CN109841800A - A kind of fluorophosphoric acid vanadium sodium and carbon complex and its preparation and application - Google Patents
A kind of fluorophosphoric acid vanadium sodium and carbon complex and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of fluorophosphoric acid vanadium sodium and carbon complex and its preparation method and application, the group of the positive electrode becomes Na3V2(PO4)2F3Carbon complex, Na3V2(PO4)2F3Carbon complex is prepared using one step of solvent heat of low temperature green, in solvent-thermal process Na3V2(PO4)2F3During carbon source is added, by the in-situ carburization of carbon source, in Na3V2(PO4)2F3Surface forms carbon-coating, obtains Na3V2(PO4)2F3Carbon complex.Compared with general solvent-thermal method, by introducing carbon source, under identical reaction conditions, in Na3V2(PO4)2F3Surface forms carbon-coating, effectively improves Na3V2(PO4)2F3Electric conductivity, and particle is reduced, to improve the high rate performance of material.Prepared Na3V2(PO4)2F3Carbon complex shows the specific discharge capacity and excellent high rate performance close to theoretical specific capacity, there is good application prospect in the equipment of portable electronic device and fast charging and discharging by electrochemical property test.
Description
Technical field
The present invention relates to sodium-ion battery technical fields, in particular to sodium-ion battery positive material field.
Background technique
The energy is the important impetus of social development, and the used energy is broadly divided into renewable energy (wind energy, water at present
Energy, solar energy etc.) and non-renewable energy resources (coal, petroleum, natural gas etc.).Due to non-renewable energy resources shortage of resources and to environment
It is seriously polluted, the development of renewable energy has been to be concerned by more and more people, but renewable energy is discontinuous, unstable, will
Its direct grid-connected can generate very big impact to power grid.Energy storage technology is the key that solution renewable energy is discontinuous, unstable
Technology.In numerous energy storage technologies, lithium ion battery has many advantages, such as that energy density is high, has extended cycle life, and is widely answered
For in various portable electronic devices and electric car, but lithium resource reserves are limited, are unevenly distributed, and limit lithium-ion electric
The large-scale development in pond.
Sodium and lithium have a similar chemistry, physical property, and the rich reserves (abundance of Na be Li 1000 times) of Na, point
Cloth is extensive, and cost is relatively low, and the development of sodium-ion battery can effectively alleviate the limited problem of lithium resource.The appearance of sodium-ion battery
Amount is limited to positive electrode, and developing positive electrode is the key that realize sodium-ion battery large-scale application, and fluorophosphoric acid vanadium sodium has
NASICON (Na super ionic conductor) structure, sodium ion deintercalation fast speed, stable structure, and voltage platform with higher and
Theoretical specific capacity is a kind of positive electrode for having very much application potential.From the point of view of current report, the preparation method of fluorophosphoric acid vanadium sodium
Mainly sol-gel method and ball-milling method, both methods are (300 DEG C -400 DEG C) and high due to needing to be pre-sintered by high temperature
Temperature is sintered into the process of phase, and energy consumption is higher, and preparation process is complicated.To realize the large-scale application of fluorophosphoric acid vanadium sodium, just
It must find that a kind of green is simple, energy consumption is lower, solvent-thermal method can form Asia because of it under lower temperature (100-300 DEG C)
Critical or critical state, to make material preferably at phase, therefore low-temperature in-site carbonization prepares high performance fluorine vanadium phosphate sodium carbon and answers
Closing object is a kind of good method for realizing its large-scale application.In solvent-thermal process Na3V2(PO4)2F3During carbon is added
Source, by the in-situ carburization of carbon source, in Na3V2(PO4)2F3Surface forms carbon-coating, obtains Na3V2(PO4)2F3Carbon complex, effectively
Ground improves the electric conductivity of material.Meanwhile in solvent-thermal process Na3V2(PO4)2F3During carbon source is added, can be effectively
Intergranular reunion is prevented, to generate more short grained Na3V2(PO4)2F3Carbon complex.Particle reduces so that sodium ion takes off
Embedding path and electrical conductance path shorten, and the deintercalation speed and electronics conduction of velocity of sodium ion are greatly improved, and
Grain reduces so that there is material the contact area of biggish specific surface area, material and carbon and electrolyte to increase, and electronics and ion exist
The transmission resistance of material interface becomes smaller, and transmission speed increases, to improve the high rate performance of material.Prepared Na3V2(PO4)2F3Carbon complex is shown close to the specific discharge capacity of theoretical specific capacity and excellent forthright again by electrochemical property test
Can, there is good application prospect in portable electronic device and fast charging and discharging equipment.
Summary of the invention
The method of high performance fluorine vanadium phosphate sodium carbon complex is prepared the present invention relates to a kind of low-temperature in-site carbonization and its in sodium
Application in ion battery.
The group of the fluorophosphoric acid vanadium sodium/carbon complex becomes Na3V2(PO4)2F3Carbon complex；
It 1) is 3:2:2:3:0~2:1 × 10 by the molar ratio of sodium, vanadium, phosphate radical, fluorine, reducing agent, carbon, additive-5~5:
0~2 ratio weighs sodium salt, vanadium source, phosphate, villiaumite, reducing agent, carbon source and additive, obtains mixture；
2) mixture of step 1) is added to temperature is that solvent is added in 100-300 DEG C of water heating kettle, reacts 3-72h；
3) mixed liquor for obtaining step 2) filters, and is cleaned 2-5 times with deionized water and ethyl alcohol respectively, in 100-150 DEG C
At a temperature of keep 1-20h, obtain Na3V2(PO4)2F3Carbon complex.
Sodium salt described in step 1) is sodium acetate, sodium sulphate, sodium oxalate, sodium citrate, sodium nitrate, sodium fluoride, carbonic acid
One of sodium, sodium bicarbonate, sodium hydroxide or two kinds or more,
Vanadium source is one of vanadium phosphate, ammonium metavanadate, vanadium acetylacetonate, vanadic anhydride or two kinds or more,
Phosphate is ammonium dihydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, potassium phosphate, sodium phosphate and phosphorus
One of sour vanadium or two kinds or more,
Villiaumite is one of ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride and hydrofluoric acid or two kinds or more.
Reducing agent described in step 1) is oxalic acid, ascorbic acid, citric acid, formic acid, malic acid, ethanedioic acid, adipic acid
One of or two kinds or more.
Solvent described in step 2) is one of water, acetone, ethyl alcohol, ethylene glycol or two kinds or more, mixture solute:
Solvent=1:(1-20) g/ml.
Carbon source described in step 1) is one of sucrose, glucose, starch, oxalic acid, cellulose or two kinds or more.
Additive described in step 1) be PEG, neopelex, ammonium hydroxide, sodium hydroxide, oxalic acid, citric acid,
One of hydrochloric acid or two kinds or more.
The Na3V2(PO4)2F3Carbon complex is applied in sodium-ion battery as positive electrode.By prepared Na3V2
(PO4)2F3Carbon complex is as anode, and metallic sodium piece is as cathode, and glass fibre membrane is as diaphragm, solute 1MNaClO4, molten
Agent EC (ethylene carbonate) and DEC (diethyl carbonate) mixture (mass ratio 1:1), additive are the FEC that mass fraction is 2%
As electrolyte, aluminium foil as collector plate, by CR2016 button shell according to anode housing, negative electrode, electrolyte, every
Film, electrolyte, anode electrode, collector anode pole housing sequence successively stack compression and be assembled into sodium-ion battery.
Beneficial effects of the present invention
Na of the invention3V2(PO4)2F3It is to be come out using the solvent heat one-step synthesis of low temperature green, with general solvent
Thermal method is compared, by introducing carbon source, under identical reaction conditions, in Na3V2(PO4)2F3Surface forms carbon-coating, effectively improves
Na3V2(PO4)2F3Electric conductivity.Meanwhile in solvent-thermal process Na3V2(PO4)2F3During carbon source is added, can be effectively
Intergranular reunion is prevented, to generate more short grained Na3V2(PO4)2F3Carbon complex.Particle reduces so that sodium ion takes off
Embedding path and electrical conductance path shorten, and the deintercalation speed and electronics conduction of velocity of sodium ion are greatly improved, and
Grain reduces so that there is material the contact area of biggish specific surface area, material and carbon and electrolyte to increase, and electronics and ion exist
The transmission resistance of material interface becomes smaller, and transmission speed increases, to improve the high rate performance of material.Prepared Na3V2(PO4)2F3Carbon complex is shown close to the specific discharge capacity of theoretical specific capacity and excellent forthright again by electrochemical property test
Can, there is good application prospect in portable electronic device and fast charging and discharging equipment.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of comparative example, embodiment 1, embodiment 2, embodiment 3.
Fig. 2 is the high rate performance figure of comparative example, embodiment 1, embodiment 2, embodiment 3.
Specific embodiment
Embodiment 1:(VPO4Low-temperature in-site carbonization preparation Na3V2(PO4)2F3Carbon complex)
Weigh 0.315g sodium fluoride (both doing Fluorine source, also do sodium source), 0.649g vanadium phosphate (had both done vanadium source, and also done phosphoric acid
Salt), 0.3gSDS (lauryl sodium sulfate), 1.2g glucose is added in the water heating kettle of 100mL, be added 25ml ethyl alcohol and
25ml deionized water reacts 48h at 180 DEG C.Gained mixed solution is filtered using filter paper, then clear with deionized water and ethyl alcohol
It washes 3 times, places into 120 DEG C of baking oven and keep 8h, obtain Na3V2(PO4)2F3Carbon complex.By prepared Na3V2(PO4)2F3Carbon complex is as anode, and metallic sodium piece is as cathode, and glass fibre membrane is as diaphragm, solute 1MNaClO4, solvent EC
(ethylene carbonate) and DEC (diethyl carbonate) mixture (mass ratio 1:1), additive are the FEC conduct that mass fraction is 2%
Electrolyte, aluminium foil is as collector plate, by CR2016 button shell according to anode housing, negative electrode, electrolyte, diaphragm, electricity
Solution liquid, anode electrode, collector anode pole housing sequence successively stack compression and be assembled into sodium-ion battery.
Embodiment 2:(NH4VO3Low-temperature in-site carbonization preparation Na3V2(PO4)2F3Carbon complex)
Weigh 0.315g sodium fluoride (both doing Fluorine source, also do sodium source), 0.585g ammonium metavanadate, 0.5752g ammonium dihydrogen phosphate,
1.0507g monohydrate potassium, 0.3g PEG-6000,0.9g starch, are added in the water heating kettle of 100mL, and 25ml acetone is added
With 25ml deionized water, 36h is reacted at 140 DEG C.Gained mixed solution is filtered using filter paper, then uses deionized water and ethyl alcohol
Cleaning 3 times, places into 120 DEG C of baking oven and keeps 8h, obtain Na3V2(PO4)2F3Carbon complex.
Embodiment 3:(V2O5Low-temperature in-site carbonization preparation Na3V2(PO4)2F3Carbon complex)
Weigh 0.278g ammonium fluoride, 0.300g sodium hydroxide, 0.455g vanadic anhydride, 0.5752g ammonium dihydrogen phosphate,
1.0507g monohydrate potassium, 1.5g sucrose, are added in the water heating kettle of 100mL, and 25ml acetone and 25ml deionization is added
Water reacts 48h at 120 DEG C.Gained mixed solution is filtered using filter paper, is then cleaned 3 times with deionized water and ethyl alcohol, then put
Enter in 120 DEG C of baking oven and keep 8h, obtains Na3V2(PO4)2F3Carbon complex.
Comparative example: (NH4VO3Solvent hot preparation Na3V2(PO4)2F3)
Weigh 0.315g sodium fluoride (both doing Fluorine source, also do sodium source), 0.585g ammonium metavanadate, 0.5752g ammonium dihydrogen phosphate,
1.0507g monohydrate potassium, is added in the water heating kettle of 100mL, 25ml acetone and 25ml deionized water is added, at 180 DEG C
Lower reaction 48h.Gained mixed solution is filtered using filter paper, is then cleaned 3 times with deionized water and ethyl alcohol, is placed into 120 DEG C
8h is kept in baking oven, obtains Na3V2(PO4)2F3。
It will be seen from figure 1 that embodiment 1, embodiment 2, the particle of embodiment 3 are all smaller compared with comparative example, this is main
It is since embodiment 1, embodiment 2, embodiment 3 joined the original of carbon source (glucose, starch, sucrose) during hydro-thermal
Cause, carbon source are carbonized during hydro-thermal, are coated on the surface of particle, so that the further growth of particle is prevented, so that particle
It is smaller.While the additive (SDS, PEG-6000) changed in embodiment 1, embodiment 2 can also subtract short grained size.Lesser
Grain makes embodiment 1, embodiment 2, the specific surface area of embodiment 3 larger, transfer of the electronics between material interface and electrolyte
Faster.And lesser particle reduces embodiment 1, embodiment 2, the sodium ion diffusion path in embodiment 3, sodium ion
Diffusion time shortens, and the deintercalation speed of sodium ion increases.Simultaneously as there is conduction in embodiment 1, embodiment 2, embodiment 3
Carbon, their electric conductivity can also be better than comparative example.These reasons can improve the high rate performance of embodiment well.
Figure it is seen that the high rate performance of embodiment 1, embodiment 2, embodiment 3 is substantially better than the forthright again of comparative example
Energy.At 0.2C, comparative example shows 105mAh g-1Specific capacity, and embodiment 1, embodiment 2, embodiment 3 show respectively
135mAh g is gone out-1、106mAh g-1、113mAh g-1Specific capacity.Under the high magnification of 10C, comparative example is shown
17mAh g-1Specific capacity, and embodiment 1, embodiment 2, embodiment 3 show 74mAh g respectively-1、76mAh g-1、
67mAh g-1Specific capacity, specific capacity of the embodiment at 10C be substantially better than comparative example.Moreover, under the high magnification of 40C, it is right
Ratio is almost without capacity, and embodiment 1, embodiment 2, embodiment 3 show 50mAh g respectively-1、72mAh g-1、
27mAh g-1Specific capacity, the high rate capability of embodiment is obviously due to comparative example.
Claims (8)
1. a kind of preparation method of fluorophosphoric acid vanadium sodium and carbon complex, it is characterised in that:, it is prepared by following steps:
It 1) is 3:2:2:3:0~2:1 × 10 by the molar ratio of sodium, vanadium, phosphate radical, fluorine, reducing agent, carbon, additive-5~5:0~2
Ratio weigh sodium salt, vanadium source, phosphate, villiaumite, reducing agent, carbon source and additive, obtain mixture；
2) mixture of step 1) is added to temperature is that solvent is added in 100-300 DEG C of water heating kettle, reacts 3-72h；
3) mixed liquor for obtaining step 2) filters, and is cleaned 2-5 times with deionized water and ethyl alcohol respectively, in 100-150 DEG C of temperature
Lower holding 1-20h, obtains Na3V2(PO4)2F3Carbon complex.
2. preparation method according to claim 1, it is characterised in that:
Sodium salt described in step 1) is sodium acetate, sodium sulphate, sodium oxalate, sodium citrate, sodium nitrate, sodium fluoride, sodium carbonate, carbon
One of sour hydrogen sodium, sodium hydroxide or two kinds or more,
Vanadium source is one of vanadium phosphate, ammonium metavanadate, vanadium acetylacetonate, vanadic anhydride or two kinds or more,
Phosphate is ammonium dihydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, potassium phosphate, sodium phosphate and vanadium phosphate
One of or two kinds or more,
Villiaumite is one of ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride and hydrofluoric acid or two kinds or more.
3. preparation method according to claim 1, it is characterised in that: reducing agent described in step 1) is oxalic acid, anti-bad
One of hematic acid, citric acid, formic acid, malic acid, ethanedioic acid, adipic acid or two kinds or more.
4. preparation method according to claim 1, it is characterised in that: solvent described in step 2) is water, acetone, second
One of alcohol, ethylene glycol or two kinds or more, mixture solute: solvent=1:(1-20) g/ml.
5. preparation method according to claim 1, it is characterised in that: carbon source described in step 1) be sucrose, glucose,
One of starch, oxalic acid, cellulose or two kinds or more.
6. preparation method according to claim 1, it is characterised in that: additive described in step 1) is PEG, dodecane
One of base benzene sulfonic acid sodium salt, ammonium hydroxide, sodium hydroxide, oxalic acid, citric acid, hydrochloric acid or two kinds or more.
7. a kind of any compound prepared of claim 1-6, is Na3V2(PO4)2F3Carbon complex.
8. a kind of application of compound described in claim 7, the Na3V2(PO4)2F3Carbon complex is applied to as positive electrode
In sodium-ion battery.
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