment 1 prepares tests the cycle performance figure of button cell under 0.1C.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of sodium-ion battery positive material Na 3v 2(PO 4) 3preparation method, the method comprises the following steps:
(1) by sodium salt, vanadic salts, phosphate, complexing agent, macromolecular compound and solvent, Na is obtained 3v 2(PO 4) 3spinning solution;
(2) by Na 3v 2(PO 4) 3spinning solution carries out electrostatic spinning, obtains Na 3v 2(PO 4) 3spinning presoma;
(3) Na is collected 3v 2(PO 4) 3spinning presoma, under an inert atmosphere to Na 3v 2(PO 4) 3spinning presoma is heat-treated, and obtains sodium-ion battery positive material Na after cooling 3v 2(PO 4) 3.
In the inventive method, for the special requirement of sodium salt, vanadic salts, phosphate, complexing agent, macromolecular compound and solvent, various sodium salts, vanadic salts, phosphate, complexing agent, macromolecular compound and the solvent that can commonly use for this area.In order to improve the sodium-ion battery positive material Na prepared 3v 2(PO 4) 3first discharge specific capacity and capability retention, under preferable case, sodium salt is at least one in sodium dihydrogen phosphate, NaOH, sodium carbonate, sodium acid carbonate, sodium chloride, sodium nitrate and sodium acetate; Vanadic salts is at least one in vanadic oxide, sodium metavanadate, sodium vanadate, sodium pyrovanadate and ammonium metavanadate; Phosphate is at least one in sodium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid; Complexing agent is citric acid, oxalic acid, ammonium citrate, ammonium oxalate, maleic acid, ascorbic acid, tartaric acid, monoethanolamine, at least one in diethanol amine, triethanolamine and edetate; Macromolecular compound is at least one in poly(ethylene oxide) (PEO), polyvinyl alcohol (PVA), polystyrene (PS), polyacrylonitrile (PAN), PLA (PLA), poly-hexyl propionamide (PCL), polyurethane (PU), polyamide (PA), cellulose acetate (CA), polyvinyl acetate (PVAc) and polyvinylpyrrolidone (PVP); Solvent is hexafluoroisopropanol, HCl solution, NaCl solution, 2,2,2-trifluoroethanol, triethanolamine, 1, at least one in 3-bis-[three (methylol) methylamino] propane, acetic acid, absolute ethyl alcohol, Hexafluoro acetone, oxolane, chloroform, carrene, DMA and water.More preferably, water is deionized water.
In the inventive method, in order to improve the sodium-ion battery positive material Na prepared 3v 2(PO 4) 3first discharge specific capacity and capability retention, in step (1), in vanadium (V), the mol ratio of vanadic salts and complexing agent is preferably 1:1-5, is more preferably 1:1-2.Respectively with sodium (Na), vanadium (V) and phosphate radical (PO 4 3-) meter, sodium salt, vanadic salts, phosphatic mol ratio are preferably 3-3.5:2:3-3.5, are more preferably 3.1-3.3:2:3-3.3.For the amount of solvent, there is no particular limitation, as long as sodium salt, vanadic salts, phosphate, complexing agent or macromolecular compound can be made to dissolve completely.
The present inventor finds under study for action, and the mixed method of sodium salt, vanadic salts, phosphate, complexing agent, macromolecular compound and solvent is for the sodium-ion battery positive material Na prepared 3v 2(PO 4) 3first discharge specific capacity and capability retention have impact, in order to improve the sodium-ion battery positive material Na prepared 3v 2(PO 4) 3first discharge specific capacity and capability retention, under preferable case, in step (1), the method for mixing comprises:
A sodium salt, vanadic salts, phosphate, complexing agent and macromolecular compound are dissolved in solvent by () respectively completely, obtain sodium salt solution, vanadic salts solution, phosphate solution, enveloping agent solution and macromolecular compound solution;
B sodium salt solution, vanadic salts solution and phosphate solution are added in enveloping agent solution by (), stir, and obtain vanadium phosphate sodium solution;
C vanadium phosphate sodium solution drops in macromolecular compound solution by (), stir, and then solution being evaporated to macromolecular compound concentration is 10wt%-30wt%, continues to stir, and obtains Na 3v 2(PO 4) 3spinning solution.
In the inventive method, for the not special requirement of the method preparing sodium salt solution, vanadic salts solution, phosphate solution, enveloping agent solution and macromolecular compound solution, as long as sodium salt, vanadic salts, phosphate, complexing agent and macromolecular compound can be made to be dissolved in solvent completely.In order to shorten manufacturing cycle and ensure effectively carrying out of follow-up complex reaction, under preferable case, in step (a), when preparing sodium salt solution, vanadic salts solution, phosphate solution and enveloping agent solution, consoluet condition comprises: at 40 DEG C-90 DEG C, stir 0.5h-2h, and mixing speed is 100rpm-1000rpm; More preferably, at 60 DEG C-80 DEG C, stir 1h-2h, mixing speed is 400rpm-800rpm.When preparing macromolecular compound solution, consoluet condition comprises: stir 2h-14h at 0-100 DEG C, and mixing speed is 100rpm-1000rpm; More preferably, stir 4h-8h at 20-30 DEG C, mixing speed is 400rpm-600rpm.
In the inventive method, in order to shorten manufacturing cycle and ensure effectively carrying out of complex reaction, under preferable case, in step (b), the condition of stirring comprises: mixing speed is 100rpm-1000rpm, is more preferably 400rpm-800rpm; Mixing time is 0.5h-4h, is more preferably 1h-2h; Whipping temp is 40 DEG C-90 DEG C, is more preferably 60 DEG C-80 DEG C.
In the inventive method, under preferable case, in step (c), the condition of the stirring carried out before evaporation comprises: mixing speed is 100rpm-1000rpm, is more preferably 400rpm-800rpm; Whipping temp is 40 DEG C-90 DEG C, is more preferably 50 DEG C-60 DEG C; Mixing time is 2h-14h, is more preferably 4h-8h.The condition of the stirring carried out after evaporation comprises: mixing speed is 100rpm-1000rpm, is more preferably 400rpm-600rpm; Whipping temp is 20 DEG C-50 DEG C, is more preferably 20 DEG C-30 DEG C; Mixing time is 2h-10h, is more preferably 4h-8h.
The present inventor finds under study for action, and solution being evaporated to macromolecular compound concentration is 10wt%-30wt%, can obtain the Na that viscosity is suitable for spinning 3v 2(PO 4) 3spinning solution.
In the inventive method, in step (2), when carrying out electrostatic spinning, can by Na 3v 2(PO 4) 3spinning solution is placed in electrostatic spinning device or syringe, uses receiver (as aluminium foil) to make collecting electrode, prepares Na by the distance of control voltage, filament mouth (as syringe needle) and receiver, spinning speed and receiver rotating speed 3v 2(PO 4) 3spinning presoma.In order to improve the sodium-ion battery positive material Na prepared 3v 2(PO 4) 3first discharge specific capacity and capability retention, under preferable case, the condition of electrostatic spinning comprises: voltage is 10kV-30kV, is more preferably 15kV-25kV; The distance of filament mouth and receiver is 10cm-30cm, is more preferably 15cm-25cm; Spinning speed is 0.01-0.5mm/min, is more preferably 0.1-0.2mm/min; Receiver rotating speed is 1-10m/h, is more preferably 4-6m/h.
In the inventive method, in step (3), inert atmosphere can be nitrogen or argon gas.Heat treatment can disposablely be carried out, and also can carry out step by step, and under preferable case, it is 300 DEG C-900 DEG C that heat treated condition comprises calcining heat, and calcination time is 6h-15h.Particularly, heat up from 20 DEG C-50 DEG C, be warming up to 300 DEG C-900 DEG C with the heating rate of 1 DEG C/min-20 DEG C/min, and calcine 6h-15h at 300 DEG C-900 DEG C.More preferably, heat treated condition comprises 300 DEG C-500 DEG C pre-burning 2h-5h, 700 DEG C-900 DEG C calcining 6h-10h.Particularly, heat up from 20 DEG C-50 DEG C, be warming up to 300 DEG C-500 DEG C with the heating rate of 5 DEG C/min-10 DEG C/min, and at 300 DEG C-500 DEG C pre-burning 2h-5h; Then be warming up to 700 DEG C-900 DEG C with the heating rate of 5 DEG C/min-10 DEG C/min, and calcine 6h-10h at 700 DEG C-900 DEG C.Sodium-ion battery positive material Na can be obtained after being cooled to 20 DEG C-50 DEG C after heat treatment 3v 2(PO 4) 3.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In following examples and comparative example, LANDCT2001A tester is purchased from Wuhan Land Electronic Co., Ltd..
Carry out the ESEM of use during scanning electron microscopic observation for QUANTAFEG250, purchased from section depending on reaching (China) Co., Ltd.
Carry out the transmission electron microscope of use during transmission electron microscope observing for HitachiH-800, purchased from HIT.
Embodiment 1
The present embodiment is for illustration of sodium-ion battery positive material Na of the present invention 3v 2(PO 4) 3preparation method.
By amount of substance than n (Na): n (V): n (PO 4 3-): n (citric acid)=3.2:2:3:3 takes 0.64g NaOH, 1.1698g ammonium metavanadate, 1.7254g ammonium dihydrogen phosphate and 2.8821g citric acid respectively, and be dissolved in 10ml, 40ml, 10ml, 10ml deionized water respectively, at 70 DEG C, stir 1.5h to dissolving completely with mixing speed 500rpm.Respectively sodium hydroxide solution, ammonium metavanadate solution, ammonium dihydrogen phosphate are poured in citric acid solution, at 80 DEG C, stir 1.5h with mixing speed 500rpm form dark blue solution.Take 2g mean molecule quantity be 1300000 polyvinylpyrrolidone be dissolved in the deionized water of 20ml, stir 6h to dissolving completely with mixing speed 500rpm at 25 DEG C.Above-mentioned dark blue solution is dropped in consoluet polyvinylpyrrolidonesolution solution, 6h is stirred with mixing speed 500rpm at 60 DEG C, then solution is evaporated to 10ml (macromolecular compound concentration is 20wt%), continues to stir 6h with mixing speed 500rpm at 25 DEG C and form uniform Na 3v 2(PO 4) 3spinning solution.
By above-mentioned Na 3v 2(PO 4) 3spinning solution joins in 5ml syringe, uses aluminium foil to make collecting electrode.Distance between syringe needle and aluminium foil is 20cm, and voltage is 20kV, and spinning speed is 0.15mm/min, and aluminium foil rotating speed is 5m/h, prepares Na 3v 2(PO 4) 3spinning presoma.
Collect Na 3v 2(PO 4) 3spinning presoma, and by gained Na 3v 2(PO 4) 3spinning presoma is placed in tube furnace, under argon gas atmosphere, heat up from 20 DEG C, 300 DEG C are warming up to 5 DEG C/min heating rate, and at 300 DEG C pre-burning 3h, be then warming up to 900 DEG C with 5 DEG C/min heating rate, and calcine 8h at 900 DEG C, be cooled to 20 DEG C after heat treatment terminates, obtain sodium-ion battery positive material Na 3v 2(PO 4) 3.
By the Na that embodiment 1 prepares 3v 2(PO 4) 3spinning presoma and sodium-ion battery positive material Na 3v 2(PO 4) 3observe under ESEM, scanning electron microscope (SEM) photograph is shown in Fig. 1.As can be seen from Fig. 1 (a), Na 3v 2(PO 4) 3spinning presoma is the dendrimers weave in of diameter 1-4um.Through argon gas atmosphere 300 DEG C of pre-burning 3h, after 900 DEG C of calcining 8h, obtain in Fig. 1 (b) in the homodisperse sodium-ion battery positive material Na of corynebacterium 3v 2(PO 4) 3.
By the sodium-ion battery positive material Na that embodiment 1 prepares 3v 2(PO 4) 3observe under transmission electron microscope, transmission electron microscope picture is shown in Fig. 2.As can be seen from Figure 2, Na 3v 2(PO 4) 3the solid tubular structure of fiber to be diameter be 300nm, inner tube layer is active material Na 3v 2(PO 4) 3, diameter is about 100nm, and the uniform coating layer of outer layer thickness is carbon, and thickness is about 50nm.
Embodiment 2
The present embodiment is for illustration of sodium-ion battery positive material Na of the present invention 3v 2(PO 4) 3preparation method.
2.4176g sodium dihydrogen phosphate, 0.91g vanadic oxide and 0.9004g oxalic acid is taken respectively than n (Na): n (V): n (oxalic acid)=3.1:2:2 by amount of substance, and be dissolved in 10ml, 40ml, 10ml deionized water respectively, at 60 DEG C, stir 2h to dissolving completely with mixing speed 400rpm.Respectively sodium dihydrogen phosphate, vanadic oxide solution are poured in oxalic acid solution, at 60 DEG C, stir 2h with mixing speed 400rpm form dark blue solution.Take 2g mean molecule quantity be 600000 poly(ethylene oxide) be dissolved in the deionized water of 20ml, stir 8h to dissolving completely with mixing speed 400rpm at 30 DEG C.Above-mentioned dark blue solution is dropped in consoluet poly(ethylene oxide) solution, 8h is stirred with mixing speed 400rpm at 50 DEG C, then solution is evaporated to 20ml (macromolecular compound concentration is 10wt%), continues to stir 8h with mixing speed 400rpm at 20 DEG C and form uniform Na 3v 2(PO 4) 3spinning solution.
By above-mentioned Na 3v 2(PO 4) 3spinning solution joins in 5ml syringe, uses aluminium foil to make collecting electrode.Distance between syringe needle and aluminium foil is 15cm, and voltage is 15kV, and spinning speed is 0.1mm/min, and aluminium foil rotating speed is 4m/h, prepares Na 3v 2(PO 4) 3spinning presoma.
Collect Na 3v 2(PO 4) 3spinning presoma, and by gained Na 3v 2(PO 4) 3spinning presoma is placed in tube furnace, under argon gas atmosphere, heat up from 50 DEG C, 500 DEG C are warming up to 5 DEG C/min heating rate, and at 500 DEG C pre-burning 2h, be then warming up to 700 DEG C with 5 DEG C/min heating rate, and calcine 10h at 700 DEG C, be cooled to 50 DEG C after heat treatment terminates, obtain sodium-ion battery positive material Na 3v 2(PO 4) 3.
Embodiment 3
The present embodiment is for illustration of sodium-ion battery positive material Na of the present invention 3v 2(PO 4) 3preparation method.
By amount of substance than n (Na): n (V): (PO 4 3-): n (citric acid)=3.3:2:3:4 takes 0.533g sodium acetate, 1.2193g sodium metavanadate, 1.9808 diammonium hydrogen phosphates and 4.86g ammonium citrate respectively, and be dissolved into the N of 10ml, 40ml, 10ml, 10ml respectively, in N-dimethylacetylamide, at 80 DEG C, stir 1h to dissolving completely with mixing speed 800rpm.Respectively sodium acetate solution, ammonium dibasic phosphate solution, sodium metavanadate solution are poured in ammonium citrate solution, at 80 DEG C, stir 1h with mixing speed 800rpm form dark blue solution.Take 2g mean molecule quantity be 100000 polyacrylonitrile be dissolved in the DMA of 20ml, stir 4h to dissolving completely with mixing speed 800rpm at 20 DEG C.Above-mentioned dark blue solution is dropped in consoluet polyacrylonitrile solution, 4h is stirred with mixing speed 800rpm at 60 DEG C, then solution is evaporated to 7ml (macromolecular compound concentration is 30wt%), continues to stir 4h with mixing speed 600rpm at 30 DEG C and form uniform Na 3v 2(PO 4) 3spinning solution.
By above-mentioned Na 3v 2(PO 4) 3spinning solution joins in 5ml syringe, uses aluminium foil to make collecting electrode.Distance between syringe needle and aluminium foil is 25cm, and voltage is 25kV, and spinning speed is 0.2mm/min, and aluminium foil rotating speed is 6m/h, prepares Na 3v 2(PO 4) 3spinning presoma.
Collect Na 3v 2(PO 4) 3spinning presoma, and by gained Na 3v 2(PO 4) 3spinning presoma is placed in tube furnace, under nitrogen atmosphere, heat up from 20 DEG C, 500 DEG C are warming up to 5 DEG C/min heating rate, and at 500 DEG C pre-burning 5h, be then warming up to 900 DEG C with 5 DEG C/min heating rate, and calcine 6h at 900 DEG C, be cooled to 30 DEG C after heat treatment terminates, obtain sodium-ion battery positive material Na 3v 2(PO 4) 3.
The Na that embodiment 2 and embodiment 3 prepare 3v 2(PO 4) 3spinning presoma and sodium-ion battery positive material Na 3v 2(PO 4) 3scanning electron microscope (SEM) photograph, sodium-ion battery positive material Na 3v 2(PO 4) 3transmission electron microscope picture all similar to Example 1, therefore not to repeat here.
Fig. 3 is the sodium-ion battery positive material Na that embodiment 1-3 prepares 3v 2(PO 4) 3x-ray diffractogram.As can be seen from Figure 3, the peak type of embodiment 1-3 is identical, and peak is similar to by force, shows that the material prepared is Na 3v 2(PO 4) 3, and there is not assorted peak in material, all diffraction maximums can well be mated with R3C space group, and the material prepared is pure phase.
Embodiment 4
The present embodiment is for illustration of sodium-ion battery positive material Na of the present invention 3v 2(PO 4) 3preparation method.
By amount of substance than n (Na): n (V): (PO 4 3-): n (ammonium oxalate)=3:2:3:2 takes 0.7949g sodium carbonate, 1.1698g ammonium metavanadate, 1.4695g phosphoric acid and 1.241g ammonium oxalate respectively, and be dissolved in 10ml, 40ml, 10ml, 10ml absolute ethyl alcohol respectively, at 40 DEG C, stir 2h to dissolving completely with mixing speed 100rpm.Respectively sodium carbonate liquor, ammonium metavanadate solution, phosphoric acid solution are poured in ammonium oxalate solution, at 40 DEG C, stir 4h with mixing speed 100rpm form dark blue solution.Take 2g mean molecule quantity be 1300000 polyvinylpyrrolidone be dissolved in the absolute ethyl alcohol of 20ml, stir 14h to dissolving completely with mixing speed 100rpm at 0 DEG C.Above-mentioned dark blue solution is dropped in consoluet polyvinylpyrrolidonesolution solution, 14h is stirred with mixing speed 100rpm at 40 DEG C, then solution is evaporated to 20ml (macromolecular compound concentration is 10wt%), continues to stir 10h with mixing speed 100rpm at 20 DEG C and form uniform Na 3v 2(PO 4) 3spinning solution.
By above-mentioned Na 3v 2(PO 4) 3spinning solution joins in 5ml syringe, uses aluminium foil to make collecting electrode.Distance between syringe needle and aluminium foil is 10cm, and voltage is 10kV, and spinning speed is 0.01mm/min, and aluminium foil rotating speed is 1m/h, prepares Na 3v 2(PO 4) 3spinning presoma.
Collect Na 3v 2(PO 4) 3spinning presoma, and by gained Na 3v 2(PO 4) 3spinning presoma is placed in tube furnace, under nitrogen atmosphere, heat up from 30 DEG C, 500 DEG C are warming up to 1 DEG C/min heating rate, and at 500 DEG C pre-burning 2h, be then warming up to 700 DEG C with 5 DEG C/min heating rate, and calcine 10h at 700 DEG C, be cooled to 20 DEG C after heat treatment terminates, obtain sodium-ion battery positive material Na 3v 2(PO 4) 3.
By the Na that embodiment 4 prepares 3v 2(PO 4) 3spinning presoma and sodium-ion battery positive material Na 3v 2(PO 4) 3observe under ESEM, scanning electron microscope (SEM) photograph is shown in Fig. 4.As can be seen from Fig. 4 (a), Na 3v 2(PO 4) 3spinning presoma is the long strip shape object weave in of diameter 50nm-100nm.Through argon gas atmosphere 500 DEG C of pre-burning 2h, after 700 DEG C of calcining 10h, obtain in Fig. 4 (b) in the homodisperse sodium-ion battery positive material Na of filament shape 3v 2(PO 4) 3.
Embodiment 5
The present embodiment is for illustration of sodium-ion battery positive material Na of the present invention 3v 2(PO 4) 3preparation method.
By amount of substance than n (Na): n (V): n (PO 4 3-): n (citric acid)=3.5:2:3:4 takes 1.47g sodium acid carbonate, 0.91g vanadic oxide, 1.7254g ammonium dihydrogen phosphate and 3.5224g ascorbic acid respectively, and be dissolved in 10ml, 40ml, 10ml, 10ml absolute ethyl alcohol respectively, at 90 DEG C, stir 0.5h to dissolving completely with mixing speed 1000rpm.Respectively sodium bicarbonate solution, vanadic oxide solution and ammonium dihydrogen phosphate are poured in ascorbic acid solution, at 90 DEG C, stir 0.5h with mixing speed 1000rpm form dark blue solution.Take 2g mean molecule quantity be the polyvinyl alcohol dissolution of 2400 in the chloroform of 20ml, stir 2h to dissolving completely with mixing speed 1000rpm at 100 DEG C.Above-mentioned dark blue solution is dropped in consoluet poly-vinyl alcohol solution, 2h is stirred with mixing speed 1000rpm at 90 DEG C, then solution is evaporated to 7ml (macromolecular compound concentration is 30wt%), continues to stir 2h with mixing speed 1000rpm at 50 DEG C and form uniform Na 3v 2(PO 4) 3spinning solution.
By above-mentioned Na 3v 2(PO 4) 3spinning solution joins in 5ml syringe, uses aluminium foil to make collecting electrode.Distance between syringe needle and aluminium foil is 30cm, and voltage is 30kV, and spinning speed is 0.5mm/min, and aluminium foil rotating speed is 10m/h, prepares Na 3v 2(PO 4) 3spinning presoma.
Collect Na 3v 2(PO 4) 3spinning presoma, and by gained Na 3v 2(PO 4) 3spinning presoma is placed in tube furnace, under argon gas atmosphere, heats up, be warming up to 900 DEG C, and calcine 10h at 900 DEG C, be cooled to 30 DEG C, obtain sodium-ion battery positive material Na after heat treatment terminates with 20 DEG C/min heating rate from 40 DEG C 3v 2(PO 4) 3.
The Na that embodiment 5 prepares 3v 2(PO 4) 3spinning presoma and sodium-ion battery positive material Na 3v 2(PO 4) 3scanning electron microscope (SEM) photograph similar to Example 4, therefore not to repeat here.
Embodiment 6
According to the method for embodiment 1, unlike, by amount of substance than n (Na): n (V): n (PO 4 3-): n (citric acid)=3:2:3:1 takes 0.6g NaOH, 1.1698g ammonium metavanadate, 1.7254g ammonium dihydrogen phosphate and 0.9607g citric acid respectively.
Embodiment 7
According to the method for embodiment 1, unlike, the distance between syringe needle and aluminium foil is 40cm, and voltage is 35kV, and spinning speed is 0.8mm/min, and aluminium foil rotating speed is 15m/h.
Embodiment 8
According to the method for embodiment 1, unlike, preparation Na 3v 2(PO 4) 3the method of spinning solution is: taking 0.64g NaOH, 1.1698g ammonium metavanadate, 1.7254 ammonium dihydrogen phosphates, 2.8821g citric acid and 2g mean molecule quantity is respectively the polyvinylpyrrolidone of 1300000, and NaOH, ammonium metavanadate, ammonium dihydrogen phosphate, citric acid and polyvinylpyrrolidone are dissolved in 90ml deionized water, at 60 DEG C, stirring 6h to dissolving completely with mixing speed 500rpm, obtaining Na 3v 2(PO 4) 3spinning solution.
Embodiment 9
According to the method for embodiment 1, unlike, preparation Na 3v 2(PO 4) 3in the method for spinning solution, all temperature conditions are 25 DEG C.
Comparative example
This comparative example prepares sodium-ion battery positive material Na for illustration of conventional solid-state method 3v 2(PO 4) 3method.
Take 2.3397g sodium dihydrogen phosphate, 1.170g ammonium metavanadate and 3.42g sucrose by amount of substance respectively than n (Na): n (V): n (sucrose)=3:2:2 to mix in stone roller alms bowl, by mixture ball milling in ball mill, 400rpm ball milling 8h, obtains presoma.Gained presoma is placed in tube furnace, under argon gas atmosphere, heat up from 20 DEG C, 300 DEG C are warming up to 5 DEG C/min heating rate, and at 300 DEG C pre-burning 3h, be then warming up to 900 DEG C with 5 DEG C/min heating rate, and calcine 8h at 900 DEG C, be cooled to 20 DEG C after heat treatment terminates, obtain sodium-ion battery positive material Na 3v 2(PO 4) 3.
Test example
Respectively by sodium-ion battery positive material Na that embodiment 1-9 and comparative example prepare 3v 2(PO 4) 3with conductive black SP (TIMCAL), binding agent PVDF (the Kynoar solution of 5%) in mass ratio 8:1:1 smear on aluminium foil make positive plate, with sodium sheet for negative pole, Celgard2400 makees barrier film, 1MNaPF used for electrolyte 6+ ethylene carbonate (EC)+diethyl carbonate (DEC), wherein the volume ratio of EC:DEC is 1:1, in the glove box being full of argon gas atmosphere, be assembled into model is that CR2025 tests button cell, tests after leaving standstill 12h on LANDCT2001A tester.
Wherein, Fig. 5 is the first charge-discharge curve of the CR2025 experiment button cell that embodiment 1 prepares.As shown in Figure 5, under the voltage of 2.5-4.0v and the multiplying power of 0.1C, only there is a voltage platform, at about 3.4v.Its initial charge specific capacity is 106.4mAh/g, corresponding to 1.8 Na +deviate from; Correspondingly, its first discharge specific capacity reaches 100.4mAh/g, corresponding to 1.7 Na +embed.This shows that this material achieves 1.7 reversible electron reactions.The first charge-discharge curve that the CR2025 that embodiment 2-9 prepares tests button cell is consistent with Fig. 5, and therefore not to repeat here.
Fig. 6 is that the CR2025 that embodiment 1 prepares tests the cycle performance figure of button cell under 0.1c.As shown in Figure 6, under the voltage of 2.5-4V and the multiplying power of 0.1C, battery energy stable circulation 50 weeks.First discharge specific capacity is 100.4mAh/g, and discharge and recharge is after 50 weeks, and specific discharge capacity is 98.3mAh/g, reaches 97.9% of first all specific discharge capacities (capability retention).The last fortnight is the activation process of material, and coulombic efficiency is 94.4% and 97.3%; From the 3rd week, coulombic efficiency was all greater than 98%.After the first discharge specific capacity of embodiment 2-9 and comparative example, 50 circulations, the result of specific discharge capacity and the capability retention of circulation after 50 weeks is as shown in table 1.
Table 1
By known for the results contrast of embodiment 1-9 in table 1 and comparative example, the sodium-ion battery positive material Na that embodiments of the invention 1-9 prepares 3v 2(PO 4) 3first discharge specific capacity apparently higher than comparative example, after circulating 50 weeks, the capability retention of embodiment 1-9 all at more than 90% of all specific discharge capacities of head, and comparative example circulate 50 weeks after capability retention be only 81.5%, be starkly lower than embodiment 1-9.
By known for the results contrast of embodiment in table 11 and embodiment 6, in vanadium, the mol ratio of vanadic salts and complexing agent is 1:1-5; And respectively in sodium, vanadium and phosphate radical, sodium salt, vanadic salts, phosphatic mol ratio are 3-3.5:2:3-3.5, first discharge specific capacity and the capability retention of circulation after 50 weeks of material can be improved further.
By known for the results contrast of embodiment in table 11 and embodiment 7, when carrying out electrostatic spinning, voltage is 10kV-30kV, the distance of filament mouth and receiver is 10cm-30cm, spinning speed is 0.01-0.5mm/min, receiver rotating speed is 1-10m/h, can improve first discharge specific capacity and the capability retention of circulation after 50 weeks of material further.
By known for the results contrast of embodiment in table 11 and embodiment 8, at preparation Na 3v 2(PO 4) 3during spinning solution, adopt the method for multi-step mixing, that is, first prepare sodium salt solution, vanadic salts solution, phosphate solution, enveloping agent solution and macromolecular compound solution; Then sodium salt solution, vanadic salts solution and phosphate solution are added in enveloping agent solution, stir, obtain vanadium phosphate sodium solution; Again vanadium phosphate sodium solution is dropped in macromolecular compound solution, stir, and solution to be evaporated to macromolecular compound concentration be 10wt%-30wt%, then continue to stir, first discharge specific capacity and the capability retention of circulation after 50 weeks of material can be improved further.
By known for the results contrast of embodiment in table 11 and embodiment 9, at preparation Na 3v 2(PO 4) 3in the process of spinning solution, at 40 DEG C-90 DEG C, prepare sodium salt solution, vanadic salts solution, phosphate solution and enveloping agent solution, sodium salt solution, vanadic salts solution and phosphate solution be added in enveloping agent solution and carry out stirring, vanadium phosphate sodium solution being dropped in macromolecular compound solution and stir at 40 DEG C-90 DEG C at 40 DEG C-90 DEG C, first discharge specific capacity and the capability retention of circulation after 50 weeks of material can be improved further.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (10)

1. a sodium-ion battery positive material Na 3v 2(PO 4) 3preparation method, it is characterized in that, the method comprises the following steps:
(1) by sodium salt, vanadic salts, phosphate, complexing agent, macromolecular compound and solvent, Na is obtained 3v 2(PO 4) 3spinning solution;
(2) by Na 3v 2(PO 4) 3spinning solution carries out electrostatic spinning, obtains Na 3v 2(PO 4) 3spinning presoma;
(3) Na is collected 3v 2(PO 4) 3spinning presoma, under an inert atmosphere to Na 3v 2(PO 4) 3spinning presoma is heat-treated, and obtains sodium-ion battery positive material Na after cooling 3v 2(PO 4) 3.
2. method according to claim 1, wherein, in step (1), in vanadium, the mol ratio of described vanadic salts and described complexing agent is 1:1-5, is preferably 1:1-2.
3. method according to claim 1, wherein, in step (1), respectively in sodium, vanadium and phosphate radical, described sodium salt, described vanadic salts, described phosphatic mol ratio are 3-3.5:2:3-3.5, are preferably 3.1-3.3:2:3-3.3.
4. method according to claim 1, wherein, in step (1), the method for described mixing comprises:
A sodium salt, vanadic salts, phosphate, complexing agent and macromolecular compound are dissolved in solvent by () respectively completely, obtain sodium salt solution, vanadic salts solution, phosphate solution, enveloping agent solution and macromolecular compound solution;
B sodium salt solution, vanadic salts solution and phosphate solution are added in enveloping agent solution by (), stir, and obtain vanadium phosphate sodium solution;
C vanadium phosphate sodium solution drops in macromolecular compound solution by (), stir, and then solution being evaporated to macromolecular compound concentration is 10wt%-30wt%, continues to stir, and obtains Na 3v 2(PO 4) 3spinning solution.
5. method according to claim 4, wherein, in step (a), when preparing sodium salt solution, vanadic salts solution, phosphate solution and enveloping agent solution, described consoluet condition comprises: at 40 DEG C-90 DEG C, stir 0.5h-2h, and mixing speed is 100rpm-1000rpm;
When preparing macromolecular compound solution, described consoluet condition comprises: stir 2h-14h at 0 DEG C-100 DEG C, and mixing speed is 100rpm-1000rpm.
6. method according to claim 4, wherein, in step (b), the condition of stirring comprises: mixing speed is 100rpm-1000rpm, and mixing time is 0.5h-4h, and whipping temp is 40 DEG C-90 DEG C.
7. method according to claim 4, wherein, in step (c), the condition of the stirring carried out before evaporation comprises: mixing speed is 100rpm-1000rpm, and whipping temp is 40 DEG C-90 DEG C, and mixing time is 2h-14h.
8. method according to claim 1, wherein, in step (2), the condition of described electrostatic spinning comprises: voltage is 10kV-30kV, is preferably 15kV-25kV; The distance of filament mouth and receiver is 10cm-30cm, is preferably 15cm-25cm; Spinning speed is 0.01-0.5mm/min, is preferably 0.1-0.2mm/min; Receiver rotating speed is 1-10m/h, is preferably 4-6m/h.
9. method according to claim 1, wherein, in step (3), described inert atmosphere is nitrogen or argon gas;
It is 300 DEG C-900 DEG C that described heat treated condition comprises calcining heat, and calcination time is 6h-15h; Preferably, described heat treated condition comprises 300 DEG C-500 DEG C pre-burning 2h-5h, 700 DEG C-900 DEG C calcining 6h-10h.
10. according to the method in claim 1-9 described in any one, wherein, described sodium salt is at least one in sodium dihydrogen phosphate, NaOH, sodium carbonate, sodium acid carbonate, sodium chloride, sodium nitrate and sodium acetate; Described vanadic salts is at least one in vanadic oxide, sodium metavanadate, sodium vanadate, sodium pyrovanadate and ammonium metavanadate; Described phosphate is at least one in sodium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid; Described complexing agent is at least one in citric acid, oxalic acid, ammonium citrate, ammonium oxalate, maleic acid, ascorbic acid, tartaric acid, monoethanolamine, diethanol amine, triethanolamine and edetate; Described macromolecular compound is at least one in poly(ethylene oxide), polyvinyl alcohol, polystyrene, polyacrylonitrile, PLA, poly-hexyl propionamide, polyurethane, polyamide, cellulose acetate, polyvinyl acetate and polyvinylpyrrolidone; Described solvent is hexafluoroisopropanol, HCl solution, NaCl solution, 2,2,2-trifluoroethanol, triethanolamine, 1, at least one in 3-bis-[three (methylol) methylamino] propane, acetic acid, absolute ethyl alcohol, Hexafluoro acetone, oxolane, chloroform, carrene, DMA and water.
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