CN108807899A - A kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole - Google Patents
A kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole Download PDFInfo
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- CN108807899A CN108807899A CN201810594100.XA CN201810594100A CN108807899A CN 108807899 A CN108807899 A CN 108807899A CN 201810594100 A CN201810594100 A CN 201810594100A CN 108807899 A CN108807899 A CN 108807899A
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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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- 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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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
The present invention relates to a kind of preparation methods of multistage spherical vanadium phosphate sodium composite positive pole.This method is using oxalic acid, vanadium source, sodium source and phosphorus source as primary raw material, and using urea as pelletizing agent and carbon source, spherical vanadium phosphate sodium presoma is formed using hydro-thermal method, after presoma is dried in a nitrogen atmosphere through two-step thermal processing to obtain the final product.The vanadium phosphate sodium composite positive pole that the present invention obtains has multistage spherical morphology, a diameter of 1 ~ 5 μm of microsphere particle, positive electrode be can be used as sodium-ion battery, in the operating voltage range of 2.5V-4.3V, under 0.1C multiplying powers, first run specific discharge capacity is up to 116.47mAh/g, under 10C multiplying powers, first discharge specific capacity is 95mAh/g, 98% or more capacity retention ratio after 100 circle of cycle.This method compared with prior art, not only increases the chemical property of positive electrode, and the method for synthesizing spherical pattern is simple and effective.
Description
Technical field
The present invention relates to a kind of preparation methods of multistage spherical vanadium phosphate sodium composite positive pole, are belonging to sodium-ion battery just
Pole field of material technology.
Background technology
Currently, compared with lithium ion battery, sodium-ion battery has element abundance, and Regional Distribution is uniform, and cost is aobvious
The multiple advantages such as reduction are write, therefore are considered as the important replacement of lithium ion battery.In addition, sodium ion is belonged to lithium ion
The Ith major element of the periodic table of elements has similar electron outside nucleus layer structure, and sodium ion radius is larger, heavier mass, increases
Ionic radius tool there are two conclusive advantage：One is that polarization caused by the larger radius of sodium ion is small so that sodium ion
Solubility in the electrolytic solution is small, to reduce sodium ion transfger impedance；What is more important ionic radius is big, forms solid knot
Structure can provide the ion transmission channel of bigger, and these structures cannot be realized with lithium.
In numerous materials, Na3V2(PO4)3(NVP) it is a kind of very potential sodium-ion battery positive material, has
NASION frame structures, this unique structure can provide migration of the open three-dimensional framework in order to sodium ion, in sodium ion
Intercalation/deintercalation during, NVP can show a charge and discharge platform in 3.4V or so, corresponding V3+/V4+Redox couple.
But the electron conductivity of this phosphate material is low, can lead to that coulombic efficiency is low, poor circulation, to influence its practicality
Property, this is the major obstacle that NVP is faced.
It since electrode material has pattern dependence, can be controlled by pattern, make NVP that there is spherical morphology, increase electricity
Pole material specific surface area, and then increase the contact area of electrolyte and electrode material, it is provided for the discharge and recharge reaction of electrode material
More reaction sites；And spherical morphology can prevent volume change from producing with the volume change in Effective Regulation charge and discharge process
Raw electrode material dusting failure phenomenon directly improves the cycle performance of NVP.In addition, carbon-coating be coated on material surface can also
Improve the electric conductivity of vanadium phosphate sodium, it is believed that it is development vanadium phosphate sodium sodium-ion battery anode to prepare the NVP/C with spherical morphology
The effective way of material.
In current research, big more options introduce carbon source, form carbon coating to obtain the structure of porous spherical, improve ratio
Surface area and electric conductivity.But this method is there is also many problems, and carbon coating is easy that uneven and thickness is not easy to control, material
It can be bad.Publication No. CN106898752A discloses a kind of porous spherical vanadium phosphate sodium/carbon pipe composite positive pole preparation side
Method, but the carbon nanotube synthesis that this method uses is not easy, and cyclical stability needs to be further increased.Publication No.
CN107845796A discloses a kind of carbon doping phosphoric acid vanadium sodium positive electrode and preparation method thereof, using collosol and gel combination high temperature
Calcining obtains presoma, then prepares buffer solution, dispersion is mixed with dopamine hydrochloride, then be separated by solid-liquid separation, dry；Most afterwards through two
Section calcining obtains the positive electrode；But this method process is complicated, performance is bad under the material high magnification of synthesis, industrialization prospect
It is bad.Publication No. CN107611367A discloses a kind of porous spherical carbon coating vanadium phosphate sodium composite positive pole and its preparation
Method, this method need that the organic solvent progress hydro-thermal that polarity is more than water is added, improve reaction cost and need to centrifuge and wash
Precipitation, complex steps.Publication No. CN105244503A discloses a kind of spherical sodium ion electrode material of classification graphene modified
The preparation method of material, this method is using spray drying, by high-temperature process, the sphere material for the graphene modified being classified,
But this method pelletizing complicated mechanism, of high cost and cycle performance need to be further increased.
Invention content
The technical problem to be solved by the present invention is to provide a kind of multi-stage ball in view of the deficiency of the prior art
The preparation method of shape vanadium phosphate sodium composite positive pole, vanadium phosphate sodium composite positive pole made from this method have multistage spherical
Pattern can be used as sodium-ion battery positive material.
A kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole, key step are as follows：
(1) sodium source, deionized water, urea are mixed, colourless solution A is made in 50 DEG C~70 DEG C stirring in water bath dissolvings；Its
In, the molar ratio of sodium element and urea is 3 in sodium source:1~5；
(2) according to Na3V2(PO4)3Stoichiometric ratio Na：V：P=3：2：3, the molar ratio of v element in oxalic acid and vanadium source
It is 1~3:1, vanadium source, phosphorus source and dissolving oxalic acid are weighed in deionized water, and blue is made in 50 DEG C~70 DEG C stirring in water bath dissolvings
Solution B；
(3) according to Na3V2(PO4)3Stoichiometric ratio Na：V：P=3：2：3, solution B made from step (2) is delayed dropwise
It is slow to be added to stirring and dissolving in solution A made from step (1), form mixed solution；
(4) mixed solution made from step (3) is fitted into water heating kettle, at 120 DEG C~180 DEG C hydro-thermal reaction 6h~
18h grinds after drying, obtains precursor powder；
(5) by precursor powder is under protective atmosphere made from step (4), through secondary heat treatment 9h~15h, natural cooling
Afterwards, multistage spherical vanadium phosphate sodium composite positive pole is obtained.
Preferably according to the present invention, Na in colourless solution A+Concentration is within the scope of 0.1mol/L~1mol/L.
Preferably according to the present invention, the sodium source is one kind in trisodium citrate, sodium carbonate, sodium acetate etc..
Preferably according to the present invention, the vanadium source is one kind in vanadic anhydride, ammonium metavanadate etc..
Preferably according to the present invention, the phosphorus source is one kind in ammonium dihydrogen phosphate, phosphoric acid etc..
Preferably according to the present invention, in step (3), the stirring and dissolving is in 50 DEG C~70 DEG C stirring in water bath 15min
~45min.
According to the present invention preferably, in step (4), the hydro-thermal reaction be at 120 DEG C~180 DEG C keep the temperature 6h~
18h。
Preferably according to the present invention, in step (5), the secondary heat treatment is specially：First it is warming up to 300 DEG C~400
DEG C heat treatment 4h~6h, takes out after natural cooling after being fully ground, sample is placed in atmosphere furnace and is warming up to 600 DEG C~800 DEG C
It is heat-treated 5h~7h.
Preferably according to the present invention, in step (5), the protective atmosphere is nitrogen, inert gas etc..
Vanadium phosphate sodium composite positive pole of the present invention can be used as sodium-ion battery positive material and be applied, specifically
Method and step is as follows：
1) vanadium phosphate sodium composite positive pole obtained is fully ground after mixing with conductive agent and binder, N- first is added
Base pyrrolidinone solvent obtains precoating refined slurries after stirring evenly；
2) precoating of step 1) is refined slurries to be coated on aluminium foil, sodium ion is obtained after being then dried electrode slice
Anode electrode slice, gained sodium-ion battery anode electrode piece are used for button-type battery.
Compared with prior art, the present invention having advantageous effect below：
First, the present invention is that organic chemistry is applied in the vanadium phosphate sodium composite positive pole for preparing spherical morphology,
Raw material forms VOC using anhydrous oxalic acid and vanadium source2O4, further, the amino in urea and VOC2O4In carboxyl between occur
Condensation reaction, forming peptide bond-CO-NH- makes urea be incorporated in vanadium phosphate sodium surface, since its surfactant properties is self-assembled into
Spherical morphology, urea pyrolysis row is at carbon coating in situ during heat treatment, to realize to Na3V2(PO4)3/ C-material shape
The control of looks simultaneously completes close carbon coating.During synthesis, urea not only acts as pelletizing agent and provides the effect of carbon source,
It is incorporated in VOC2O4Surface can also effectively control Na3V2(PO4)3Crystallite dimension realizes nanosizing, shortens sodium ion in positive electrode
In transmission path, to improve Na3V2(PO4)3The electric conductivity and specific capacity of positive electrode.
Secondly, the present invention creates a high temperature and high pressure environment using hydro-thermal method, and crystal growth is in non-oppression state, system
The advantages that crystal powder obtained has grain development complete, and granularity is small, and particle agglomeration is lighter, and this method does not need special set
It is standby；After secondary heat treatment, synthesis has obtained the vanadium phosphate sodium composite positive pole of function admirable, in 2.5V-4.3V voltage models
In enclosing, first discharge specific capacity is up to 116.47mAh/g under 0.1C, close to Na3V2(PO4)3Theoretical specific capacity, under 10C multiplying powers,
First discharge specific capacity is up to 95mAh/g, 98% or more capacity retention ratio after cycle 100 is enclosed, and can be used as positive electrode for making
Standby sodium-ion battery, improves the chemical property of sodium-ion battery positive material, reduces and prepares difficulty and cost.
Description of the drawings
Fig. 1 is the XRD diagram for the vanadium phosphate sodium composite positive pole that embodiment 1 synthesizes；Wherein ordinate is diffracted intensity, horizontal
Coordinate is angle of diffraction (2 θ).
Fig. 2 is the SEM figures for the vanadium phosphate sodium composite positive pole that embodiment 1 synthesizes.
Fig. 3 is the first run charging and discharging curve figure for the vanadium phosphate sodium composite positive pole that embodiment 1 synthesizes；Wherein ordinate is
Voltage, abscissa are specific capacities.
Fig. 4 is the high-multiplying power discharge specific capacity figure for the vanadium phosphate sodium composite positive pole that embodiment 1 synthesizes；Wherein ordinate is
Specific discharge capacity, abscissa are cycle-indexes.
Specific implementation mode
The present invention is described in further details with reference to embodiment and attached drawing, it is described be explanation of the invention without
It is to limit.
Embodiment 1
A kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole, is as follows：
(1) it weighs two citric acid monohydrate trisodiums 2.941g and urea 1.5015g is dissolved in 40ml deionized waters, 60 DEG C of water
Colourless solution A is made in bath stirring, fully dissolving；
(2) ammonium metavanadate 2.3398g, ammonium dihydrogen phosphate 3.4509g and anhydrous oxalic acid 2.7009g are weighed and is dissolved in 40ml
In ionized water, blue solution B is made in 60 DEG C of stirring in water bath, fully dissolving；
(3) solution B is slowly added into solution A dropwise, 60 DEG C of stirring in water bath 30min, forms mixed solution；
(4) mixed solution obtained by step (3) being fitted into water heating kettle, the hydro-thermal reaction 12h at 160 DEG C is ground after drying,
Obtain precursor powder；
(5) under nitrogen protection by precursor powder, 350 DEG C of heat treatment 5h are first warming up to, natural cooling is abundant after taking out
Grinding, then be placed in atmosphere furnace and be warming up to 700 DEG C of heat treatment 6h.After natural cooling, the vanadium phosphate sodium of multistage spherical morphology is obtained
Composite positive pole.
As shown in Figure 1, the electrode obtained material and Na3V2(PO4)3The control of PDF#45-0319 cards is good, occurs consistent
Crystalline phase diffraction maximum, show resulting materials be vanadium phosphate sodium.In addition, SEM tests are carried out to it, as shown in Fig. 2, under scanning electron microscope
The pattern of multi-stage ball can be observed, grain diameter is at 1~5 μm.
Also, electrochemistry is carried out to the vanadium phosphate sodium composite positive pole of multistage spherical morphology made from the embodiment 1
It can test.Detailed process is as follows：
The vanadium phosphate sodium combination electrode material is prepared into electrode using rubbing method.By vanadium phosphate sodium composite positive pole,
Acetylene black and Kynoar (PVDF) press 80:10:10 mass ratio is fully ground mixing, and N-Methyl pyrrolidone solvent is added
The precoating obtained after stirring evenly refines slurry；Above-mentioned precoating is refined slurry to be respectively coated on aluminium foil, it is dry through 110 DEG C of vacuum
Dry 12h is cut into the disk of diameter 10mm after natural cooling using sheet-punching machine, obtains sodium-ion battery anode electrode piece.
According to negative electrode casing-stainless (steel) wire-sodium piece-electrolyte-diaphragm-electrolyte-positive plate-stainless (steel) wire-anode cover
Sequence is assembled successively, is recycled sealing machine by cell sealing, is obtained CR2016 type button sodium half-cells.It is filled in indigo plant electricity CT2001A
Discharge instrument carries out charge-discharge test to battery.Test results are shown in figure 3, it is known that：Multistage spherical morphology made from embodiment 1
Vanadium phosphate sodium composite positive pole is in 2.5V-4.3V voltage ranges, and first discharge specific capacity is 116.47mAh/g under 0.1C；
Figure 4, it is seen that the material, in 2.5V-4.3V voltage ranges, first discharge specific capacity is 95mAh/g, cycle under 10C
After 100 circles, 98% or more capacity retention ratio.
Embodiment 2
A kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole, is as follows：
(1) it weighs two citric acid monohydrate trisodiums 2.941g and urea 0.75075g is dissolved in 40ml deionized waters, 50 DEG C
Colourless solution A is made in stirring in water bath, fully dissolving；
(2) ammonium metavanadate 2.3398g, ammonium dihydrogen phosphate 3.4509g and anhydrous oxalic acid 2.7009g are weighed and is dissolved in 40ml
In ionized water, blue solution B is made in 50 DEG C of stirring in water bath, fully dissolving；
(3) solution B is slowly added into solution A dropwise, 50 DEG C of stirring in water bath 15min, forms mixed solution；
(4) mixed solution is fitted into water heating kettle, the hydro-thermal reaction 6h at 140 DEG C grinds after drying, obtains precursor
End；
(5) under nitrogen protection by precursor powder, 300 DEG C of heat treatment 4h are first warming up to, natural cooling is abundant after taking out
Grinding, then be placed in atmosphere furnace and be warming up to 600 DEG C of heat treatment 5h.The vanadium phosphate sodium that multistage spherical morphology is obtained after natural cooling is multiple
Close positive electrode.
Electrochemical property test is carried out according to step described in embodiment 1, in 2.5V-4.3V voltage ranges, under 0.1C
First discharge specific capacity is 106mAh/g.
Embodiment 3
A kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole, is as follows：
(1) it weighs two citric acid monohydrate trisodiums 2.941g and urea 3.003g is dissolved in 40ml deionized waters, 80 DEG C of water
Colourless solution A is made in bath stirring, fully dissolving；
(2) ammonium metavanadate 2.3398g, ammonium dihydrogen phosphate 3.4509g and anhydrous oxalic acid 2.7009g are weighed and is dissolved in 40ml
In ionized water, blue solution B is made in 80 DEG C of stirring in water bath, fully dissolving；
(3) solution B is slowly added into solution A dropwise, 80 DEG C of stirring in water bath 45min, forms mixed solution；
(4) mixed solution is fitted into water heating kettle, the hydro-thermal reaction 18h at 180 DEG C grinds after drying, obtains presoma
Powder；
(5) under nitrogen protection by precursor powder, 400 DEG C of heat treatment 6h are first warming up to, natural cooling is abundant after taking out
Grinding, then be placed in atmosphere furnace and be warming up to 800 DEG C of heat treatment 7h.The vanadium phosphate sodium that multistage spherical morphology is obtained after natural cooling is multiple
Close positive electrode.
Electrochemical property test is carried out according to step described in embodiment 1, in 2.5V-4.3V voltage ranges, under 0.1C
First discharge specific capacity is 111mAh/g.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (10)
1. a kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole, it is characterised in that with oxalic acid, vanadium source, sodium source and
Phosphorus source is as primary raw material, and using urea as pelletizing agent and carbon source, spherical vanadium phosphate sodium presoma is formed using hydro-thermal method；By phosphorus
After sour vanadium sodium presoma drying, through two-step thermal processing up to multistage spherical vanadium phosphate sodium composite positive pole under protective atmosphere.
2. a kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole according to claim 1, feature exist
In a diameter of 1 ~ 5 μm of the microsphere particle of the multistage spherical vanadium phosphate sodium composite positive pole.
3. a kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole, it is characterised in that key step is as follows：
（1）Sodium source, water, urea are mixed, colourless solution A is made in stirring and dissolving；Wherein, the sodium element in sodium source and urea
Molar ratio is 1:8~9；
（2）Molar ratio according to v element in oxalic acid and vanadium source is 3~4:1, vanadium source, phosphorus source and dissolving oxalic acid are weighed in water,
Blue solution B is made in stirring and dissolving；
（3）By step（2）Solution B obtained is added dropwise to step（1）It is molten to form mixing for stirring and dissolving in solution A obtained
Liquid；
（4）By step（3）Mixed solution obtained, which is fitted into water heating kettle, carries out hydro-thermal reaction, and then drying grinding, obtains forerunner
Body powder；
（5）By step（4）Precursor powder obtained is under protective atmosphere, through secondary heat treatment 9h~15h, after natural cooling,
Obtain multistage spherical vanadium phosphate sodium composite positive pole.
4. a kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole according to claim 3, feature exist
In sodium source, vanadium source, phosphorus source according to Na3V2(PO4)3Stoichiometric ratio Na：V：P = 3：2：3 feed intake；Na in colourless solution A+It is dense
Degree is within the scope of 0.1mol/L ~ 1mol/L.
5. a kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole according to claim 3, feature exist
In the sodium source be trisodium citrate, sodium carbonate, one kind in sodium acetate；The vanadium source is vanadic anhydride, metavanadic acid
One kind in ammonium；The phosphorus source is one kind in ammonium dihydrogen phosphate, phosphoric acid.
6. a kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole according to claim 3, feature exist
In step（1）,（2）,（3）The temperature of middle stirring and dissolving is 50 DEG C~70 DEG C；Step（3）In, the stirring and dissolving be in
50 DEG C~70 DEG C stirring in water bath 15min~45min.
7. a kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole according to claim 3, feature exist
In step（4）In, the hydro-thermal reaction is heat preservation 6h~18h at 120 DEG C~180 DEG C.
8. a kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole according to claim 3, feature exist
In step（5）In, the secondary heat treatment is specially：First it is warming up to 300 DEG C~400 DEG C heat treatment 4h~6h, natural cooling
It takes out afterwards after being fully ground, sample is placed in atmosphere furnace and is warming up to 600 DEG C~800 DEG C heat treatment 5h~7h.
9. the spherical vanadium phosphate sodium composite positive pole of multistage prepared by one of claim 1-8 the methods.
10. spherical vanadium phosphate sodium composite positive pole the answering as sodium-ion battery positive material of multistage described in claim 9
With.
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| CN110092366A (en) * | 2019-04-25 | 2019-08-06 | 西北工业大学 | A kind of multiple phase calcium phosphate vanadium sodium electrode material and preparation method thereof |
| CN110092366B (en) * | 2019-04-25 | 2023-03-31 | 西北工业大学 | Complex-phase vanadium sodium phosphate electrode material and preparation method thereof |
| CN110518214A (en) * | 2019-09-02 | 2019-11-29 | 齐鲁工业大学 | A kind of nitrogen hydrogen original position codope soft carbon/vanadium phosphate sodium composite material and preparation method and application |
| CN114975992A (en) * | 2022-05-31 | 2022-08-30 | 西安交通大学 | Preparation method of transition metal ion doped sodium vanadium phosphate cathode material |
| CN115966691A (en) * | 2022-12-20 | 2023-04-14 | 济南大学 | Micro co-doped modified sodium vanadium phosphate monocrystal micro-flower and preparation method and application thereof |
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