CN108963209A - Sodium-ion battery positive material and its preparation method and application - Google Patents
Sodium-ion battery positive material and its preparation method and application Download PDFInfo
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- CN108963209A CN108963209A CN201810666777.XA CN201810666777A CN108963209A CN 108963209 A CN108963209 A CN 108963209A CN 201810666777 A CN201810666777 A CN 201810666777A CN 108963209 A CN108963209 A CN 108963209A
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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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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 present invention relates to nano materials and electrochemical field, disclose a kind of binder free sodium-ion battery Na flexible3V2(PO4)3The preparation method of/C combination electrode.The present invention is to go water as solvent, it is subject to thickener to adjust solution viscosity, then addition vanadium source, complexing agent, sodium source, phosphoric acid source compound are prepared into spinning solution, it obtains spinning precursor by electrostatic spinning technique, then the spinning precursor of collection is subjected to hot-pressing processing and pre-oxidation treatment, is then sintered to obtain Na in inert gas3V2(PO4)3/ fiber C film, resulting fiber size is uniform, diameter is small, specific surface is big, it can be directly cut into circular electric pole piece, for showing higher charging and discharging capacity in sodium-ion battery and well following bad stability, and the preparation method simple process, reaction condition parameter is easily controllable, is advantageously implemented large-scale production.
Description
Technical field
The invention belongs to nano materials and electrochemical field, and in particular to a kind of sodium-ion battery positive material Na3V2
(PO4)3The preparation method of/C.
Background technique
From portable electronic device to noticeable electric car at present, storage of the lithium ion battery as high-energy density
Energy device is widely used.Although present lithium ion battery occupies leading position in consumption market, due to lithium
Earth's crust reserves few (0.002% or so) and be unevenly distributed so that lithium ion battery will face resource and price in future
Dual bottleneck.Sodium element is abundant, cheap, and has similar chemical property with lithium, and sodium-ion battery is applied to energy storage
Field has sustainable use and commercialized advantage and great potential.
The Na for having sodium superionic conductors (NASICON) structure3V2(PO4)3, due to its sodium ion three-dimensional diffusion, relatively
High voltage platform (3.4V), high theory specific energy (400Whkg-1) and outstanding thermal stability by Na3V2(PO4)3At
For one of most promising sodium ion positive electrode at present.Traditional technology is based primarily upon high temperature solid-state method, sol-gel method, water
Thermal method prepares Na3V2(PO4)3/ C, these techniques have following advantage and disadvantage:
(1) high temperature solid-state method
High temperature solid-state method is a kind of traditional flouring technology, although having the shortcomings that its is intrinsic, such as energy consumption is high, low efficiency, powder
Body is not thin enough, is easily mixed into impurity etc..But the method has, and the powder granule soilless sticking of preparation, fillibility are good, at low cost, yield is big,
The advantages that preparation process is simple.
(2) sol-gel method
The raw material as used in sol-gel method is dispersed to the solution in solvent and forming low viscosity first, because
This, so that it may the uniformity for obtaining molecular level in a short period of time is likely between reactant when forming gel
It is uniformly mixed on molecular level.Due to passing through solution reaction step, then mixing one slightly with being just easy to equal and quantitative
Secondary element realizes the Uniform Doped on molecular level.
Compared with solid phase reaction, chemically react easy progress, and only need lower synthesis temperature, it is considered that molten
Component is diffused in nanometer range in one gel rubber system of glue, and when solid phase reaction in micron range, therefore diffusion of components is
Reaction is easy to carry out, and temperature is lower.The disadvantage is that used cost of material is more expensive, some raw materials are organic matter, to health
It is harmful；It is longer the time required to usually entire sol-gel process, often need a few days or a few weeks；There are a large amount of micropores in gel,
Many gases and organic matter will be escaped again in drying process, and generates contraction.
(3) hydro-thermal method
Its great advantage is generally to be not required to high temperature sintering to directly obtain crystalline powder, avoids that be likely to form particle hard
Reunite, also eliminates grinding and thus bring impurity.It can control nanoparticle by adjusting reaction condition in water-heat process
Crystal structure, crystal habit and crystal grain purity.Not only the small monocrystal of one pack system can have been prepared, but also bi-component or multicomponent can be prepared
Special compound powder.The powder body materials such as metal, oxide and composite oxides can be prepared.The granularity model of gained powder body material
Usually 0.1 μm to several microns is enclosed, some can achieve tens nanometers.Obtained powder purity height, good dispersion, uniformly,
Narrowly distributing, soilless sticking, crystal form be good, controlled shape, is conducive to depollution of environment etc..The disadvantage is that: hydro-thermal method needs high temperature and pressure step, makes
It is stronger to the dependence of production equipment, while also considerably increasing economic cost and time cost.
In general, traditional handicraft, is all to use that Na is first made3V2(PO4)3/ C powder material, then by itself and bonding agent system
At slurry, coating film forming.Lead to existing Na3V2(PO4)3/ C powder material application procedures are complicated, at high cost, and due to its particle knot
The presence of structure and binder leads to the defects of electrode is big just like internal resistance, and specific capacity is low, and high rate performance is weak, poor circulation.
Summary of the invention
The object of the present invention is to provide a kind of sodium-ion battery positive material Na3V2(PO4)3/ C and preparation method thereof, with solution
Certainly high expensive caused by traditional preparation methods complex process, or the Na of preparation3V2(PO4)3The unstable technology of/C particle is asked
Topic.
Another object of the present invention is to provide a kind of sodium-ion battery positive plate containing the positive electrode and sodium from
Sub- battery is undesirable with the chemical property for solving the problems, such as existing sodium-ion battery positive plate and battery.
In order to achieve the above-mentioned object of the invention, an aspect of of the present present invention provides a kind of sodium ion positive electrode Na3V2
(PO4)3The preparation method of/C.A kind of the preparation method comprises the following steps sodium ion positive electrode Na3V2(PO4)3The system of/C
Preparation Method, comprising the following steps:
Component including vanadium source, complexing agent, sodium source, phosphoric acid source compound and adhesion agent is configured to spinning solution in water；
The spinning solution is subjected to electrostatic spinning processing, obtains fiber film precursor；
The fiber film precursor of the preparation is subjected to hot-pressing processing, then in oxygenous environment in being pre-oxidized
Processing；
Fiber film precursor after the pre-oxidation treatment is passed through into sintering processes, Na is prepared3V2(PO4)3/ C receives
Rice tunica fibrosa.
Preferably, the preparation method of the spinning solution are as follows: vanadium source, complexing agent, sodium source, phosphoric acid source compound are dissolved in water
In, solution is formed, is then added in the aqueous solution of polyvinyl alcohol, is stood after mixed processing and obtains spinning solution.
Preferably, the vanadium source includes one of vanadic anhydride, ammonium metavanadate, sodium vanadate, sodium metavanadate or several
Kind；
Preferably, the adhesion agent includes polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polystyrene, poly- ammonia
One or more of ester, polyethylene oxide；
Preferably, the complexing agent includes anhydrous oxalic acid, citric acid, ascorbic acid, maleic acid, tartaric acid, ethanedioic acid, apple
One or more of tartaric acid, lactic acid；
Preferably, the sodium source includes sodium dihydrogen phosphate, sodium phosphate, sodium carbonate, sodium nitrate, sodium oxalate, sodium acetate, sulfuric acid
One or more of sodium, sodium hydroxide, sodium formate, sodium citrate；
Preferably, the source of phosphoric acid includes sodium dihydrogen phosphate, sodium phosphate, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus
One or more of sour three ammoniums.
Preferably, the vanadium source and complexing agent molar ratio are 1:1-1:2.
Preferably, the adhesion agent and the mass ratio in vanadium source are 6:1-8:1.
Preferably, the process conditions of the electrostatic spinning processing are as follows: voltage is selected as 15KV-30KV；Receiver and syringe needle
Distance is 10cm-20cm；Spinning rate is 0.1ml/h-0.6ml/h；Drum rotation speed is 500r/min-1000r/min；In syringe needle
Diameter is 0.4mm-0.8mm.
Fiber in the tunica fibrosa is the fiber of nanoscale.
Preferably, the hot-pressing processing technique, be under the pressure of 2-6Kg at 100 DEG C -130 DEG C hot-pressing processing 10-
20h；
The pre-oxidation process be by the fiber film precursor after the hot-pressing processing in air with 1 DEG C/min-5 DEG C/
The heating rate of min is heated to 220 DEG C of -260 DEG C of heat preservation 2-5h and is handled.
Preferably, the sintering includes the sintering twice in protection atmosphere, and simultaneous organic carbon acts on, initially
Sintering temperature is 300-400 DEG C, time 2-6h；Double sintering temperature is 600-900 DEG C, time 5-10h.
Another aspect of the present invention provides a kind of Na3V2(PO4)3/ C sodium-ion battery positive material.The Na3V2
(PO4)3/ C sodium-ion battery positive material the present invention is by sodium ion positive electrode Na of the present invention3V2(PO4)3The preparation method of/C
It prepares.
Another aspect of the invention provides a kind of sodium-ion battery positive plate.The sodium-ion battery positive plate be by
Na of the present invention3V2(PO4)3The clipped processing of/C sodium ion positive electrode is formed.
Another aspect of the present invention provides a kind of sodium-ion battery.The sodium-ion battery includes the positive plate.
Compared with prior art, the Na3V2(PO4)3On the one hand the preparation method of/C positive electrode material is the Static Spinning used
Silk technical treatment film forming, avoids cumbersome flouring technology；On the other hand conductive agent and positive electrode integral sintering are formed,
Without using bonding agent, current-collector, while simplifying technique, it is thus also avoided that declined using electric property caused by bonding agent.
The sodium-ion battery positive material is the Na prepared by electrostatic spinning technique3V2(PO4)3/ fiber C film, passes through spy
Different heat treatment and pre-oxidation and sintering process can prepare free-standing electrode material, avoid using auxiliary additive (such as
Binder) and current-collector, so that the ion of the positive electrode of the sodium-ion battery, the travelling speed of electronics is fast, and internal resistance is small, polarization
Act on small, energy density is big.
The positive plate of the sodium-ion battery is due to containing the sodium-ion battery positive material, so that the sodium-ion battery
Positive plate ion, the travelling speed of electronics is fast, and internal resistance is small, and polarization is small, and energy density is big.
The sodium-ion battery contains the positive plate, and due to the ion of the positive plate, the travelling speed of electronics is fast, interior
Hinder small, polarization is small, and energy density is big, so that the battery has, specific capacity is high, good rate capability, and good cycle etc. is excellent
Point.
Detailed description of the invention
Fig. 1 is Na in the embodiment of the present invention3V2(PO4)3The X ray diffracting spectrum of/C-material
Fig. 2 is Na in the embodiment of the present invention3V2(PO4)3The SEM spectrum of/C-material
Fig. 3 is Na in the embodiment of the present invention3V2(PO4)3The TEM map of/C-material
Fig. 4 is charging and discharging curve and cycle performance pattern three times before electrode material in the embodiment of the present invention
Fig. 5 is the high rate performance test result of electrode material in the embodiment of the present invention
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The embodiment of the present invention is prepared for binder free Na by electrostatic spinning technique3V2(PO4)3/ fiber C positive electrode, institute
Obtaining positive electrode has many advantages, such as specific capacity height, good rate capability.Below by way of specific embodiments and the drawings to the present invention make into
One step is described in detail.
Specific above-mentioned general formula is Na3V2(PO4)3The nano-fiber electrode material of/C is to form Na3V2(PO4)3It raw material and leads
The molding of electric agent source in-situ sintering, avoids using bonding agent, therefore energy density is higher.Specific sodium ion positive electrode Na3V2
(PO4)3Preparation method includes the following steps:
Component including vanadium source, complexing agent, sodium source, phosphoric acid source compound and adhesion agent is configured to by step (1) in water
Spinning solution；
Step (2) handles configured spinning solution progress electrostatic spinning to obtain fiber film precursor.
Fiber film precursor is carried out hot-pressing processing by step (3), then by fiber film precursor in oxygenous environment
Carry out pre-oxidation treatment.
The fiber film precursor after pre-oxidation treatment is obtained Na by sintering by step (4)3V2(PO4)3/ C nano
Fiber positive electrode.
Vanadium source, sodium source, source of phosphoric acid described in specific above-mentioned steps (1) are according to chemical formula Na3V2(PO4)3In element
Learn metering such as molar ratio add, i.e., vanadium source, sodium source, V, Na in source of phosphoric acid, P element molar ratio be 2:3:3, can be in error
It is fluctuated in the range of permission.
In the particular embodiment, the vanadium source include vanadic anhydride, ammonium metavanadate, sodium vanadate, in sodium metavanadate
One or more；If not considering reaction effect and raw material being ready availability that row other vanadium sources commonly used in the trade can also be used；The sodium salt
Including sodium dihydrogen phosphate, sodium phosphate, sodium carbonate, sodium nitrate, sodium oxalate, sodium acetate, sodium sulphate, sodium hydroxide, sodium formate, lemon
One or more of sour sodium；The source of phosphoric acid includes sodium dihydrogen phosphate, sodium phosphate, phosphoric acid, ammonium dihydrogen phosphate, phosphoric acid hydrogen two
One or more of ammonium, triammonium phosphate.
The complexing agent includes anhydrous oxalic acid, citric acid, ascorbic acid, maleic acid, tartaric acid, ethanedioic acid, malic acid, cream
One or more of acid.What is selected herein is carboxyl as complexing group, if not considering, this field is also can be selected in complexing power
Other complexing agents；During the spinning process, complexing agent is pentavalent vanadium ion in the present embodiment in conjunction with high valence ion, so that
The interference effect of high valence ion is shielded, and eliminates high valence ion to the adverse effect of electrostatic spinning process.
In one embodiment, it controls the vanadium source and complexing agent molar ratio is 1:1-1:2.Equivalent or excessive complexing agent can
Sufficiently to eliminate vanadium ion to the adverse effect of electrostatic spinning process.
In one embodiment, the mass ratio for controlling the adhesion agent and vanadium source is that 6:1-8:1 can satisfy the viscous of spinning solution
Degree requires.
The fiber in tunica fibrosa in the step (2) is nanoscale fiber, by adjusting the technique item of electrostatic spinning
Part can be realized.The membrane material of the enough energy of gained nanofiber has excellent chemical property.Selection condition are as follows: voltage is selected as
15KV-30KV；Receiver and syringe needle distance are 10cm-20cm；Spinning rate is 0.1ml/h-0.6ml/h；Drum rotation speed is
500r/min-1000r/min；Syringe needle internal diameter is 0.4mm-0.8mm.
There are two effects for hot-pressing processing described in the step (3), will be big in tunica fibrosa while being compacted tunica fibrosa
Partial removing moisture.Oxygenous environment in the pre-oxidation treatment can be air and be also possible to other aerobic environments.Institute
State hot-pressing processing technique, be under the pressure of 2-6Kg at 100 DEG C -130 DEG C hot-pressing processing 10-20h；The pre-oxidation process
It is that the fiber film precursor after the hot-pressing processing is heated to 220 in air with the heating rate of 1 DEG C/min-5 DEG C/min
DEG C -260 DEG C of heat preservation 2-5h are handled.
The protection atmosphere of sintering processes described in the step (4) can be nitrogen environment, ar gas environment, vacuum, or
Other inert gas environments.The sintering is carried out in the case where protecting atmosphere, is acted on along with organic carbon, and there are secondary burnings
Knot.Initial sintering temperature is 300-400 DEG C, time 2-6h；Double sintering temperature is 600-900 DEG C, time 5-10h.
Process of the preparation method due to avoiding traditional flouring technology, while electrode slice one sinter molding is also kept away
Exempt from using additive, while guaranteeing performance, has greatly simplified reducing costs for technique.
Based on sodium ion positive electrode Na above3V2(PO4)3On the basis of the preparation method of/C, the embodiment of the present invention is also mentioned
A kind of Na is supplied3V2(PO4)3/ C sodium-ion battery positive material.The nanoscale of tunica fibrosa transports the electrode material ion
Ability is strong, and specific capacity is high, forthright good again, while can further increase energy density without using bonding agent and reduce internal resistance, reduces pole
Change.
On the one hand, the embodiment of the invention also provides a kind of sodium-ion battery positive plates.The positive plate of traditional handicraft includes,
Active material, bonding agent, conductive agent.And the sodium ion positive plate is due to being integral sintering molding, it is only positive by sodium ion
Material Na3V2(PO4)3/ C itself can be formed by, and while structure greatly simplifies, also reduces polarization, reduces internal resistance, excellent
Electric property is changed.
Meanwhile the embodiment of the invention also provides a kind of sodium-ion batteries.The structure of the sodium-ion battery anode can be with
It is conventional sodium-ion battery, is also possible to the improvement carried out according to conventional sodium-ion battery.In one embodiment, the sodium ion
Battery includes anode, diaphragm, cathode, and the anode, diaphragm, cathode are stacked gradually, and be wound, and battery battery core is made；
And the battery core is installed in battery case, electrolyte is filled in battery case.Regardless of which kind of knot the sodium-ion battery is
Structure, positive plate are sodium-ion battery positive plate described above.
Embodiment 1
Present embodiments provide a kind of sodium ion positive electrode Na3V2(PO4)3/C.The sodium ion positive electrode Na3V2
(PO4)3/ C preparation method includes the following steps:
(1) configuration of spinning solution: 25ml deionized water is measured in beaker, is added 3.5g polyvinyl alcohol (PVA), then exists
Half an hour formation polyvinyl alcohol water solution is stood after 70 DEG C of stirring 3h, then weighs 0.4680g ammonium metavanadate, 0.7202g without water plant
Acid, 0.6902g ammonium dihydrogen phosphate, 0.4920g sodium acetate are dissolved in 8ml deionized water, are slowly added dropwise again after dissolution completely
It into polyvinyl alcohol water solution, is maintained under 70 DEG C and stirring condition and is added dropwise, close heating device later and held at room temperature by it
Continue stirring 5h and stand 2h and forms uniform spinning solution；
(2) electrostatic spinning: configured spinning solution in step (1) is encased in the syringe of 30ml, syringe connects electricity
Source anode, roller receiver connect power cathode, and syringe and receiver are in same level height, and receiving distance is 15cm, electricity
Pressure is 20KV, and syringe needle model 21, it is 0.4ml/h that syringe, which promotes rate, and drum rotation speed 800r/min, spinning 20h are obtained
To tunica fibrosa；
(3) hot-pressing processing and pre-oxidation: the spinning precursor in collection step (2) is under the pressure of 2-6Kg 100 in drying box
DEG C dry 10h, is then heated to 260 DEG C of pre- oxygen of heat preservation 3h progress in air by precursor fibre with 2 DEG C/min heating rate
Change；
(4) it is sintered: pretreated tunica fibrosa in step (3) being cut into the square that side length is 3cm or so, then will
Tunica fibrosa is clipped in two layers of thickness as 0.1cm, between the potsherd of side length 4cm, puts it into tube furnace 350 DEG C in an ar atmosphere
It is pre-sintered 5h, is then sintered 8h in Ar atmosphere at 700 DEG C；
(5) prepared by positive electrode: by sintering tunica fibrosa after cooling in step (4) directly in button cell sheet-punching machine undershoot
It is cut into circular positive plate.
With the present embodiment product Na3V2(PO4)3For/C electrode material, structure is determined by X-ray diffractometer.Attached drawing 1
Shown X ray diffracting spectrum (XRD) shows Na3V2(PO4)3Miscellaneous peak is not present in/C-material, all diffraction maximums can be good
It is matched with R3C space group, the material being prepared is pure phase.
TEM image in attached SEM shown in Fig. 2 and attached drawing 3 shows the Na prepared by us3V2(PO4)3Nanometer fiber net
Network structure, nanofiber diameter 200nm or so, size is uniform, and the Na of size about 50nm is coated in nanofiber3V2(PO4)3
Particle, the interlaced formation three-dimensional network-like structure of nanofiber have good structural stability.
Embodiment 2
Present embodiments provide a kind of sodium ion positive electrode Na3V2(PO4)3/C.The sodium ion positive electrode Na3V2
(PO4)3/ C preparation method includes the following steps:
(1) configuration of spinning solution: 25ml deionized water is measured in beaker, is added 3.5g polyvinyl alcohol (PVA), then exists
Half an hour formation polyvinyl alcohol water solution is stood after 70 DEG C of stirring 3h, then weighs 0.4680g ammonium metavanadate, 0.7202g without water plant
Acid, 0.6902g ammonium dihydrogen phosphate, 0.3180g sodium carbonate are dissolved in 8ml deionized water, are slowly added dropwise again after dissolution completely
It into polyvinyl alcohol water solution, is maintained under 70 DEG C and stirring condition and is added dropwise, close heating device later and held at room temperature by it
Continue stirring 5h and stand 2h and forms uniform spinning solution；
(2) electrostatic spinning: configured spinning solution in step (1) is encased in the syringe of 30ml, syringe connects electricity
Source anode, roller receiver connect power cathode, and syringe and receiver are in same level height, and receiving distance is 15cm, electricity
Pressure is 20KV, and syringe needle model 21, it is 0.4ml/h that syringe, which promotes rate, and drum rotation speed 800r/min, spinning 20h are obtained
To tunica fibrosa；
(3) hot-pressing processing and pre-oxidation: the spinning precursor in collection step (2) is under the pressure of 2-6Kg 100 in drying box
DEG C dry 10h, is then heated to 260 DEG C of pre- oxygen of heat preservation 3h progress in air by precursor fibre with 2 DEG C/min heating rate
Change；
(4) it is sintered: pretreated tunica fibrosa in step (3) being cut into the square that side length is 3cm or so, then will
Tunica fibrosa is clipped in two layers of thickness as 0.1cm, between the potsherd of side length 4cm, puts it into tube furnace 350 DEG C in an ar atmosphere
It is pre-sintered 5h, is then sintered 8h in Ar atmosphere at 700 DEG C；
(5) prepared by positive electrode: by sintering tunica fibrosa after cooling in step (4) directly in button cell sheet-punching machine undershoot
It is cut into circular positive plate.
Embodiment 3
Present embodiments provide a kind of sodium ion positive electrode Na3V2(PO4)3/C.The sodium ion positive electrode Na3V2
(PO4)3/ C preparation method includes the following steps:
(1) configuration of spinning solution: 25ml deionized water is measured in beaker, is added 3.5g polyvinyl alcohol (PVA), then exists
Half an hour formation polyvinyl alcohol water solution is stood after 70 DEG C of stirring 3h, then weighs 0.4680g ammonium metavanadate, 0.7202g without water plant
Acid, 0.7199g sodium dihydrogen phosphate are dissolved in 8ml deionized water, and it is water-soluble to be slowly dropped to polyvinyl alcohol again after dissolution completely
It in liquid, is maintained under 70 DEG C and stirring condition and is added dropwise, close heating device later and be continuously stirred at room temperature 5h by it and stand
2h forms uniform spinning solution.
(2) electrostatic spinning: configured spinning solution in step (1) is encased in the syringe of 30ml, syringe connects electricity
Source anode, roller receiver connect power cathode, and syringe and receiver are in same level height, and receiving distance is 15cm, electricity
Pressure is 20KV, and syringe needle model 21, it is 0.4ml/h that syringe, which promotes rate, and drum rotation speed 800r/min, spinning 20h are obtained
To tunica fibrosa.
(3) hot-pressing processing and pre-oxidation: the spinning precursor in collection step (2) is under the pressure of 2-6Kg 100 in drying box
DEG C dry 10h, is then heated to 260 DEG C of pre- oxygen of heat preservation 3h progress in air by precursor fibre with 2 DEG C/min heating rate
Change.
(4) it is sintered: pretreated tunica fibrosa in step (3) being cut into the square that side length is 3cm or so, then will
Tunica fibrosa is clipped in two layers of thickness as 0.1cm, between the potsherd of side length 4cm, puts it into tube furnace 350 DEG C in an ar atmosphere
It is pre-sintered 5h, is then sintered 8h in Ar atmosphere at 700 DEG C.
(5) prepared by positive electrode: by sintering tunica fibrosa after cooling in step (4) directly in button cell sheet-punching machine undershoot
It is cut into circular positive plate.
Embodiment 4
Present embodiments provide a kind of sodium ion positive electrode Na3V2(PO4)3/C.The sodium ion positive electrode Na3V2
(PO4)3/ C preparation method includes the following steps:
(1) configuration of spinning solution: 25ml deionized water is measured in beaker, is added 3.5g polyvinyl alcohol (PVA), then exists
Half an hour formation polyvinyl alcohol water solution is stood after 70 DEG C of stirring 3h, then weighs 0.4680g ammonium metavanadate, 0.7202g without water plant
Acid, 0.7199g sodium dihydrogen phosphate are dissolved in 8ml deionized water, and it is water-soluble to be slowly dropped to polyvinyl alcohol again after dissolution completely
It in liquid, is maintained under 70 DEG C and stirring condition and is added dropwise, close heating device later and be continuously stirred at room temperature 5h by it and stand
2h forms uniform spinning solution.
(2) electrostatic spinning: configured spinning solution in step (1) is encased in the syringe of 30ml, syringe connects electricity
Source anode, roller receiver connect power cathode, and syringe and receiver are in same level height, and receiving distance is 15cm, electricity
Pressure is 20KV, and syringe needle model 21, it is 0.6ml/h that syringe, which promotes rate, and drum rotation speed 800r/min, spinning 20h are obtained
To tunica fibrosa.
(3) hot-pressing processing and pre-oxidation: the spinning precursor in collection step (2) is under the pressure of 2-6Kg 100 in drying box
DEG C dry 10h, is then heated to 260 DEG C of pre- oxygen of heat preservation 3h progress in air by precursor fibre with 2 DEG C/min heating rate
Change.
(4) it is sintered: pretreated tunica fibrosa in step (3) being cut into the square that side length is 3cm or so, then will
Tunica fibrosa is clipped in two layers of thickness as 0.1cm, between the potsherd of side length 4cm, puts it into tube furnace 350 DEG C in an ar atmosphere
It is pre-sintered 5h, is then sintered 8h in Ar atmosphere at 700 DEG C.
(5) prepared by positive electrode: by sintering tunica fibrosa after cooling in step (4) directly in button cell sheet-punching machine undershoot
It is cut into circular positive plate.
The positive electrode Na that will be prepared in embodiment 1-4 respectively3V2(PO4)3/ fiber C film is directly prepared into positive plate, with
Sodium piece is cathode, and Celgard2400 glass fibre makees diaphragm, and electrolyte is with the NaClO4 and 2 volume % of 1mol/L (with carbonic acid third
Enester meter) fluorinated ethylene carbonate (FEC) carbonic allyl ester solution, stand 12h after on LAND CT2001A tester
It is tested.
Wherein, Fig. 4 is the preceding charging and discharging curve three times and cycle performance pattern of sample in embodiment 1, as seen from the figure,
Under the voltage of 2.8-4.0V and the multiplying power of 0.1C, a voltage platform is only existed, in 3.4V or so.Its first discharge specific capacity is
107mAh/g；First charge-discharge efficiency is 92%, and capacity is almost undamped after 100 circulations, shows good cyclicity
Energy.
Test results are shown in figure 5 for the high rate performance of electrode material in embodiment 1.The material shows excellent forthright again
Can, in high magnification 30C, it can still release the specific capacity of 30mAh/g.
After tested, the positive electrode correlation chemical property that other embodiments provide is similar to Example 1.
Claims (10)
1. a kind of sodium ion positive electrode Na3V2(PO4)3The preparation method of/C, it is characterised in that: the following steps are included:
Component including vanadium source, complexing agent, sodium source, phosphoric acid source compound and adhesion agent is dissolved in the water and is configured to spinning solution；
The spinning solution is subjected to electrostatic spinning processing, obtains fiber film precursor；
The fiber film precursor of the preparation is subjected to hot-pressing processing, then in oxygenous environment in carrying out at pre-oxidation
Reason；
Fiber film precursor after the pre-oxidation treatment is passed through into sintering processes, Na is prepared3V2(PO4)3/ fiber C film.
2. preparation method as described in claim 1, it is characterised in that: the preparation method of the spinning solution are as follows: will include vanadium source,
Complexing agent, sodium source, source of phosphoric acid compound component are dissolved in the water, and form solution, are then added in the aqueous solution of adhesion agent, mix
It is stood after processing and obtains spinning solution.
3. preparation method as described in claim 1, it is characterised in that: the vanadium source includes vanadic anhydride, ammonium metavanadate, just
One or more of sodium vanadate, sodium metavanadate；And/or
The adhesion agent includes polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polystyrene, polyurethane, polyethylene oxide
One or more of；And/or
The complexing agent include anhydrous oxalic acid, citric acid, ascorbic acid, maleic acid, tartaric acid, ethanedioic acid, malic acid, in lactic acid
One or more；And/or
The sodium source includes sodium dihydrogen phosphate, sodium phosphate, sodium carbonate, sodium nitrate, sodium oxalate, sodium acetate, sodium sulphate, hydroxide
One or more of sodium, sodium formate, sodium citrate；And/or
The source of phosphoric acid includes sodium dihydrogen phosphate, sodium phosphate, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, one in triammonium phosphate
Kind is several.
4. preparation method as described in claim 1, it is characterised in that: the vanadium source is 1:1-1:2 with complexing agent molar ratio；
And/or
The adhesion agent and the mass ratio in vanadium source are 6:1-8:1.
5. preparation method as described in claim 1, it is characterised in that: the process conditions of the electrostatic spinning processing are as follows: voltage
It is selected as 15KV-30KV；Receiver and syringe needle distance are 10cm-20cm；Spinning rate is 0.1ml/h-0.6ml/h；Roller turns
Speed is 500r/min-1000r/min；Syringe needle internal diameter is 0.4mm-0.8mm；And/or
Fiber in the tunica fibrosa is the fiber of nanoscale.
6. preparation method as described in claim 1, it is characterised in that: the hot-pressing processing technique is under the pressure of 2-6Kg
The hot-pressing processing 10-20h at 100 DEG C -130 DEG C；
The pre-oxidation process is by the fiber film precursor after the hot-pressing processing in air with 1 DEG C/min-5 DEG C/min
Heating rate is heated to 220 DEG C of -260 DEG C of heat preservation 2-5h and is handled.
7. preparation method as described in claim 1, it is characterised in that: the sintering includes the burning twice in protection atmosphere
Knot, the effect of simultaneous organic carbon, initial sintering temperature are 300-400 DEG C, time 2-6h；Double sintering temperature is
600-900 DEG C, time 5-10h.
8. a kind of Na3V2(PO4)3/ C sodium-ion battery positive material, it is characterised in that: the Na3V2(PO4)3/ C sodium-ion battery
Positive electrode is prepared by preparation method as claimed in claim 1 to 7.
9. a kind of sodium-ion battery positive plate, it is characterised in that: the sodium-ion battery positive plate is by according to any one of claims 8
Na3V2(PO4)3The clipped processing of/C sodium ion positive electrode is formed.
10. a kind of sodium-ion battery, it is characterised in that include the positive plate, the positive plate is sodium as claimed in claim 9
Ion battery positive plate.
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| CN113584620A (en) * | 2021-06-29 | 2021-11-02 | 中南大学 | Na3M2XO6Particle-assembled hollow fiber and preparation method and application thereof |
| CN114613997A (en) * | 2022-03-09 | 2022-06-10 | 武汉理工大学 | Manganese-titanium-chromium-sodium phosphate self-supporting electrode material and preparation method and application thereof |
| CN115602822A (en) * | 2022-11-28 | 2023-01-13 | 武汉理工大学三亚科教创新园（Cn） | Preparation method of tin quantum dot embedded nitrogen-doped carbon nanofiber negative electrode material |
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| CN112563565A (en) * | 2020-11-13 | 2021-03-26 | 上海空间电源研究所 | Preparation method of lithium-sodium ion mixed solid electrolyte and solid-state mixed battery |
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| CN112758984A (en) * | 2021-01-18 | 2021-05-07 | 欣旺达电动汽车电池有限公司 | Banded ZnMoO4, preparation method thereof and battery comprising banded ZnMoO4 |
| CN112758984B (en) * | 2021-01-18 | 2023-10-31 | 欣旺达动力科技股份有限公司 | Ribbon ZnMoO4, preparation method thereof and battery comprising ribbon ZnMoO4 |
| CN113584620A (en) * | 2021-06-29 | 2021-11-02 | 中南大学 | Na3M2XO6Particle-assembled hollow fiber and preparation method and application thereof |
| CN113584620B (en) * | 2021-06-29 | 2022-06-14 | 中南大学 | Na3M2XO6Particle-assembled hollow fiber and preparation method and application thereof |
| CN114613997A (en) * | 2022-03-09 | 2022-06-10 | 武汉理工大学 | Manganese-titanium-chromium-sodium phosphate self-supporting electrode material and preparation method and application thereof |
| CN115602822A (en) * | 2022-11-28 | 2023-01-13 | 武汉理工大学三亚科教创新园（Cn） | Preparation method of tin quantum dot embedded nitrogen-doped carbon nanofiber negative electrode material |
| CN115602822B (en) * | 2022-11-28 | 2023-03-21 | 武汉理工大学三亚科教创新园 | Preparation method of tin quantum dot embedded nitrogen-doped carbon nanofiber negative electrode material |
| CN115818611A (en) * | 2022-12-13 | 2023-03-21 | 大连融科储能集团股份有限公司 | Mg-doped sodium vanadium phosphate, mg-doped sodium vanadium fluorophosphate, and preparation methods and applications thereof |
| CN115832289A (en) * | 2023-02-20 | 2023-03-21 | 河南工学院 | Flexible vanadium manganese sodium phosphate/carbon composite cathode material for sodium ion battery and preparation method thereof |
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Application publication date: 20181207 |