CN107195886B - A kind of pyrophosphoric acid vanadium sodium@carbon composite anode material, preparation and application - Google Patents
A kind of pyrophosphoric acid vanadium sodium@carbon composite anode material, preparation and application Download PDFInfo
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- CN107195886B CN107195886B CN201710407975.XA CN201710407975A CN107195886B CN 107195886 B CN107195886 B CN 107195886B CN 201710407975 A CN201710407975 A CN 201710407975A CN 107195886 B CN107195886 B CN 107195886B
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Abstract
The invention discloses a kind of preparation methods of sodium-ion battery pyrophosphoric acid vanadium sodium positive electrode, prepare the pyrophosphoric acid vanadium sodium of carbon coating micro-sphere structure.Vanadium source and carbon source prepare the vanadium oxide of cladding carbon-coating in advance by hydro-thermal, pre-sintering, 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 carbon-coated micro-sphere structure after calcining, washing, drying.In addition, the invention also discloses using sodium-ion battery positive material made from the preparation method.Prepared material is the secondary microballoon that a nano particle is formed, which is used for sodium-ion battery, shows excellent chemical property, has industrial applications prospect.
Description
Technical field
The invention belongs to sodium-ion battery fields, and in particular to a kind of sodium-ion battery positive material and preparation method thereof.
Background technique
Currently, the fossil fuels such as coal, petroleum are still main for electric resources.It is unreasonable however as the mankind, without section
The exploitation and utilization of system, in addition the not system of recycling, unreasonable, not scientific, fossil energy day is becoming tight.In order to solve this
Problem, extensive electricity storage technology become an important field of research.Wherein, secondary cell due to energy with higher it is close
Degree and transformation efficiency become the preferential selection of extensive storage, and with the lithium ion having extended cycle life and energy density is high
Battery is considered as most promising secondary cell.Since the 1990s, lithium ion battery successfully came out, in electricity
Electrical automobile, mancarried electronic aid etc. have obtained quite being widely applied, but being constantly progressive and sending out with lithium ion battery
The raising of the demand and requirement of exhibition and people to secondary cell, a series of hidden danger and problem have also gradually been exposed to people
The visual field in, therefore it is extremely urgent to develop a kind of cheap, sustainable development battery system.
Sodium and lithium are located at same main group, have similar physics and chemical property, and sodium resource reserve is abundant, can be continuous
Slave seawater in extract.Although sodium ion radius is larger for lithium, standard electrochemical current potential is lower, lead to 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, low in cost, highly-safe sodium-ion battery has quite wide prospect, and it is most important will certainly to become the rear lithium epoch
One of developing direction.
Currently, based on the considerations of developing material cost and application prospect, studied in sodium-ion battery it is more, most by section
It grinds personnel's concern and surely belongs to sodium-ion battery positive material.The storage sodium positive electrode reported at present mainly has polyanionic chemical combination
Object, prussian blue sodium salt and transition metal oxide.Transition metal oxide has cobalt acid sodium, sodium manganate etc., it is characterized in that
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 a kind of complex containing transition metal of appraising at the current rate, it is this kind of
Compound has complete cubic, has three-dimensional space structure, and there is a large amount of coordination gaps, 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 (coke) phosphate, fluorophosphate etc..Phosphate compound is often stabilized with fast sodium ion conductor or olivine structural,
Structural framework containing biggish ion channel and Three-dimensional Open.The frame structure of transition metal phosphate is relatively stable, uses
When anode in charge and discharge process, there is preferable cyclical stability and higher security performance, but this kind of material is main
The disadvantage is that electronic conductivity is low, sodium ion causes by force sodium ion diffusion velocity slower with phosphate backbone binding force, volume energy
Density is small, and capacity attenuation is big when high-multiplying power discharge.And the synthesis of this kind of material mainly all uses high temperature solid-state method, and it is at high cost,
And preparation process complex process, easily causes environmental pollution.And in a series of this positive electrode, polyanionic compound by
It is concerned in characteristics such as its high voltage, long circulating and excellent safeties.
Summary of the invention
An object of the present disclosure is to provide a kind of pyrophosphoric acid vanadium sodium@carbon composite anode material.
The present invention second is designed to provide a kind of preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode material, it is intended to mention
For a kind of simple process, reproducible, low in cost, environmental-friendly preparation method.
Third of the present invention is designed to provide the application in sodium-ion battery field of the anode composite material, it is intended to
By the positive electrode, the chemical property of sodium-ion battery is promoted.
A kind of pyrophosphoric acid vanadium sodium carbon composite anode material, which is characterized in that for by the pyrophosphoric acid vanadium sodium nanometer for being coated with carbon
The micro-spherical particle that particle assembles.
The partial size for being coated with the pyrophosphoric acid vanadium sodium nano particle of carbon is 100-200nm；Specific surface area is 20-400m2/g；Packet
Covering carbon layers having thicknesses is 5-40nm.
The partial size 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
Diameter is 100-200nm, the microballoon that second particle is 5-30 μm of partial size.
The present invention also provides the preparation methods of the pyrophosphoric acid vanadium sodium@carbon composite anode material described in one kind, will include carbon
The solution in source and vanadium source carries out hydro-thermal reaction, and hydro-thermal reaction product is carried out level-one sintering, packet oxidation of coal vanadium is made；It will be obtained
It is spray-dried after packet oxidation of coal vanadium, sodium source, phosphorus source wet ball grinding, obtains presoma；What presoma carried out that second level is sintered described answers
Close positive electrode.
Vanadium source and carbon source are originally first first carried out hydro-thermal and level-one sintering processes, made in vanadium oxide by the method for the present invention
Surface in situ be coated with carbon material layer, the packet oxidation of coal vanadium is made, then packet oxidation of coal vanadium and sodium source and phosphorus source are carried out
Mixing, sintering obtain the composite positive pole.The present invention is compared to preparations sides such as one pot of hydro-thermal or direct ball milling mixings
Method, composite positive pole performance obtained are more excellent；In addition, the method for the present invention simple process, reproducible, low in cost, ring
Border is friendly.
Preparation method of the present invention, key are preparation route of the invention, that is to say vanadium source and the carbon source preferentially
Hydro-thermal-level-one, which is sintered, is made packet oxidation of coal vanadium；Then ball milling, spraying, double sintering, assembling obtain the second particle again.
It, can be into addition, the control of the parameters such as described hydrothermal reaction condition, Na, V, P element molar ratio and sintering process temperature of cooperation
One step promotes the electric property of composite positive pole obtained.
In the present invention, vanadium source and carbon source are dissolved and/or disperse to obtain the solution in a solvent, followed by
Hydro-thermal reaction.The solvent can be for water or with water infinitely than miscible solvent, for example, the alcohol or acetone etc. of C1~4；Institute
The alcohol for C1~4 stated is, for example, methanol, ethyl alcohol, isopropanol etc..
Preferably, the solvent medium of hydro-thermal reaction is water and/or ethyl alcohol.
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 preparatory packet carbon；Then carbon-coated nanosphere knot is 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 partial size 100-200nm nano particle formed 5~
30 μm of secondary microballoon, and a nanoparticle surface is evenly coated carbon-coating, carbon coating is realized while by material nano, very
The good disadvantage for solving pyrophosphoric acid vanadium sodium electron conduction difference.Using material obtained as sodium-ion battery anode, can express
Good high rate performance and long circulating stability energy out.In addition, the method for the present invention simple process, reproducible, low in cost, environment
It is friendly, it can be achieved that industrial mass production.
Preferably, the carbon source is reproducibility compound.
Further preferably, the carbon source is at least one of glucose, citric acid, oxalic acid, lactose, galactolipin.
Still more preferably, the carbon source is at least one of glucose, citric acid, oxalic acid.
The vanadium source is at least one compound of trivalent, tetravalence, pentavalent vanadium.The vanadium source can be water-soluble under room 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, the vanadium source is at least one of vanadium trioxide, vanadic anhydride, ammonium metavanadate.
Preferably, the molar ratio in carbon source and vanadium source is 0.1-10 when hydro-thermal reaction.It is obtained in the preferred proportional region
Vanadium oxide in vanadium be V3+, packet carbon layers having thicknesses are moderate and more uniform.Ratio is excessively high, and carbon-coating is too thick, and ratio is too low, then will appear V4 +And V5+。
Further preferably, the carbon source and the molar ratio in vanadium source are 1-10.
Still more preferably, the carbon source and the molar ratio in vanadium source are 1-5；Most preferably 1~2.
Preferably, the initial concentration of the carbon source is 0.01-10g/mL before hydro-thermal reaction.The preferred concentration model
The hydrothermal product dispersibility for enclosing interior preparation is more preferable, and granularity is more evenly.Excessive concentration, particle agglomeration phenomenon are serious, and concentration is too low, then
Yield is too low.
Further preferably, the initial concentration of the carbon source is 0.01-1g/mL；It is still more preferably 0.01-0.1g/
mL。
Preferably, hydrothermal temperature is 120-200 DEG C；Further preferably 150-200 DEG C
Under the preferred hydrothermal temperature, the preferred reaction time is 10-25h；Further preferably 10-20h.
Level-one sintering process carries out under protective atmosphere.The protective atmosphere is preferably nitrogen, argon gas and hydrogen argon
At least one of gaseous mixture (5% hydrogen).
Preferably, the temperature of level-one sintering is 450-850 DEG C.It is sintered at such a temperature, resulting carbon coating layer is more equal
Even and electric conductivity is preferable.
Further preferably, level-one sintering temperature is 500-700 DEG C；It is still more preferably 500-650 DEG C；Most preferably
550-650℃。
The heating rate of level-one sintering process is 1-10 DEG C/min, and rate of temperature fall is 1-10 DEG C/min.Preferably rise at this,
Rate of temperature fall is more advantageous to the regularity for guaranteeing material morphology structure.
Further preferably, the heating rate of level-one sintering process is 4-8 DEG C/min, and rate of temperature fall is 2-6 DEG C/min.
In the present invention, calcine carbon coating vanadium oxide made from hydro-thermal and sodium source, phosphorus source ball milling, mist projection granulating to obtain carbon packet
The pyrophosphoric acid vanadium sodium microballoon covered.The inventors discovered that the preferable regulation of grain diameter, packet carbon layers having thicknesses and uniformity both contributes to
Further promote the chemical property of material.The present invention passes through to raw material selection and proportion, and spray drying and sintering schedule
To regulate and control grain diameter and carbon layers having thicknesses and uniformity.
The sodium source can preferably dissolve in aqueous solution and ionizable release Na+Compound.
Preferably, the 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 sodium carbonate, sodium acetate, sodium oxalate, disodium-hydrogen, at least one in sodium dihydrogen phosphate
Kind.
Phosphorus source can preferably dissolve in aqueous solution and ionizable release PO4 3-Compound.
Preferably, the 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 also found by numerous studies, and sodium source, the Na, V in vanadium source and phosphorus source, the control of P element molar ratio are existed
In suitable range, facilitate the electric property for promoting composite positive pole obtained.
Preferably, the ratio of sodium source, the Na, V in vanadium source and phosphorus source, P element molar ratio 0.5-10: 1: 0.1-10 mixes.
By the Na in sodium source, the V in vanadium source, the P in phosphorus source ratio in the preferred scope, help to reduce burnt phosphorus obtained
Sour vanadium sodium impurity is less, and object is compared pure.Each ratio does not control 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, V in phosphorus source, P element molar ratio 0.5-7: 1: 0.1-5.
Still more preferably, sodium source, vanadium source and Na, V in phosphorus source, P element molar ratio 1-5: 1: 0.1-2.
Most preferably, sodium source, vanadium source and Na, V in phosphorus source, P element molar 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, ethyl alcohol and acetone.Material and ball milling pearl mass ratio when 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 5-25h.Under the ball milling system, raw material
Between be uniformly 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 the preferred rotational speed of ball-mill, preferred Ball-milling Time is 5-25h；Further preferably 10-15h；Ball
Time consuming is 5-25h；Further preferably 5-10h.
In the method for the present invention, spherical precursor is obtained after the ball milling and mist projection granulating, presoma is by obtaining carbon
The pyrophosphoric acid vanadium sodium nanosphere of cladding.
Existing routine, maturation method can be used in spray-drying process；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, operating pressure 4-10MPa, atomizer rotating speed
For 15000-20000rad/min.
Preferably, second level sintering carries out under protective atmosphere, the protective atmosphere is preferably nitrogen, argon gas
It is at least one.
Preferably, second level sintering temperature is 450-850 DEG C.In the association of ball milling condition above-mentioned and raw material selection, proportion
With under, then cooperate the calcination temperature, the positive electrode of chondritic obtained is that partial size 100-200nm nano particle is formed
5~30 μm of the secondary microballoon of (assembling), and a nanoparticle surface is evenly coated carbon-coating, realizes while by material nano
Carbon coating, shows good high rate performance and long circulating stability energy.
Further preferably, second level sintering temperature is 500-700 DEG C.It is available by partial size 100- in preferred range
5~30 μm of the secondary microballoon that 200nm nano particle is formed improves high rate performance and cycle performance.
Still more preferably, 500-650 DEG C of second level sintering temperature；Most preferably 550-650 DEG C.
The heating rate of second level sintering process is 1-10 DEG C/min, and rate of temperature fall is 1-10 DEG C/min.Preferably rise at this,
Rate of temperature fall is more advantageous to the regularity for guaranteeing material morphology structure.
Further preferably, the heating rate of second level sintering process is 4-8 DEG C/min, and rate of temperature fall is 2-6 DEG C/min.
Under the second level sintering temperature and heating-cooling rate, preferred soaking time is 10-40h；Further preferably
For 10-15h.
The sintered product of second level obtains the positive electrode by washing, drying.
A kind of preparation method of preferred sodium-ion battery pyrophosphoric acid vanadium sodium positive electrode of the present invention, specifically includes following step
It is rapid:
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 calcines 10-15h at 550-650 DEG C, and product is washed, is dried to obtain the vanadium oxide of pre- packet carbon；The carbon source is
At least one of glucose, citric acid, oxalic acid, lactose, galactolipin；The molar ratio of the carbon source and vanadium source is 0.1-10；
Step (b): in Na, V, P element molar ratio 3.5-5: 1: 1.3-1.8 ratio by sodium source, phosphorus source and pre- packet 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, and calcination temperature is 550-650 DEG C, and calcination time is
10-15h, heating rate are 4-8 DEG C/min；Calcined product is washed, is dried to obtain carbon-coated pyrophosphoric acid vanadium sodium nanosphere.
The invention also includes a kind of using pyrophosphoric acid vanadium sodium@carbon composite anode material made from the preparation method, is
The micro-spherical particle that pyrophosphoric acid vanadium sodium nano particle by being coated with carbon assembles.
It that is to say, the microballoon that the present invention is agglomerated by the nano particle (microballoon) of several carbon-coated pyrophosphoric acid vanadium sodium
Shape particle (secondary microballoon).
The partial size of the nano particle of the carbon-coated pyrophosphoric acid vanadium sodium is 100-200nm；The anode composite material
The partial size 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 that partial size 100-200nm nano particle is formed
Secondary microballoon, and a nanoparticle surface is evenly coated carbon-coating, realizes carbon coating while by material nano, solves well
The disadvantage for pyrophosphoric acid vanadium sodium electron conduction difference of having determined.Using material obtained as sodium-ion battery anode, can express good
High rate performance and long circulating stability energy.
It is the present invention also provides pyrophosphoric acid vanadium sodium/carbon composite anode material application described in one kind, the anode is compound
Material is used as sodium ion positive electrode.
Preferably, the application, is applied to and prepares sodium-ion battery anode.
The cladding of carbon-coating not only increases the electron conduction of material, in the subsequent sintering process for forming pyrophosphoric acid vanadium sodium
In also a degree of growth for inhibiting particle, be advantageously implemented material nano, then cooperate mist projection granulating obtained micro-
Ball presoma obtains nanoscale primary particle during the sintering process, controls certain sintering temperature and sintering time, obtains 5
~30 μm of second particle.The material is the secondary microballoon that the nanoscale primary particle of packet carbon is constituted, and shortens electronics and particle
Migration path, there is good electron conduction and particle conductive, very good solution pyrophosphate high rate performance difference
Problem, while also there is good cyclical stability.
Technical solution of the present invention bring the utility model has the advantages that
1) the method preparation carbon coating pyrophosphoric acid vanadium sodium nanosphere that the present invention is matched using solid, liquid, the anode
Material is the secondary microballoon that nanoscale primary particle is constituted, which is used as to the anode of sodium-ion battery, can solve burnt phosphorus
The disadvantage that acid system high rate performance is poor, cyclical stability is bad has excellent chemical property.
2) in preparation method of the present invention, by the selection of the reproducibility carbon source, carbon source and vanadium source weight ratio, described
Ball milling and calcining mechanism etc. mutually cooperate with, and can be regulated and controled well the partial size of particle and cladding carbon-coating uniformity, in turn
It is obviously improved the chemical property of resulting positive electrode.
3) sodium-ion battery positive material pyrophosphoric acid vanadium sodium voltage platform prepared by the present invention can reach 4V or more, Ke Yishi
The high-energy density of existing sodium-ion battery.
4) operation is simple and reliable for preparation method of the invention, reproducible, strong operability, it is environmental-friendly, be suitble to it is large quantities of
Amount production, and low cost of raw materials, have wide industrial applications prospect.
Detailed description of the invention
[Fig. 1] is the scanning electron microscope (SEM) photograph of sodium-ion battery positive material made from embodiment 1；
[Fig. 2] is the discharge cycles figure of sodium-ion battery positive material made from embodiment 1.
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention；And the protection scope of the claims in the present invention
It is not limited by the example.
Following embodiment and comparative example, the spray drying parameters, unless specified or limited otherwise, inlet temperature exists
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 revolving speed in 15000-20000rad/min.
Embodiment 1
The vanadic anhydride (0.01mol) and 5g citric acid (0.026mol) for weighing 2g first, are dissolved in 100ml deionized water
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, at 180 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 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
Dry 2h is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) In
Ball milling 7h in alcoholic media, revolving speed are 200 revs/min；Spherical precursor is obtained by spray drying.Presoma is in nitrogen atmosphere
Under be heated to 600 DEG C in tube furnace with the speed of 4 DEG C/min, calcining 15h obtains black powder；Finally by black powder go from
Three times, ethanol wash is twice, dry for sub- water washing, obtains final products (Na7V3(P2O7)4).The scanning electron microscope of product obtained
Figure is shown in Fig. 1；Known by Fig. 1, composite positive pole made from the present embodiment has nano particle (primary of packet carbon pyrophosphoric acid vanadium sodium
Grain grain) microballoon that is agglomerated into；, a grain diameter is 150nm nanometers, and specific grain surface product is 250-300m2/ g, carbon coated
Layer is with a thickness of 10nm, 30 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance.Fig. 2 is positive electrode made from the present embodiment in current density
The specific discharge capacity and cycle efficieny data of 160mA/g (2C).
By Fig. 2 test result it is found that the sodium electricity anode of this example preparation has good chemical property；In 160mA/g
Under the current density of (2C), first circle capacity is that 68mAh/g is still able to maintain the specific capacity of 62mAh/g after circulation 50 is enclosed.
Embodiment 2
The ammonium metavanadate (0.025mol) and 7.5g glucose (0.04mol) for weighing 3g first are dissolved in 100ml deionized water
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, at 180 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 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
Dry 2h is to get pre- packet oxidation of coal vanadium.
Take pre- packet oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 5g (0.04mol), sodium carbonate 4.5g (0.042mol) ball
7h is ground, revolving speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma is under nitrogen atmosphere in tube furnace
600 DEG C are heated to the speed of 4 DEG C/min, calcining 15h obtains black powder；Black powder deionized water is finally washed three
Secondary, ethanol wash is twice, dry, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；Its grain diameter 150nm, specific grain surface product are 200-300m2/ g, cladding carbon layers having thicknesses be 10nm, two
20-30 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance.Under the current density of 160mA/g (2C), first circle specific capacity is
67mAh/g is able to maintain the specific capacity of 60mAh/g after circulation 50 is enclosed.As 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 acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 150 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mo1) ball
7h is ground, revolving speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma is under nitrogen atmosphere in tube furnace
600 DEG C are heated to the speed of 4 DEG C/min, calcining 15h obtains black powder；Black powder deionized water is finally washed three
Secondary, ethanol wash is twice, dry, obtains final products (Na7V3(P2O7)4)。
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 120nm, specific grain surface product is 180-250m2/ g, cladding carbon layers having thicknesses be 8nm, two
25-30 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance.Under the current density of 160mA/g (2C), first circle capacity is
68mAh/g is able to maintain the specific capacity of 63mAh/g after circulation 50 is enclosed.As it can be seen that hydrothermal temperature is down to 150 DEG C, material property base
Originally it remains unchanged.
Embodiment 4
The vanadic anhydride (0.022mol V) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionization
In water, stirring forms homogeneous solution, the aqueous solution is poured into ptfe autoclave, then by the polytetrafluoroethylene (PTFE)
Reaction kettle is put into stainless steel water heating kettle and seals, and finally the stainless steel water heating kettle is placed in homogeneous reactor, at 180 DEG C
It carries out hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.056mol
Na) ball milling 7h, revolving speed are 200 revs/min；Spherical precursor is obtained by spray drying.Presoma is under nitrogen atmosphere in pipe
550 DEG C are heated to the speed of 4 DEG C/min in formula furnace, calcining 15h obtains black powder；Finally black powder deionization is washed
It washs three times, ethanol wash is twice, dry, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 150nm, specific grain surface product is 200-250m2/ g, cladding carbon layers having thicknesses be 15nm, two
20-25 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance.Under the current density of 160mA/g (2C), first circle capacity is
67mAh/g is able to maintain the specific capacity of 56mAh/g after circulation 50 is enclosed.
Embodiment 5
The ammonium metavanadate (0.017mol) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 180 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained above, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball
7h is ground, revolving speed is 200 revs/min；Spherical precursor is obtained by spray drying.Presoma is under nitrogen atmosphere in tube furnace
650 DEG C are heated to the speed of 4 DEG C/min, calcining 15h obtains black powder；Black powder deionized water is finally washed three
Secondary, ethanol wash is twice, dry, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 120nm, specific grain surface product is 250-300m2/ g, cladding carbon layers having thicknesses be 10nm, two
25-30 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance.Under the current density of 160mA/g (2C), first circle capacity is
72mAh/g is able to maintain the specific capacity of 63mAh/g after circulation 50 is enclosed.
Embodiment 6
The ammonium metavanadate (0.017mol) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 180 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, revolving speed are 200 revs/min；Spherical precursor is obtained by spray drying.Presoma under nitrogen atmosphere in tube furnace with
The speed of 4 DEG C/min is heated to 550 DEG C, and calcining 15h obtains black powder；Finally three times by the washing of black powder deionized water,
Ethanol wash is twice, dry, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 150nm, specific grain surface product is 250-300m2/ g, cladding carbon layers having thicknesses be 12nm, two
25-30 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance.Under the current density of 160mA/g (2C), first circle capacity is
70mAh/g is able to maintain the specific capacity of 62mAh/g after circulation 50 is enclosed.
Embodiment 7
The ammonium metavanadate (0.017mol) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 180 DEG C into
Row hydro-thermal reaction 15 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, revolving speed are 200 revs/min；Spherical precursor is obtained by spray drying.Presoma under nitrogen atmosphere in tube furnace with
The speed of 4 DEG C/min is heated to 650 DEG C, and calcining 15h obtains black powder；Finally three times by the washing of black powder deionized water,
Ethanol wash is twice, dry, obtains final products pyrophosphoric acid vanadium sodium (Na7V3(P2O7)4)。
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 120nm, specific grain surface product is 180-250m2/ g, cladding carbon layers having thicknesses be 15nm, two
25-30 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance.Under the current density of 160mA/g (2C), first circle capacity is
70mAh/g is able to maintain the specific capacity of 64mAh/g after circulation 50 is enclosed.
Embodiment 8
The vanadic anhydride (0.011mol) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 180 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained, ammonium dihydrogen phosphate 3.45g (0.03mol), sodium acetate 2.3g (0.028mol) ball
7h is ground, revolving speed is 200 revs/min.Presoma is heated to 600 DEG C in tube furnace under nitrogen atmosphere with the speed of 4 DEG C/min,
Calcining 15h obtains black powder；Finally three times by the washing of black powder deionized water, ethanol wash is twice, dry, obtains final
Product (Na7V3 (P2O7) 4).
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 120nm, specific grain surface product is 180-250m2/ g, cladding carbon layers having thicknesses be 8nm, two
25-30 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance；Test result shows the sodium electricity cathode electrochemistry of this example preparation
Performance is poor；Under the current density of 160mA/g (2C), first circle specific discharge capacity is 71mA/g, is kept after 50 circle of circulation
The specific capacity of 64mAh/g.
Comparative example 1
The vanadic anhydride (0.011mol) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 180 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, revolving speed are 200 revs/min.Presoma is heated to 600 DEG C in tube furnace under nitrogen atmosphere with the speed of 4 DEG C/min, forges
It burns 15h and obtains black powder；Finally three times by the washing of black powder deionized water, ethanol wash is twice, dry, is finally produced
Product (Na7V3(P2O7)4)。
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；Its grain diameter 700nm, specific grain surface product are 80-100m2/ g, cladding carbon layers having thicknesses are 20nm, secondary
70-80 μm of microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance；Test result shows the sodium electricity cathode electrochemistry of this example preparation
Performance is poor；Under the current density of 160mA/g (2C), first circle specific discharge capacity is only 45mA/g, is kept after 50 circle of circulation
The specific capacity of 22mAh/g.Not by spray drying, material primary particle is larger, and the second particle of formation is bigger, so that particle
Transmission path increases, and high rate performance and cyclical stability are deteriorated.
Comparative example 2
Vanadic anhydride (0.011mol), the 5g citric acid (0.026mol), 3.5g sodium dihydrogen phosphate of 2g are weighed first
(0.03mol) and 3g sodium carbonate (0.028mol), is added in clean ball grinder, adds 150g agate bead and 40mL ethyl alcohol,
The ball milling of 12h is carried out, rotational speed of ball-mill is 500 revs/min.Ball milling product is placed in 70 DEG C of baking ovens dry 12h.Desciccate
Spherical precursor is obtained by spray drying.Presoma is heated under nitrogen atmosphere in tube furnace with the speed of 4 DEG C/min
600 DEG C, calcining 15h obtains black powder；Finally three times by the washing of black powder deionized water, ethanol wash is twice, dry, obtains
To final products (Na7V3(P2O7)4)。
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 600nm, specific grain surface product is 80-120m2/ g, cladding carbon layers having thicknesses be 40nm, two
70-80 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance；Under the current density of 160mA/g (2C), first circle capacity is
48mA/g is able to maintain the specific capacity of 38mAh/g after circulation 50 is enclosed.The result shows that preparing the system of packet oxidation of coal vanadium without hydro-thermal
Standby but direct 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 in the subsequent sintering process, and calcines not uniform enough the institute of products therefrom carbon coating layer
It causes.
Comparative example 3
Vanadic anhydride (0.011mol), the 5g citric acid (0.026mol), 3.5g sodium dihydrogen phosphate of 2g are weighed first
(0.03mol) and 3g sodium carbonate (0.028mol) is added in 100mL deionized water, and stirring forms homogeneous solution, will be described water-soluble
Liquid pours into ptfe autoclave, and then the ptfe autoclave is put into stainless steel water heating kettle and is sealed,
Finally the stainless steel water heating kettle is placed in homogeneous reactor, is carried out hydro-thermal reaction 10 hours at 180 DEG C.Hydrothermal product is put
Dry 12h is placed in 70 DEG C of baking ovens.Desciccate obtains spherical precursor by spray drying.Presoma under nitrogen atmosphere
600 DEG C are heated to the speed of 4 DEG C/min in tube furnace, calcining 15h obtains black powder；Finally by black powder deionized water
Three times, ethanol wash is twice, dry for washing, obtains final products (Na7V3(P2O7)4)。
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 400nm, specific grain surface product is 80-100m2/ g, cladding carbon layers having thicknesses be 25nm, two
50-60 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance；Under the current density of 160mA/g (2C), first circle capacity is
54mA/g is able to maintain the specific capacity of 38mAh/g after circulation 50 is enclosed.The result shows that without pre- packet carbon but direct step water
Heat, the high rate performance of calcining resulting materials 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, high rate performance decline.
Comparative example 4
The vanadic anhydride (0.011mol) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 230 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, revolving speed are 200 revs/min.Presoma is heated to 600 DEG C in tube furnace under nitrogen atmosphere with the speed of 4 DEG C/min, forges
It burns 15h and obtains black powder；Finally three times by the washing of black powder deionized water, ethanol wash is twice, dry, is finally produced
Product (Na7V3 (P2O7) 4).
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a 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.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance；Test result shows the sodium electricity cathode electrochemistry of this example preparation
Performance is poor；Under the current density of 160mA/g (2C), first circle specific discharge capacity is only 45mA/g, is kept after 50 circle of circulation
The specific capacity of 34mAh/g.Hydrothermal temperature is increased to 230 DEG C, has exceeded preferred scope, in the case where other conditions are constant,
High rate performance and cyclical stability decline are more, it is seen that the control of hydrothermal condition is affected to Morphological control of material.
Comparative example 5
The vanadic anhydride (0.011mol) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 100 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, revolving speed are 200 revs/min.Presoma is heated to 600 DEG C in tube furnace under nitrogen atmosphere with the speed of 4 DEG C/min, forges
It burns 15h and obtains black powder；Finally three times by the washing of black powder deionized water, ethanol wash is twice, dry, is finally produced
Product (Na7V3 (P2O7) 4).
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 400-700nm, specific grain surface product is 80-100m2/ g, cladding carbon layers having thicknesses are 30-
50nm, 60-85 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance；Test result shows the sodium electricity cathode electrochemistry of this example preparation
Performance is poor；Under the current density of 160mA/g (2C), first circle specific discharge capacity is only 45mA/g, is kept after 50 circle of circulation
The specific capacity of 34mAh/g.Hydrothermal temperature is dropped to 100 DEG C, other conditions are constant, and the decline of material high rate performance is more, may
It is that hydrothermal temperature is lower, product grain is larger and uneven.
Comparative example 6
The vanadic anhydride (0.011mol) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 180 DEG C into
Row hydro-thermal reaction 30 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, revolving speed are 200 revs/min.Presoma is heated to 600 DEG C in tube furnace under nitrogen atmosphere with the speed of 4 DEG C/min, forges
It burns 15h and obtains black powder；Finally three times by the washing of black powder deionized water, ethanol wash is twice, dry, is finally produced
Product (Na7V3 (P2O7) 4).
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 600-700nm, specific grain surface product is 80-100m2/ g, cladding carbon layers having thicknesses are 20-
40nm, 60-80 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance；Test result shows the sodium electricity cathode electrochemistry of this example preparation
Performance is poor；Under the current density of 160mA/g (2C), first circle specific discharge capacity is only 44mA/g, is kept after 50 circle of circulation
The specific capacity of 32mAh/g.The hydro-thermal time is increased into 30h, other conditions are constant, high rate performance and cyclical stability decline compared with
It is more, it is seen that the control of hydrothermal condition is affected to Morphological control of material.
Comparative example 7
The vanadic anhydride (0.011mol) and 5g citric acid (0.026mol) for weighing 2g first are dissolved in 100ml deionized water
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, at 180 DEG C into
Row hydro-thermal reaction 10 hours.Hydrothermal product is placed in 70 DEG C of baking ovens dry 12h.Then under the protective atmosphere of nitrogen, In
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 is to get pre- packet oxidation of coal vanadium.
By pre- packet oxidation of coal vanadium obtained, sodium dihydrogen phosphate 3.5g (0.03mol), sodium carbonate 3g (0.028mol) ball milling
7h, revolving speed are 200 revs/min.Presoma is heated to 600 DEG C in tube furnace under nitrogen atmosphere with the speed of 4 DEG C/min, forges
It burns 45h and obtains black powder；Finally three times by the washing of black powder deionized water, ethanol wash is twice, dry, is finally produced
Product (Na7V3 (P2O7) 4).
Composite positive pole made from the present embodiment has the nano particle (primary particle grain) of packet carbon pyrophosphoric acid vanadium sodium to reunite
At microballoon；, a grain diameter 700nm, specific grain surface product is 80-100m2/ g, cladding carbon layers having thicknesses be 35nm, two
78-80 μm of secondary microspherulite diameter.
Use pyrophosphoric acid vanadium sodium material manufactured in the present embodiment for working electrode, sodium is to be assembled into button cell to electrode,
Under the current density of 160mA/g (2C), test loop performance；Test result shows the sodium electricity cathode electrochemistry of this example preparation
Performance is poor；Under the current density of 160mA/g (2C), first circle specific discharge capacity is only 45mA/g, is kept after 50 circle of circulation
The specific capacity of 34mAh/g.Second level calcination time is increased into 45h from 15h, exceeds 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 (9)
1. a kind of preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode material, which is characterized in that will be molten comprising carbon source and vanadium source
Liquid carries out hydro-thermal reaction, and hydro-thermal reaction product is carried out level-one sintering, packet oxidation of coal vanadium is made；By packet oxidation of coal vanadium obtained,
It is spray-dried after sodium source, phosphorus source wet ball grinding, obtains presoma；Presoma carries out second level and is sintered to obtain the composite positive pole；
The carbon source is at least one of glucose, citric acid, oxalic acid, lactose, galactolipin；
The hydrothermal temperature is 120-200 DEG C；Reaction time is 10-25h；
The temperature of level-one sintering and double sintering is 450 aloneoC-850℃ ；Time is 10-40h alone；
The composite positive pole is the micro-spherical particle assembled by the pyrophosphoric acid vanadium sodium nano particle for being coated with carbon.
2. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode material as described in claim 1, which is characterized in that be coated with
The partial size of the pyrophosphoric acid vanadium sodium nano particle of carbon is 100-200nm；The partial size of the micro-spherical particle of the composite positive pole is
5-30μm；Specific surface area is 20-400 ㎡/g；Cladding carbon layers having thicknesses are 5-40nm.
3. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode material as described in claim 1, which is characterized in that described
Vanadium source is at least one of vanadium trioxide, vanadic anhydride, ammonium metavanadate, vanadyl acetylacetonate, vanadium acetylacetonate；
Carbon source and the molar ratio in vanadium source are 0.1-10.
4. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode material as described in claim 1, which is characterized in that hydro-thermal is anti-
Answering temperature is 150-200 DEG C；Reaction time is 10-20h.
5. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode material as described in claim 1, which is characterized 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 sodium pyrophosphate, phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate, disodium-hydrogen, at least one in sodium dihydrogen phosphate
Kind.
6. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode material as described in claim 1, which is characterized in that sodium source, vanadium
The ratio mixing of Na, V of source and phosphorus source, P element molar ratio 0.5-10:1:0.1-10.
7. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode material as described in claim 1, which is characterized in that wet process ball
The medium of honed journey is for water or with water infinitely than miscible at least one of solvent；Rotational speed of ball-mill is 150-550 revs/min；
Ball-milling Time is 5-25h.
8. the preparation method of pyrophosphoric acid vanadium sodium@carbon composite anode material as described in claim 1, which is characterized in that level-one is burnt
The temperature of knot and double sintering is 500-700 DEG C alone；Time is 10-15h alone.
9. the pyrophosphoric acid vanadium sodium@carbon composite anode material answers made from a kind of any one of claim 1 ~ 8 preparation method
With, which is characterized in that it is used as sodium-ion battery positive material.
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| 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 |
| CN108767237B (en) * | 2018-06-04 | 2021-04-27 | 福州大学 | One-step synthesis of carbon-supported hollow spherical vanadium trioxide compound and preparation method and application thereof |
| 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 |
| 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 |
| 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 |
| 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 |
| CN111446429B (en) * | 2020-03-27 | 2021-12-21 | 珠海冠宇电池股份有限公司 | Poly-polyanion cathode material and preparation method and application thereof |
| 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 |
| 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 |
| 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 |
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