CN107195886A - A kind of pyrophosphoric acid vanadium sodium@carbon composite anode materials, preparation and application - Google Patents
A kind of pyrophosphoric acid vanadium sodium@carbon composite anode materials, preparation and application Download PDFInfo
- Publication number
- CN107195886A CN107195886A CN201710407975.XA CN201710407975A CN107195886A CN 107195886 A CN107195886 A CN 107195886A CN 201710407975 A CN201710407975 A CN 201710407975A CN 107195886 A CN107195886 A CN 107195886A
- Authority
- CN
- China
- Prior art keywords
- sodium
- vanadium
- carbon
- source
- pyrophosphoric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of sodium-ion battery pyrophosphoric acid vanadium sodium positive electrode, the pyrophosphoric acid vanadium sodium of carbon coating micro-sphere structure is prepared.Vanadium source and carbon source are by hydro-thermal, the pre-sintered vanadium oxide for preparing cladding carbon-coating in advance, again with sodium source and phosphorus source ball milling, then microspheroidal presoma is obtained by mist projection granulating, presoma obtains the pyrophosphoric acid vanadium sodium of the micro-sphere structure of carbon coating after calcining, washing, dry.In addition, the invention also discloses using sodium-ion battery positive material made from described preparation method.Prepared material is the secondary microballoon of a nano particle formation, and the material is used for sodium-ion battery, excellent chemical property is shown, with industrial applications prospect.
Description
Technical field
The invention belongs to sodium-ion battery field, and in particular to a kind of sodium-ion battery positive material and preparation method thereof.
Background technology
At present, the fossil fuel such as coal, oil is still main power supply resource.However as the mankind it is unreasonable, without section
The exploitation and utilization of system, add the not system of recycling, unreasonable, not science, and fossil energy day is becoming tight.In order to solve this
Problem, extensive electricity storage technology becomes an important field of research.Wherein, secondary cell is due to close with higher energy
Degree and transformation efficiency, become the prioritizing selection of extensive storing up electricity, and with the lithium ion having extended cycle life and energy density is high
Battery is considered as most promising secondary cell.From 1990s since lithium ion battery successfully comes out, it is in electricity
Obtain quite being widely applied in terms of electrical automobile, mancarried electronic aid, but with the continuous progressive and hair of lithium ion battery
Exhibition and people are to the demand of secondary cell and the raising of requirement, and a series of hidden danger and problem have also gradually been exposed to people
The visual field among, therefore it is extremely urgent to develop a kind of cheap, sustainable development battery system.
Sodium and lithium are located at same main group, and with similar physics and chemical property, and sodium resource reserve is abundant, can be continuous
From seawater extract.Although for lithium, sodium ion radius is larger, standard electrochemical current potential is relatively low, causes sodium ion
The energy density and power density of battery are relatively low, but following increase and battery size size with the market demand is excellent
Change, with low cost, safe sodium-ion battery has quite wide prospect, the rear lithium epoch will certainly be turned into most important
One of developing direction.
At present, studied in the consideration based on developing material cost and application prospect, sodium-ion battery it is more, most by section
Grind personnel's concern and surely belong to sodium-ion battery positive material.The storage sodium positive electrode reported at present mainly has polyanionic chemical combination
Thing, prussian blue sodium salt and transition metal oxide.Transition metal oxide has the sour sodium of cobalt, sodium manganate etc., and its feature is
Electronic conductivity is good, and capacity is higher, but their cycle performance is very poor, and overcharge resistance performance can be poor with thermal stability.Pu Lu
Scholar's indigo plant class sodium salt NaxMy[Fe(CN)6] (M=Fe, Co, Ni, Cu etc.) be the complex that a class contains transition metal of appraising at the current rate, this kind of
Compound has complete cubic, with three-dimensional space structure, there are a large amount of coordination spaces, is conducive to sodium ion
Reversible abjection and insertion, but the capacity attenuation mechanism of this kind of compound is unclear.Polyanionic compound mainly has transition
Metal (Jiao) phosphate, fluorophosphate etc..Phosphate compound is often stabilized with fast sodium ion conductor or olivine structural,
Structural framework containing larger ion channel and Three-dimensional Open.The frame structure of transition metal phosphate is relatively stable, uses
When positive pole in charge and discharge process, with preferable cyclical stability and higher security performance, but this kind of material is main
Have the disadvantage that electronic conductivity is low, sodium ion causes by force sodium ion diffusion velocity slower with phosphate backbone adhesion, volume energy
Density is small, and capacity attenuation is big during high-multiplying power discharge.And the synthesis of this kind of material mainly all uses high temperature solid-state method, cost is high,
And preparation process complex process, easily causes environmental pollution.And in a series of this positive electrode, polyanionic compound by
Received much concern in characteristics such as its high voltage, long circulating and excellent securities.
The content of the invention
An object of the present disclosure is to provide a kind of pyrophosphoric acid vanadium sodium@carbon composite anode materials.
Second purpose of the invention is to provide a kind of preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode materials, it is intended to carry
For a kind of simple, reproducible, with low cost, the environment-friendly preparation method of technique.
3rd purpose of the invention is the application in sodium-ion battery field of the anode composite material described in offer, it is intended to
By described positive electrode, the chemical property of sodium-ion battery is lifted.
A kind of pyrophosphoric acid vanadium sodium carbon composite anode material, it is characterised in that be the pyrophosphoric acid vanadium sodium nanometer by being coated with carbon
The micro-spherical particle that particle assembles.
The particle diameter for being coated with the pyrophosphoric acid vanadium sodium nano particle of carbon is 100-200nm；Specific surface area is 20-400m2/g；Bag
Carbon layers having thicknesses are covered for 5-40nm.
The particle diameter of the micro-spherical particle of the composite positive pole is 5-30 μm.
The micro-spherical particle of the composite positive pole is the second particle assembled by primary particle；Primary particle grain
Footpath is 100-200nm, and second particle is the microballoon of 5-30 μm of particle diameter.
Present invention also offers a kind of preparation method of described pyrophosphoric acid vanadium sodium@carbon composite anode materials, carbon will be included
The solution in source and vanadium source carries out hydro-thermal reaction, and hydro-thermal reaction product is carried out into one-level sintering, and bag oxidation of coal vanadium is made；Will be obtained
It is spray-dried after bag oxidation of coal vanadium, sodium source, phosphorus source wet ball grinding, obtains presoma；Presoma carry out two grades sinter described answer
Close positive electrode.
The inventive method, originally first makes in vanadium source and the advanced water-filling heat of carbon source and one-level sintering processes in vanadium oxide
Surface in situ be coated with carbon material layer, described bag oxidation of coal vanadium is made, then bag oxidation of coal vanadium and sodium source and phosphorus source are carried out
Mixing, sintering obtains described composite positive pole.The present invention is compared to preparation sides such as one pot of hydro-thermal or direct ball milling mixings
Method, obtained composite positive pole performance is more excellent；In addition, the inventive method technique is simple, reproducible, with low cost, ring
Border is friendly.
Preparation method of the present invention, key is the syntheti c route of the present invention, that is to say preferential by vanadium source and described carbon source
Bag oxidation of coal vanadium is made in hydro-thermal-one-level sintering；Subsequent ball milling, spraying, double sintering again, assembling obtain described second particle.
In addition, coordinating the control of the parameters such as described hydrothermal reaction condition, Na, V, P element mol ratio and sintering process temperature, it can enter
The electric property of the obtained composite positive pole of one step lifting.
In the present invention, vanadium source and carbon source are dissolved and/or disperse in a solvent, to obtain described solution, followed by
Hydro-thermal reaction.Described solvent can be for water or unlimited than miscible solvent with water, for example, alcohol or acetone of C1~4 etc.；Institute
The alcohol for C1~4 stated is, for example, methanol, ethanol, isopropanol etc..
Preferably, the solvent medium of hydro-thermal reaction is water and/or ethanol.
A kind of preferred preparation method of the present invention, carbon source and vanadium source are dissolved in ethanol medium, are made by hydro-thermal, sintering
Obtain the vanadium oxide of advance bag carbon；The nanoparticle knot of carbon coating is then obtained with sodium source and phosphorus source ball milling, mist projection granulating, calcining again
The pyrophosphoric acid vanadium sodium of structure.The positive electrode of chondritic produced by the present invention be particle diameter 100-200nm nano particles formation 5~
30 μm of secondary microballoon, and a uniform carbon-coating of nanoparticle Surface coating, realize carbon coating, very while by material nano
The good shortcoming for solving pyrophosphoric acid vanadium sodium electron conduction difference.Using obtained material as sodium-ion battery positive pole, it can show
Go out good high rate performance and long circulating stability energy.In addition, the inventive method technique is simple, reproducible, with low cost, environment
Close friend, can be achieved industrial production in enormous quantities.
Preferably, the carbon source is reproducibility compound.
Further preferably, described carbon source is at least one of glucose, citric acid, oxalic acid, lactose, galactolipin.
Still more preferably, described carbon source is at least one of glucose, citric acid, oxalic acid.
Described vanadium source is trivalent, tetravalence, at least one compound of pentavalent vanadium.Described vanadium source can be molten for water at normal temperature
Property compound, or it is difficult to the oxide of water-soluble vanadium；The for example, oxide of vanadium or its organic and inorganic salt.
Preferably, vanadium source is vanadium trioxide, vanadic anhydride, ammonium metavanadate, vanadyl acetylacetonate, vanadium acetylacetonate
At least one of.
Further preferably, described vanadium source is at least one of vanadium trioxide, vanadic anhydride, ammonium metavanadate.
Preferably, during hydro-thermal reaction, the mol ratio in carbon source and vanadium source is 0.1-10.Obtained in the preferred proportion
Vanadium oxide in vanadium be V3+, bag carbon layers having thicknesses are moderate and more uniform.Ratio is too high, and carbon-coating is too thick, and ratio is too low, then V occurs4 +And V5+。
Further preferably, described carbon source and the mol ratio in vanadium source are 1-10.
Still more preferably, described carbon source and the mol ratio in vanadium source are 1-5；Most preferably 1~2.
Preferably, before hydro-thermal reaction, the initial concentration of described carbon source is 0.01-10g/mL.The preferred concentration model
The hydrothermal product dispersiveness for enclosing interior preparation is more preferable, and granularity is evenly.Excessive concentration, particle agglomeration phenomenon are serious, and concentration is too low, then
Yield is too low.
Further preferably, the initial concentration of described carbon source is 0.01-1g/mL；Still more preferably it is 0.01-0.1g/
mL。
Preferably, hydrothermal temperature is 120-200 DEG C；More preferably 150-200 DEG C
Under described preferred hydrothermal temperature, the reaction time preferably is 10-25h；More preferably 10-20h.
One-level sintering process is carried out under protective atmosphere.Described protective atmosphere is preferably nitrogen, argon gas and hydrogen argon
At least one of gaseous mixture (5% hydrogen).
Preferably, the temperature of one-level sintering is 450-850 DEG C.Sinter at such a temperature, the carbon coating layer of gained is more equal
It is even and electric conductivity is preferable.
Further preferably, one-level sintering temperature is 500-700 DEG C；Still more preferably it is 500-650 DEG C；Most preferably
550-650℃。
The heating rate of one-level sintering process is 1-10 DEG C/min, and rate of temperature fall is 1-10 DEG C/min.The preferred liter,
Rate of temperature fall is more beneficial for ensureing the regularity of material morphology structure.
Further preferably, the heating rate of one-level sintering process is 4-8 DEG C/min, and rate of temperature fall is 2-6 DEG C/min.
In the present invention, carbon coating vanadium oxide made from hydro-thermal and sodium source, phosphorus source ball milling, mist projection granulating calcining are obtained into carbon bag
The pyrophosphoric acid vanadium sodium microballoon covered.The inventors discovered that, grain diameter, the preferable regulation and control of bag carbon layers having thicknesses and uniformity are both contributed to
Further lift the chemical property of material.The present invention passes through to raw material selection and proportioning, and spray drying and sintering schedule
To regulate and control grain diameter and carbon layers having thicknesses and uniformity.
The sodium source is preferably that can in aqueous dissolve and ionizable discharge Na+Compound.
Preferably, described sodium source is sodium carbonate, sodium acetate, sodium oxalate, sodium pyrophosphate, disodium-hydrogen, di(2-ethylhexyl)phosphate
At least one of hydrogen sodium.
Further preferably, sodium source is at least one in sodium carbonate, sodium acetate, sodium oxalate, disodium-hydrogen, sodium dihydrogen phosphate
Kind.
Phosphorus source is preferably that can in aqueous dissolve and ionizable discharge PO4 3-Compound.
Preferably, described phosphorus source be sodium pyrophosphate, phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate, disodium-hydrogen,
At least one of sodium dihydrogen phosphate.
Further preferably, phosphorus source is at least one of phosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate.
The present inventor be also found by numerous studies, and sodium source, the Na in vanadium source and phosphorus source, V, the control of P element mol ratio are existed
In suitable scope, help to lift the electric property of obtained composite positive pole.
Preferably, the ratio mixing of sodium source, the Na in vanadium source and phosphorus source, V, P element mol ratio 0.5-10: 1: 0.1-10.
The ratio of P by the V in the Na in sodium source, vanadium source, in phosphorus source helps to reduce obtained burnt phosphorus in described preferred scope
Sour vanadium sodium impurity is less, and thing is compared pure.Each ratio is not controlled in the preferred scope, is all also easy to produce vanadium phosphate sodium, pyrophosphoric acid
The impurity such as sodium, sodium phosphate.
Further preferably, sodium source, vanadium source and Na in phosphorus source, V, P element mol ratio 0.5-7: 1: 0.1-5.
Still more preferably, sodium source, vanadium source and Na in phosphorus source, V, P element mol ratio 1-5: 1: 0.1-2.
Most preferably, sodium source, vanadium source and Na in phosphorus source, V, P element mol ratio 3.5-5: 1: 1.3-1.8.In preferred parameter
Collaboration under, gained pyrophosphoric acid vanadium sodium impurity is less, and chemical property is more excellent.
Preferably, ball-milling medium is at least one of water, ethanol and acetone.Material and ball milling pearl mass ratio during ball milling
For 0.05-0.1, the mass ratio of ball milling pearl and medium is 2-4.
Preferably, rotational speed of ball-mill is 150-550 revs/min, Ball-milling Time is 5-25h.Under the ball milling system, raw material
Between be well mixed, and the carbon-coating coated in advance will not fall off, and more conducively be made that topography uniformity is good, cladding carbon-coating is thin and uniform
Microballoon.
Further preferably, rotational speed of ball-mill is 150-250 revs/min.
Under described preferred rotational speed of ball-mill, Ball-milling Time preferably is 5-25h；More preferably 10-15h；Ball
Consume time as 5-25h；More preferably 5-10h.
In the inventive method, spherical precursor is obtained after described ball milling and mist projection granulating, presoma is by obtaining carbon
The pyrophosphoric acid vanadium sodium nanoparticle of cladding.
Spray-drying process can use existing routine, maturation method；The inlet temperature of currently preferred spray drying is
180-220 DEG C, 200-250 DEG C of outlet temperature；Charging rate is 45-55g/min, and operating pressure is 4-10MPa, atomizer rotating speed
For 15000-20000rad/min.
Preferably, two grades are sintered under protective atmosphere and carry out, described protective atmosphere is preferably nitrogen, argon gas
It is at least one.
Preferably, two grades of sintering temperatures are 450-850 DEG C.In foregoing ball milling condition and raw material selection, the association of proportioning
With under, then coordinate described calcining heat, the positive electrode of obtained chondritic is formed for particle diameter 100-200nm nano particles
5~30 μm of the secondary microballoon of (assembling), and a uniform carbon-coating of nanoparticle Surface coating, are realized while by material nano
Carbon coating, shows good high rate performance and long circulating stability energy.
Further preferably, two grades of sintering temperatures are 500-700 DEG C.In preferred range, it can obtain by particle diameter 100-
5~30 μm of secondary microballoon of 200nm nano particles formation, improves high rate performance and cycle performance.
Still more preferably, two grades of 500-650 DEG C of sintering temperatures；Most preferably 550-650 DEG C.
The heating rate of two grades of sintering processes is 1-10 DEG C/min, and rate of temperature fall is 1-10 DEG C/min.The preferred liter,
Rate of temperature fall is more beneficial for ensureing the regularity of material morphology structure.
Further preferably, the heating rate of two grades of sintering processes is 4-8 DEG C/min, and rate of temperature fall is 2-6 DEG C/min.
Under two grades of described sintering temperatures and heating-cooling speed, soaking time preferably is 10-40h；Further preferably
For 10-15h.
Described positive electrode is made by washing, drying in product after two grades of sintering.
A kind of preparation method of preferred sodium-ion battery pyrophosphoric acid vanadium sodium positive electrode of the present invention, specifically includes following step
Suddenly：
Step (a)：Vanadium source and carbon source are dissolved in deionized water the hydro-thermal 10-20h at 120-200 DEG C；Hydrothermal product exists
Protective atmosphere, calcine 10-15h at 550-650 DEG C, product is scrubbed, be dried to obtain the vanadium oxide of pre- bag carbon；Described carbon source is
At least one of glucose, citric acid, oxalic acid, lactose, galactolipin；Described carbon source and the mol ratio in vanadium source are 0.1-10；
Step (b)：In Na, V, P element mol ratio 3.5-5: 1: 1.3-1.8 ratio by sodium source, phosphorus source and pre- bag carbon oxygen
Change vanadium in 150-250 revs/min of lower ball milling 5-10h, then spray drying obtains spherical precursor；
Step (c)：Presoma made from step (b) is calcined, calcining heat is 550-650 DEG C, calcination time is
10-15h, heating rate is 4-8 DEG C/min；Calcined product is scrubbed, be dried to obtain the pyrophosphoric acid vanadium sodium nanoparticle of carbon coating.
Present invention additionally comprises a kind of using pyrophosphoric acid vanadium sodium@carbon composite anode materials made from described preparation method, it is
The micro-spherical particle assembled by the pyrophosphoric acid vanadium sodium nano particle for being coated with carbon.
It that is to say, the microballoon that the present invention is agglomerated into by the nano particle (microballoon) of the pyrophosphoric acid vanadium sodium of some carbon coatings
Shape particle (secondary microballoon).
The particle diameter of the nano particle of the pyrophosphoric acid vanadium sodium of described carbon coating is 100-200nm；Described anode composite material
The particle diameter of the micro-spherical particle of material is 5-30 μm.
The positive electrode of chondritic produced by the present invention is 5~30 μm of particle diameter 100-200nm nano particles formation
Secondary microballoon, and a uniform carbon-coating of nanoparticle Surface coating, carbon coating is realized while by material nano, well solution
The shortcoming for pyrophosphoric acid vanadium sodium electron conduction difference of having determined.Using obtained material as sodium-ion battery positive pole, it can show good
High rate performance and long circulating stability energy.
Present invention also offers a kind of application of described pyrophosphoric acid vanadium sodium/carbon composite anode material, the positive pole is combined
Material is used as sodium ion positive electrode.
Preferably, described application, is applied to and prepares sodium-ion battery positive pole.
The cladding of carbon-coating not only increases the electron conduction of material, in the sintering process of follow-up formation pyrophosphoric acid vanadium sodium
In also a certain degree of growth for inhibiting particle, be advantageously implemented material nano, then coordinate micro- obtained by mist projection granulating
Ball presoma, nano level primary particle, the certain sintering temperature of control and sintering time are obtained in sintering process, 5 are obtained
~30 μm of second particle.The secondary microballoon that the material is constituted for the nanoscale primary particle of bag carbon, shortens electronics and particle
Migration path, with good electron conduction and particle conductive, pyrophosphate high rate performance difference is solved well
Problem, while also having good cyclical stability.
The beneficial effect that technical scheme is brought：
1) method that the present invention is engaged using solid, liquid prepares carbon coating pyrophosphoric acid vanadium sodium nanoparticle, described positive pole
Material is the secondary microballoon that nanoscale primary particle is constituted, and the material is used as to the positive pole of sodium-ion battery, burnt phosphorus can be solved
The shortcoming that acid system high rate performance is poor, cyclical stability is bad, with excellent chemical property.
2) in preparation method of the present invention, by the selection of described reproducibility carbon source, carbon source and vanadium source weight than, it is described
Ball milling and calcining mechanism etc. are mutually cooperateed with, and can be regulated and controled the particle diameter of particle and cladding carbon-coating uniformity well, and then
It is obviously improved the chemical property of the positive electrode of gained.
3) sodium-ion battery positive material pyrophosphoric acid vanadium sodium voltage platform prepared by the present invention can reach more than 4V, Ke Yishi
The high-energy-density of existing sodium-ion battery.
4) operation is simple and reliable for preparation method of the invention, reproducible, workable, environment-friendly, suitable large quantities of
Amount production, and low cost of raw materials, with wide industrial applications prospect.
Brief description of the drawings
【Fig. 1】The scanning electron microscope (SEM) photograph of sodium-ion battery positive material made from embodiment 1；
【Fig. 2】The discharge cycles figure of the sodium-ion battery positive material made from embodiment 1.
Embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Following examples and comparative example, described spray drying parameters, unless specified or limited otherwise, its inlet temperature exist
180-220 DEG C, outlet temperature is at 200-250 DEG C；Charging rate is in 45-55g/min, and operating pressure is in 4-10MPa, mist
Change device rotating speed in 15000-20000rad/min.
Embodiment 1
2g vanadic anhydride (0.01mol) and 5g citric acids (0.026mol) is weighed first, is dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 180 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then in nitrogen or the protective atmosphere of argon gas
Under, 600 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, at 70 DEG C
2h is dried, pre- bag oxidation of coal vanadium is produced.
Pre- bag oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) are existed
Ball milling 7h in alcoholic media, rotating speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma is in nitrogen atmosphere
Under with 4 DEG C/min speed be heated to 600 DEG C in tube furnace, calcining 15h obtains black powder；Finally by black powder go from
Sub- water washing three times, ethanol wash twice, is dried, obtains final products (Na7V3(P2O7)4).The ESEM of obtained product
Figure is shown in Fig. 1；Known by Fig. 1, composite positive pole made from the present embodiment has the nano particle of bag carbon pyrophosphoric acid vanadium sodium (once
Grain grain) microballoon that is agglomerated into；, its grain diameter is 150nm nanometers, and specific grain surface product is 250-300m2/ g, carbon coated
Thickness degree is 10nm, secondary 30 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance.Fig. 2 is positive electrode made from the present embodiment in current density
160mA/g (2C) specific discharge capacity and cycle efficieny data.
From Fig. 2 test results, sodium electricity prepared by this example is just having good chemical property；In 160mA/g
Under the current density of (2C), first circle capacity is 68mAh/g, after circulation 50 is enclosed, and remains to keep 62mAh/g specific capacity.
Embodiment 2
The ammonium metavanadate (0.025mol) and 7.5g glucose (0.04mol) for weighing 3g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 180 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then in nitrogen or the protective atmosphere of argon gas
Under, 600 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, at 70 DEG C
2h is dried, pre- bag oxidation of coal vanadium is produced.
Take pre- bag oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 5g (0.04mol), sodium carbonate 4.5g (0.042mol) ball
7h is ground, rotating speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma under nitrogen atmosphere in tube furnace
600 DEG C are heated to 4 DEG C/min speed, calcining 15h obtains black powder；Black powder deionized water is finally washed three
Secondary, ethanol wash twice, is dried, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；Its grain diameter 150nm, specific grain surface product is 200-300m2/ g, cladding carbon layers having thicknesses are 10nm, two
Secondary 20-30 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance.Under 160mA/g (2C) current density, first circle specific capacity is
After 67mAh/g, the circle of circulation 50,60mAh/g specific capacity can be kept.It can be seen that, reproducibility carbon source is changed into glucose by citric acid,
High rate performance and cycle performance are slightly decreased.
Embodiment 3
The vanadic anhydride (0.01mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 150 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
600 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
By pre- bag oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mo1) ball
7h is ground, rotating speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma under nitrogen atmosphere in tube furnace
600 DEG C are heated to 4 DEG C/min speed, calcining 15h obtains black powder；Black powder deionized water is finally washed three
Secondary, ethanol wash twice, is dried, obtains final products (Na7V3(P2O7)4)。
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 120nm, specific grain surface product is 180-250m2/ g, cladding carbon layers having thicknesses are 8nm, two
Secondary 25-30 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance.Under 160mA/g (2C) current density, first circle capacity is
After 68mAh/g, the circle of circulation 50,63mAh/g specific capacity can be kept.It can be seen that, hydrothermal temperature is down to 150 DEG C, material property base
This holding is constant.
Embodiment 4
The vanadic anhydride (0.022mol V) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionizations
In water, stirring forms homogeneous solution, the aqueous solution is poured into ptfe autoclave, then by the polytetrafluoroethylene (PTFE)
Reactor is put into stainless steel water heating kettle and sealed, and finally the stainless steel water heating kettle is placed in homogeneous reactor, at 180 DEG C
Carry out hydro-thermal reaction 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
650 DEG C of high temperature sintering 15h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
By pre- bag oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.056mol
Na) ball milling 7h, rotating speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma under nitrogen atmosphere in pipe
550 DEG C are heated to 4 DEG C/min speed in formula stove, calcining 15h obtains black powder；Finally black powder deionization is washed
Wash three times, ethanol wash twice, is dried, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 150nm, specific grain surface product is 200-250m2/ g, cladding carbon layers having thicknesses are 15nm, two
Secondary 20-25 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance.Under 160mA/g (2C) current density, first circle capacity is
After 67mAh/g, the circle of circulation 50,56mAh/g specific capacity can be kept.
Embodiment 5
The ammonium metavanadate (0.017mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 180 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
650 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
By pre- bag oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball
7h is ground, rotating speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma under nitrogen atmosphere in tube furnace
650 DEG C are heated to 4 DEG C/min speed, calcining 15h obtains black powder；Black powder deionized water is finally washed three
Secondary, ethanol wash twice, is dried, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 120nm, specific grain surface product is 250-300m2/ g, cladding carbon layers having thicknesses are 10nm, two
Secondary 25-30 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance.Under 160mA/g (2C) current density, first circle capacity is
After 72mAh/g, the circle of circulation 50,63mAh/g specific capacity can be kept.
Embodiment 6
The ammonium metavanadate (0.017mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 180 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
650 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
Will obtained pre- bag oxidation of coal vanadium, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, rotating speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma under nitrogen atmosphere in tube furnace with
4 DEG C/min speed is heated to 550 DEG C, and calcining 15h obtains black powder；Finally black powder deionized water is washed three times,
Ethanol wash twice, is dried, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 150nm, specific grain surface product is 250-300m2/ g, cladding carbon layers having thicknesses are 12nm, two
Secondary 25-30 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance.Under 160mA/g (2C) current density, first circle capacity is
After 70mAh/g, the circle of circulation 50,62mAh/g specific capacity can be kept.
Embodiment 7
The ammonium metavanadate (0.017mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 180 DEG C
Water-filling thermal response 15 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
650 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
Will obtained pre- bag oxidation of coal vanadium, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, rotating speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma under nitrogen atmosphere in tube furnace with
4 DEG C/min speed is heated to 650 DEG C, and calcining 15h obtains black powder；Finally black powder deionized water is washed three times,
Ethanol wash twice, is dried, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 120nm, specific grain surface product is 180-250m2/ g, cladding carbon layers having thicknesses are 15nm, two
Secondary 25-30 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance.Under 160mA/g (2C) current density, first circle capacity is
After 70mAh/g, the circle of circulation 50,64mAh/g specific capacity can be kept.
Embodiment 8
The vanadic anhydride (0.011mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 180 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
600 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
Will obtained pre- bag oxidation of coal vanadium, ammonium dihydrogen phosphate 3.45g (0.03mol), sodium acetate 2.3g (0.028mol) ball
7h is ground, rotating speed is 200 revs/min.Presoma in being heated to 600 DEG C in tube furnace with 4 DEG C/min speed under nitrogen atmosphere,
Calcining 15h obtains black powder；Finally black powder deionized water is washed three times, ethanol wash twice, is dried, obtain final
Product (Na7V3 (P2O7) 4).
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 120nm, specific grain surface product is 180-250m2/ g, cladding carbon layers having thicknesses are 8nm, two
Secondary 25-30 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance；Test result shows, the electric negative pole electrochemistry of sodium prepared by this example
Poor-performing；Under 160mA/g (2C) current density, first circle specific discharge capacity is holding after 71mA/g, the circle of circulation 50
64mAh/g specific capacity.
Comparative example 1
The vanadic anhydride (0.011mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 180 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
600 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
Will obtained pre- bag oxidation of coal vanadium, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, rotating speed is 200 revs/min.Presoma is forged in being heated to 600 DEG C in tube furnace with 4 DEG C/min speed under nitrogen atmosphere
Burn 15h and obtain black powder；Finally black powder deionized water is washed three times, ethanol wash twice, is dried, finally produced
Product (Na7V3(P2O7)4)。
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；Its grain diameter 700nm, specific grain surface product is 80-100m2/ g, cladding carbon layers having thicknesses are 20nm, secondary
70-80 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance；Test result shows, the electric negative pole electrochemistry of sodium prepared by this example
Poor-performing；Under 160mA/g (2C) current density, first circle specific discharge capacity is only 45mA/g, is kept after the circle of circulation 50
22mAh/g specific capacity.Not by spray drying, material primary particle is larger, and the second particle of formation is bigger so that particle
Transmission path increase, high rate performance and cyclical stability are deteriorated.
Comparative example 2
2g vanadic anhydride (0.011mol), 5g citric acids (0.026mol), 3.5g sodium dihydrogen phosphates is weighed first
(0.03mol) and 3g sodium carbonate (0.028mol), adds in clean ball grinder, adds 150g agate beads and 40mL ethanol,
12h ball milling is carried out, rotational speed of ball-mill is 500 revs/min.Ball milling product is positioned in 70 DEG C of baking ovens and dries 12h.Desciccate
Spherical precursor is obtained by spray drying.Presoma in tube furnace under nitrogen atmosphere with 4 DEG C/min speed in being heated to
600 DEG C, calcining 15h obtains black powder；Finally black powder deionized water is washed three times, ethanol wash twice, is dried, obtained
To final products (Na7V3(P2O7)4)。
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 600nm, specific grain surface product is 80-120m2/ g, cladding carbon layers having thicknesses are 40nm, two
Secondary 70-80 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance；Under 160mA/g (2C) current density, first circle capacity is
After 48mA/g, the circle of circulation 50,38mAh/g specific capacity can be kept.As a result show, the system of bag oxidation of coal vanadium is prepared without hydro-thermal
It is standby but directly ball milling, the high rate performance for calcining resulting materials are poor, it may be possible to without the carbon-coating coated in advance, presoma
The growth of pyrophosphoric acid vanadium sodium crystal is not affected by limitation, and not uniform enough the institute of calcining products therefrom carbon coating layer during follow-up sintering
Cause.
Comparative example 3
2g vanadic anhydride (0.011mol), 5g citric acids (0.026mol), 3.5g sodium dihydrogen phosphates is weighed first
(0.03mol) and 3g sodium carbonate (0.028mol), is added in 100mL deionized waters, and stirring forms homogeneous solution, will be described water-soluble
Liquid is poured into ptfe autoclave, and then the ptfe autoclave is put into stainless steel water heating kettle and sealed,
Finally the stainless steel water heating kettle is placed in homogeneous reactor, hydro-thermal reaction is carried out at 180 DEG C 10 hours.Hydrothermal product is put
It is placed in 70 DEG C of baking ovens and dries 12h.Desciccate obtains spherical precursor by spray drying.Presoma under nitrogen atmosphere
600 DEG C are heated to 4 DEG C/min speed in tube furnace, calcining 15h obtains black powder；Finally by black powder deionized water
Washing three times, ethanol wash twice, is dried, obtains final products (Na7V3(P2O7)4)。
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 400nm, specific grain surface product is 80-100m2/ g, cladding carbon layers having thicknesses are 25nm, two
Secondary 50-60 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance；Under 160mA/g (2C) current density, first circle capacity is
After 54mA/g, the circle of circulation 50,38mAh/g specific capacity can be kept.As a result show, without pre- bag carbon but direct step water
Hot, calcining resulting materials high rate performances are poor, it may be possible to which, without the carbon-coating coated in advance, presoma is in follow-up sintering mistake
The growth of pyrophosphoric acid vanadium sodium crystal is not affected by limitation in journey, causes grain diameter larger, and high rate performance declines.
Comparative example 4
The vanadic anhydride (0.011mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 230 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
600 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
Will obtained pre- bag oxidation of coal vanadium, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, rotating speed is 200 revs/min.Presoma is forged in being heated to 600 DEG C in tube furnace with 4 DEG C/min speed under nitrogen atmosphere
Burn 15h and obtain black powder；Finally black powder deionized water is washed three times, ethanol wash twice, is dried, finally produced
Product (Na7V3 (P2O7) 4).
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 400nm, specific grain surface product is 50-80m2/ g, cladding carbon layers having thicknesses are 35nm, secondary
60-80 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance；Test result shows, the electric negative pole electrochemistry of sodium prepared by this example
Poor-performing；Under 160mA/g (2C) current density, first circle specific discharge capacity is only 45mA/g, is kept after the circle of circulation 50
34mAh/g specific capacity.Hydrothermal temperature is increased to 230 DEG C, beyond preferred scope, in the case where other conditions are constant,
High rate performance and cyclical stability decline more, it is seen that the control of hydrothermal condition is larger on Morphological control influence of material.
Comparative example 5
The vanadic anhydride (0.011mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 100 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
600 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
Will obtained pre- bag oxidation of coal vanadium, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, rotating speed is 200 revs/min.Presoma is forged in being heated to 600 DEG C in tube furnace with 4 DEG C/min speed under nitrogen atmosphere
Burn 15h and obtain black powder；Finally black powder deionized water is washed three times, ethanol wash twice, is dried, finally produced
Product (Na7V3 (P2O7) 4).
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 400-700nm, specific grain surface product is 80-100m2/ g, cladding carbon layers having thicknesses are 30-
50nm, secondary 60-85 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance；Test result shows, the electric negative pole electrochemistry of sodium prepared by this example
Poor-performing；Under 160mA/g (2C) current density, first circle specific discharge capacity is only 45mA/g, is kept after the circle of circulation 50
34mAh/g specific capacity.Hydrothermal temperature is dropped to 100 DEG C, other conditions are constant, the decline of material high rate performance is more, may
It is that hydrothermal temperature is relatively low, product grain is larger and uneven.
Comparative example 6
The vanadic anhydride (0.011mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 180 DEG C
Water-filling thermal response 30 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
600 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
Will obtained pre- bag oxidation of coal vanadium, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, rotating speed is 200 revs/min.Presoma is forged in being heated to 600 DEG C in tube furnace with 4 DEG C/min speed under nitrogen atmosphere
Burn 15h and obtain black powder；Finally black powder deionized water is washed three times, ethanol wash twice, is dried, finally produced
Product (Na7V3 (P2O7) 4).
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 600-700nm, specific grain surface product is 80-100m2/ g, cladding carbon layers having thicknesses are 20-
40nm, secondary 60-80 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance；Test result shows, the electric negative pole electrochemistry of sodium prepared by this example
Poor-performing；Under 160mA/g (2C) current density, first circle specific discharge capacity is only 44mA/g, is kept after the circle of circulation 50
32mAh/g specific capacity.The hydro-thermal time is increased into 30h, other conditions are constant, high rate performance and cyclical stability decline compared with
It is many, it is seen that the control of hydrothermal condition is larger on Morphological control influence of material.
Comparative example 7
The vanadic anhydride (0.011mol) and 5g citric acids (0.026mol) for weighing 2g first are dissolved in 100ml deionized waters
In, stirring forms homogeneous solution, and the aqueous solution is poured into ptfe autoclave, then that the polytetrafluoroethylene (PTFE) is anti-
Answer kettle to be put into stainless steel water heating kettle and seal, finally the stainless steel water heating kettle is placed in homogeneous reactor, entered at 180 DEG C
Water-filling thermal response 10 hours.Hydrothermal product is positioned in 70 DEG C of baking ovens and dries 12h.Then under the protective atmosphere of nitrogen,
600 DEG C of high temperature sintering 12h in tube furnace, product through deionized water wash three times, then with ethanol wash twice, in 70 DEG C of dryings
2h, produces pre- bag oxidation of coal vanadium.
Will obtained pre- bag oxidation of coal vanadium, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, rotating speed is 200 revs/min.Presoma is forged in being heated to 600 DEG C in tube furnace with 4 DEG C/min speed under nitrogen atmosphere
Burn 45h and obtain black powder；Finally black powder deionized water is washed three times, ethanol wash twice, is dried, finally produced
Product (Na7V3 (P2O7) 4).
The nano particle (primary particle grain) that composite positive pole made from the present embodiment has bag carbon pyrophosphoric acid vanadium sodium is reunited
Into microballoon；, its grain diameter 700nm, specific grain surface product is 80-100m2/ g, cladding carbon layers having thicknesses are 35nm, two
Secondary 78-80 μm of microspherulite diameter.
Pyrophosphoric acid vanadium sodium material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 160mA/g (2C) current density, test loop performance；Test result shows, the electric negative pole electrochemistry of sodium prepared by this example
Poor-performing；Under 160mA/g (2C) current density, first circle specific discharge capacity is only 45mA/g, is kept after the circle of circulation 50
34mAh/g specific capacity.Two grades of calcination times are increased into 45h from 15h, beyond preferred scope, and other conditions are constant, material
Chemical property degradation, it may be possible to because calcination time increase causes grain diameter to increase, deterioration in material properties.
Claims (10)
1. a kind of pyrophosphoric acid vanadium sodium carbon composite anode material, it is characterised in that described composite positive pole is by being coated with carbon
The micro-spherical particle that assembles of pyrophosphoric acid vanadium sodium nano particle.
2. pyrophosphoric acid vanadium sodium@carbon composite anode materials as claimed in claim 1, it is characterised in that be coated with the pyrophosphoric acid of carbon
The particle diameter of vanadium sodium nano particle is 100-200nm；The particle diameter of the micro-spherical particle of the composite positive pole is 5-30 μm；Compare table
Area is 20-400m2/g；Cladding carbon layers having thicknesses are 5-40nm.
3. the preparation method of the pyrophosphoric acid vanadium sodium@carbon composite anode materials described in a kind of claim 1 or 2, it is characterised in that will
Solution comprising carbon source and vanadium source carries out hydro-thermal reaction, and hydro-thermal reaction product is carried out into one-level sintering, and bag oxidation of coal vanadium is made；Will
It is spray-dried after obtained bag oxidation of coal vanadium, sodium source, phosphorus source wet ball grinding, obtains presoma；Presoma carries out two grades and sinters to obtain institute
The composite positive pole stated.
4. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode materials as claimed in claim 3, it is characterised in that described
Vanadium source is at least one of vanadium trioxide, vanadic anhydride, ammonium metavanadate, vanadyl acetylacetonate, vanadium acetylacetonate；
The carbon source is reproducibility carbon source；Preferably at least one of glucose, citric acid, oxalic acid, lactose, galactolipin；
Carbon source and the mol ratio in vanadium source are 0.1-10.
5. the preparation method of the pyrophosphoric acid vanadium sodium@carbon composite anode materials as described in claim 3 or 4, it is characterised in that hydro-thermal
Reaction temperature is 120-200 DEG C；Reaction time is 10-25h.
6. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode materials as claimed in claim 3, it is characterised in that sodium source is
Sodium carbonate, sodium acetate, sodium oxalate, sodium pyrophosphate, phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate, disodium-hydrogen, biphosphate
At least one of sodium；
Phosphorus source is at least one in sodium pyrophosphate, phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate, disodium-hydrogen, sodium dihydrogen phosphate
Kind.
7. the preparation method of the pyrophosphoric acid vanadium sodium@carbon composite anode materials as described in claim 3 or 6, it is characterised in that sodium
Source, the Na in vanadium source and phosphorus source, V, the ratio mixing of P element mol ratio 0.5-10: 1: 0.1-10.
8. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode materials as claimed in claim 3, it is characterised in that wet method ball
The medium of honed journey is water or unlimited than at least one of miscible solvent with water；Rotational speed of ball-mill is 150-550 revs/min；
Ball-milling Time is 5-25h.
9. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode materials as claimed in claim 3, it is characterised in that one-level is burnt
The temperature of knot and double sintering is 450 DEG C -850 DEG C alone；Time is 10-40h alone.
10. a kind of application of the pyrophosphoric acid vanadium sodium@carbon composite anode materials described in any one of claim 1~2, its feature exists
In as sodium-ion battery positive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710407975.XA CN107195886B (en) | 2017-06-01 | 2017-06-01 | A kind of pyrophosphoric acid vanadium sodium@carbon composite anode material, preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710407975.XA CN107195886B (en) | 2017-06-01 | 2017-06-01 | A kind of pyrophosphoric acid vanadium sodium@carbon composite anode material, preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107195886A true CN107195886A (en) | 2017-09-22 |
| CN107195886B CN107195886B (en) | 2019-11-05 |
Family
ID=59876981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710407975.XA Expired - Fee Related CN107195886B (en) | 2017-06-01 | 2017-06-01 | A kind of pyrophosphoric acid vanadium sodium@carbon composite anode material, preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107195886B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767237A (en) * | 2018-06-04 | 2018-11-06 | 福州大学 | The hollow ball shape vanadium trioxide compound and its preparation method and application that one-step synthesis method carbon is supported |
| CN109192982A (en) * | 2018-09-05 | 2019-01-11 | 四川大学 | The synthetic method of sulfuric acid ferrisodium positive electrode |
| CN109659505A (en) * | 2017-10-10 | 2019-04-19 | 中国科学院大连化学物理研究所 | A kind of NaVP2O7Application in sodium-ion battery anode |
| CN109775680A (en) * | 2018-08-07 | 2019-05-21 | 上海紫剑化工科技有限公司 | A kind of vanadium phosphate sodium nanometer sheet and its preparation method and application |
| CN109841809A (en) * | 2019-01-04 | 2019-06-04 | 三峡大学 | A kind of preparation method of Na3V2 (PO4) 3/C porous microsphere sodium-ion battery positive material |
| CN111293307A (en) * | 2018-12-06 | 2020-06-16 | 中国科学院大连化学物理研究所 | Carbon-supported sodium vanadium fluorophosphate and preparation and application thereof |
| CN111446429A (en) * | 2020-03-27 | 2020-07-24 | 珠海冠宇电池股份有限公司 | Poly-polyanion cathode material and preparation method and application thereof |
| CN113054184A (en) * | 2019-12-27 | 2021-06-29 | 深圳新宙邦科技股份有限公司 | Symmetric sodium-ion battery and preparation method thereof |
| CN113285072A (en) * | 2021-07-24 | 2021-08-20 | 南杰智汇(深圳)科技有限公司 | Pyrophosphate composite material, sodium ion battery anode, sodium ion battery cathode and sodium ion battery |
| CN113328086A (en) * | 2021-08-03 | 2021-08-31 | 南杰智汇(深圳)科技有限公司 | Pyrophosphate composite material, preparation method and application thereof, and sodium ion battery |
| CN116864660A (en) * | 2023-09-04 | 2023-10-10 | 浙江华宇钠电新能源科技有限公司 | Sodium vanadium phosphate positive electrode material and battery for vehicle |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186290A (en) * | 2007-12-11 | 2008-05-28 | 深圳市贝特瑞新能源材料股份有限公司 | Anode material vanadium lithium phosphate and preparation method thereof |
| CN101795963A (en) * | 2007-09-06 | 2010-08-04 | 威伦斯技术公司 | Method of making active materials for use in secondary electrochemical cells |
| WO2014102531A4 (en) * | 2012-12-28 | 2014-10-30 | Faradion Ltd | Metal-containing compounds |
| US20150303474A1 (en) * | 2012-11-28 | 2015-10-22 | Faradion Limited | Metal-containing compounds |
| CN106784727A (en) * | 2017-01-17 | 2017-05-31 | 东莞市迈科新能源有限公司 | A kind of polyanionic sodium-ion battery positive material and preparation method thereof |
-
2017
- 2017-06-01 CN CN201710407975.XA patent/CN107195886B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101795963A (en) * | 2007-09-06 | 2010-08-04 | 威伦斯技术公司 | Method of making active materials for use in secondary electrochemical cells |
| CN101186290A (en) * | 2007-12-11 | 2008-05-28 | 深圳市贝特瑞新能源材料股份有限公司 | Anode material vanadium lithium phosphate and preparation method thereof |
| US20150303474A1 (en) * | 2012-11-28 | 2015-10-22 | Faradion Limited | Metal-containing compounds |
| WO2014102531A4 (en) * | 2012-12-28 | 2014-10-30 | Faradion Ltd | Metal-containing compounds |
| CN106784727A (en) * | 2017-01-17 | 2017-05-31 | 东莞市迈科新能源有限公司 | A kind of polyanionic sodium-ion battery positive material and preparation method thereof |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659505A (en) * | 2017-10-10 | 2019-04-19 | 中国科学院大连化学物理研究所 | A kind of NaVP2O7Application in sodium-ion battery anode |
| CN108767237A (en) * | 2018-06-04 | 2018-11-06 | 福州大学 | The hollow ball shape vanadium trioxide compound and its preparation method and application that one-step synthesis method carbon is supported |
| CN109775680A (en) * | 2018-08-07 | 2019-05-21 | 上海紫剑化工科技有限公司 | A kind of vanadium phosphate sodium nanometer sheet and its preparation method and application |
| CN109775680B (en) * | 2018-08-07 | 2022-06-10 | 上海紫剑化工科技有限公司 | Sodium vanadium phosphate nanosheet and preparation method and application thereof |
| CN109192982A (en) * | 2018-09-05 | 2019-01-11 | 四川大学 | The synthetic method of sulfuric acid ferrisodium positive electrode |
| CN109192982B (en) * | 2018-09-05 | 2021-08-24 | 四川大学 | Method for synthesizing sodium ferric sulfate anode material |
| CN111293307B (en) * | 2018-12-06 | 2021-06-29 | 中国科学院大连化学物理研究所 | Carbon-supported sodium vanadium fluorophosphate and preparation and application thereof |
| CN111293307A (en) * | 2018-12-06 | 2020-06-16 | 中国科学院大连化学物理研究所 | Carbon-supported sodium vanadium fluorophosphate and preparation and application thereof |
| CN109841809A (en) * | 2019-01-04 | 2019-06-04 | 三峡大学 | A kind of preparation method of Na3V2 (PO4) 3/C porous microsphere sodium-ion battery positive material |
| CN113054184A (en) * | 2019-12-27 | 2021-06-29 | 深圳新宙邦科技股份有限公司 | Symmetric sodium-ion battery and preparation method thereof |
| CN113054184B (en) * | 2019-12-27 | 2023-03-10 | 深圳新宙邦科技股份有限公司 | Symmetric sodium-ion battery and preparation method thereof |
| CN111446429A (en) * | 2020-03-27 | 2020-07-24 | 珠海冠宇电池股份有限公司 | Poly-polyanion cathode material and preparation method and application thereof |
| CN113285072A (en) * | 2021-07-24 | 2021-08-20 | 南杰智汇(深圳)科技有限公司 | Pyrophosphate composite material, sodium ion battery anode, sodium ion battery cathode and sodium ion battery |
| CN113285072B (en) * | 2021-07-24 | 2021-11-02 | 南杰智汇(深圳)科技有限公司 | Pyrophosphate composite material, sodium ion battery anode, sodium ion battery cathode and sodium ion battery |
| CN113328086A (en) * | 2021-08-03 | 2021-08-31 | 南杰智汇(深圳)科技有限公司 | Pyrophosphate composite material, preparation method and application thereof, and sodium ion battery |
| CN113328086B (en) * | 2021-08-03 | 2021-11-02 | 南杰智汇(深圳)科技有限公司 | Pyrophosphate composite material, preparation method and application thereof, and sodium ion battery |
| CN116864660A (en) * | 2023-09-04 | 2023-10-10 | 浙江华宇钠电新能源科技有限公司 | Sodium vanadium phosphate positive electrode material and battery for vehicle |
| CN116864660B (en) * | 2023-09-04 | 2023-12-15 | 浙江华宇钠电新能源科技有限公司 | Sodium vanadium phosphate positive electrode material and battery for vehicle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107195886B (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107195886B (en) | A kind of pyrophosphoric acid vanadium sodium@carbon composite anode material, preparation and application | |
| CN103066280B (en) | spherical lithium iron phosphate anode material and preparation method thereof | |
| CN101834291B (en) | Preparation method of submicron level LiniO.5MnO.5O2 cathode material | |
| CN101728526B (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN102332583B (en) | Method for preparing lithium iron phosphate anode material with carbon-coated surface for lithium battery | |
| CN105161314B (en) | Nano-nickel oxide/nickel/graphene composite material and its preparation method and application | |
| CN103606660A (en) | Alumina-coated granules, as well as preparation method and application thereof | |
| CN101908628A (en) | Transition metal composite oxide catalytic material and microwave preparation method thereof | |
| CN105938904A (en) | Composite positive electrode material for sodium-ion battery and preparation method of composite positive electrode material | |
| CN106876705A (en) | A kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite | |
| CN102694185A (en) | Composite electrocatalyst material used for Li-air batteries and preparation method thereof | |
| CN105428633A (en) | Method for preparing titanium niobate mesoporous microspheres | |
| CN107017398B (en) | A kind of pyrophosphoric acid vanadium sodium/carbon composite anode material, preparation and its application | |
| CN107808958A (en) | Preparation method of ferroso-ferric oxide/nitrogen-doped graphene composite and products thereof and application | |
| CN107017394B (en) | A kind of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material, preparation and application | |
| CN110391417A (en) | The preparation method of one type monocrystalline lithium-rich manganese-based anode material | |
| CN107146883A (en) | Pyrophosphoric acid cobalt sodium/carbon anode composite material, preparation and its application of a kind of core shell structure | |
| CN102790210A (en) | Method for preparing cathode material lithium manganate of lithium ion battery by supercritical hydrothermal reaction | |
| CN106784726A (en) | Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof | |
| CN103500829B (en) | The preparation method of LiFePO 4 | |
| CN102110508A (en) | Preparation method of iron-based magnetic material/carbon composite powder | |
| CN110492076B (en) | Preparation method of two-dimensional porous hexagonal metal oxide nanosheet composite material and application of composite material in potassium ion battery | |
| CN109473682B (en) | Supported binuclear perovskite type oxide carbon nano microsphere catalyst, and preparation method and application thereof | |
| CN110474039B (en) | Sodium-ion battery positive electrode material and preparation method and application thereof | |
| CN103474629A (en) | Semi-hollow bicontinuous line-structure coaxial nanowire material in H2V3O8/graphene tube, as well as preparation method and application of material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191105 Termination date: 20210601 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |