CN108199028A - A kind of NaVPO4F/C composite materials and preparation method thereof - Google Patents
A kind of NaVPO4F/C composite materials and preparation method thereof Download PDFInfo
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- CN108199028A CN108199028A CN201810020890.0A CN201810020890A CN108199028A CN 108199028 A CN108199028 A CN 108199028A CN 201810020890 A CN201810020890 A CN 201810020890A CN 108199028 A CN108199028 A CN 108199028A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- 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
A kind of porous NaVPO of 3D4A certain amount of cationic surfactant is dissolved in the mixed solution of alcohol and water by F/C composite materials and preparation method thereof, and 1 ~ 4h of stirring at normal temperature obtains I liquid；Vanadium source and a certain amount of reducing agent are added in I liquid, 1 ~ 4h of stirring at normal temperature obtains II liquid；Sodium source, phosphorus source and Fluorine source are added in II liquid, stirring at normal temperature 6 ~ for 24 hours, 80 DEG C of dry 10 ~ 48h obtain carbon-coated NaVPO4F presomas；Then 700 ~ 800 DEG C are heated in non-oxidizing atmosphere, 2 12h of constant temperature is to get the porous NaVPO of 3D4F/C composite materials.This method has synthesis cycle short, and synthesis condition controls simplicity, and synthetic method is simple, and the advantages of being easy to mass produce, and obtained material morphology is uniform, in 3D cellulars.
Description
Technical field
The invention belongs to sodium-ion battery positive material fields, are related to a kind of fluorophosphoric acid vanadium sodium (NaVPO4F) the system of material
The standby and its application in sodium-ion battery field.
Background technology
With the development of electric automobile market, lithium ion battery obtains unprecedented development.Sodium-ion battery is due to sodium reserves
It is abundant, of low cost, it is increasingly becoming the research hotspot of energy field in recent years.Sodium-ion battery has similar to lithium ion battery
Physicochemical properties and similar storage mechanism, and because there is no alloying reaction, sodium-ion battery between sodium and aluminium
Positive and negative anodes collector can be used relative low price aluminium foil, so as to further reduce sodium-ion battery cost.In electricity
Sub- consumer product area, sodium-ion battery are difficult to be competed with lithium ion battery, but act on energy storage device for power grid, sodium ion
Battery then has natural advantage and potentiality.
Fluorophosphoric acid vanadium sodium NaVPO4F is a kind of novel polyanionic material, and stable structure, there are tetragonal crystal systems and monocline
Two kinds of structures of crystallographic system, belong to sodium-ion battery positive material.For the first time tetragonal crystal system was synthesized in 2002 by J.Barker
NaVPO4F, and done using lithium piece to electrode, applied to mixed ion battery, the charging and discharging capacities of 0.1C for the first time are respectively
101mAh/g and 95mAh/g, charging/discharging voltage platform is respectively in 3.88/3.85V and 4.43/4.39V；The ion-conductance of material in itself
Conductance and electronic conductivity are relatively low, cause material discharging specific capacity and cycle performance poor.Maowen Xu etc. are by adding dimension life
Plain C utilizes one step high―temperature nuclei NaVPO of hydro-thermal method as carbon source and reducing agent4F/C composite materials keep the temperature 6h in 800 DEG C of argon gas
Carbon-coated NaVPO is made4F.The material synthesized is monoclinic system, carbon content 1.4%, is discharged for the first time under 0.1C multiplying powers
Capacity is 101mAh/g, and specific discharge capacity is 82mAh/g under 0.5C multiplying powers.This method technique is cumbersome, complicated for operation, and prepares
Material granule it is larger, carbon coating is uneven, the shortcomings of causing battery high rate performance bad.
At present, Chinese patent CN103594716A discloses a kind of two step high temperature solid-state method of sol-gal process and prepares carbon coating
Sodium-ion battery positive material NaVPO4F by the way that a certain proportion of vanadium source, phosphorus source and carbon source is soluble in water, is heated
Stirring forms green colloidal sol, calcines 2~10h after vacuum drying under 650~850 DEG C, inert atmosphere, obtains VPO4, then by one
The NaF of certainty ratio carries out solid phase mixing, and 2~10h is calcined under 650~850 DEG C, inert atmosphere, obtains NaVPO4F/C.The party
Material prepared by method is 112mAh/g in 0.05C discharge capacities, and 0.2C discharge capacities are only the 62.6% of 0.05C, material
High rate performance it is poor.This method is complicated for operation, and flow is longer, and energy consumption is higher.Therefore, specific discharge capacity is improved, improves multiplying power
Performance, can make it possible its application on sodium-ion battery anode, develop and optimize NaVPO4The synthetic method of F materials is shown
It must be highly desirable.
Invention content
The problem to be solved in the present invention is to overcome the deficiencies of the prior art and provide a kind of sodium-ion battery anode of low cost
Material NaVPO4The preparation method of F/C improves its specific discharge capacity, improves its high rate performance.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of porous NaVPO of 3D4F/C composite materials, which is characterized in that raw material include cationic surfactant, vanadium source,
Reducing agent, sodium source, phosphorus source and Fluorine source.
A kind of porous sodium-ion battery positive material NaVPO of 3D4The preparation method of F/C, includes the following steps：
A certain amount of cationic surfactant is dissolved in the mixed solution of alcohol and water, 1~4h of stirring at normal temperature obtains I
Liquid；Vanadium source and a certain amount of reducing agent are added in I liquid, 1~4h of stirring at normal temperature obtains II liquid；Sodium source, phosphorus source and Fluorine source are added in
In II liquid, stirring at normal temperature 6~for 24 hours, 80 DEG C of dry 10~48h obtain carbon-coated NaVPO4F presomas；Then non-oxide
700~800 DEG C are heated in property atmosphere, constant temperature 2-12h is to get the porous NaVPO of 3D4F/C composite materials.
The reducing agent dosage is reduced into 1~5 times of the required theoretical molar amount of trivalent vanadium for vanadium.
The cationic surfactant is with other substance total moles than control 0.01~0.1.
The alcohol is controlled with water volume ratio 12~3.
The sodium source, vanadium source, phosphorus source and Fluorine source carry out dispensing according to the molar ratio of sodium, vanadium, phosphorus, fluorine element for 1: 1: 1: 1.
The present invention's preferably includes：
The cationic surfactant is one or more of DTAC, DTAB, CTAB, CTAC, TDBAC.
The Fluorine source is one or more of sodium fluoride, vanadium trifluoride or ammonium fluoride.
The sodium source is sodium hydroxide, sodium fluoride, sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium metavanadate, positive vanadium
One or more of sour sodium and sodium dihydrogen phosphate.
The vanadium source is one or more of vanadic anhydride, ammonium metavanadate, three vanadium oxides, carbonic acid vanadium, vanadium trifluoride.
Phosphorus source is in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, triammonium phosphate and ammonium phosphate
It is one or more of.
The reducing agent is ethanedioic acid, adipic acid, malonic acid, oxalic acid, formaldehyde, n-butyric acie, anti-sepsis acid, citric acid, sugarcane
One or more of sugar, glucose and vitamin C, the reducing agent also acts as the effect of carbon source.
The invention has the advantages that：
Room temperature reduction provided by the invention-high-temperature heat treatment prepares the porous sodium-ion battery positive material NaVPO of 3D4F/C
Method compared with existing preparation method, has the following advantages：
For traditional sodium-ion battery positive material NaVPO4Long flow path, high energy consumption, material property difference etc. existing for F preparations
Problem, inventor pass through long-term research, have obtained the preparation method of the present invention.By adding cationic surfactant
The reduction of high price vanadium is carried out at normal temperatures and pressures, solves the energy consumption problem that previous mechanical activation is brought.Cationic surface is lived
Property agent surface-active be to be embodied by obtaining positively charged surface-active ion after its hydrolysis.Single surfactant point
Son is surrounded after being dissolved in water by water completely, and hydrophilic group is attracted by water, and lipophilic group is repelled by water, so as to make surface-active
Agent ionic adsorption is in solution surface.After adsorption saturation, if the concentration of surfactant continues to increase, inside solution
Surfactant will take another kind to flee from mode, its total energy is made to reach minimum, and the lipophilic group in molecule leads at this time
Intermolecular attraction is crossed mutually to associate together, and in hydrophilic basal orientation water, so as to form micelle.And cation surface activating
The surface active agent ion that agent ionizes out is assembled in the solution, forms the micella of specific shape, one end of hydrophilic group is inside, simultaneously
Attract the anionic group in solution by electrostatic interaction, hydrophobic group is connected with each other.When pentavalent vanadium is reduced into trivalent in solution
Vanadium and combined with phosphate anion generation precipitation after, be limited in the glue that cationic surfactant surrounds in growth course
Shu Zhong, and grown as template.So as to prepare the porous sodium-ion battery positive materials of the uniform 3D of pattern
NaVPO4F/C composite materials.This method synthesis condition is simple, easy to operate, and technological process is short, and low energy consumption, and production cost is small.It should
With a process for preparing NaVPO4The voltage range of F/C 2.0~4.2V at normal temperatures and pressures, specific discharge capacity is high under 1C multiplying powers
Up to 108mAh/g, the specific discharge capacity under 5C discharge-rates remains to remain 79mAh/g, and after recycling 100 times, capacity retention ratio exists
More than 90%, material has excellent chemical property.
In addition, the further advantage of the present invention is, using high price vfanadium compound as vanadium source, to thus greatly reduce material
Cost, more favorably use process of industrialization.
In conclusion the present invention is that a kind of synthesis cycle is short, synthesis condition control is easy, and synthetic method is simple, is easy to big
Large-scale production prepares sodium fluorophosphate vanadium for positive pole material of sodium-ion battery NaVPO4The method of F/C.
Description of the drawings
Fig. 1 is the XRD spectrum of sample in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of No. 2 samples in embodiment 1；
Fig. 3 is first charge-discharge curve graph of No. 1 sample under different multiplying in embodiment 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of sample 2 in embodiment 2；
Fig. 5 is the scanning electron microscope (SEM) photograph of sample 3 in embodiment 2；
Fig. 6 is the XRD spectrum of sample in embodiment 3；
Fig. 7 is the scanning electron microscope (SEM) photograph of sample in embodiment 3；
Fig. 8 is the scanning electron microscope (SEM) photograph of sample in embodiment 4.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and detailed description.Those skilled in the art should manage
Solution, following embodiment is intended to illustrate invention, is not limitation of the invention further.
Embodiment 1：
CTAB (being 1: 20 with other substance integral molar quantity ratios) is dissolved in the mixed solution of alcohol and water (volume ratio 8: 1)
In, stirring at normal temperature 3h obtains I liquid；Ammonium metavanadate and oxalic acid are added in I liquid, stirring at normal temperature (according to 2 times of additions of theoretical amount)
2h obtains II liquid；Sodium fluoride, ammonium dihydrogen phosphate are added in II liquid, stirring at normal temperature 8h, 80 DEG C of dryings for 24 hours, obtain carbon-coated
NaVPO4F presomas；Then 700~800 DEG C are heated in argon gas atmosphere, calcining at constant temperature 4h is to get the porous NaVPO of 3D4F/C
Composite material.The product of gained is dressed up into button cell and surveys its charging and discharging capacity and high rate performance, is carried out under different multiplying
Charge and discharge, first discharge specific capacity are shown in Table 1.
The experiment condition and result of 1 embodiment 1 of table
Embodiment 2：
CTAB (being 1: 20 with other substance integral molar quantity ratios) is dissolved in the mixed solution of alcohol and water (volume ratio 8: 1)
In, stirring at normal temperature 3h obtains I liquid；Ammonium metavanadate and oxalic acid are added in I liquid, stirring at normal temperature (according to 2 times of additions of theoretical amount)
2h obtains II liquid；Sodium fluoride, ammonium dihydrogen phosphate are added in II liquid, stirring at normal temperature 8h, 80 DEG C of dryings for 24 hours, obtain carbon-coated
NaVPO4F presomas；Then 750 DEG C are heated in argon gas atmosphere, calcining at constant temperature 2-8h is to get the porous NaVPO of 3D4F/C is compound
Material.The product of gained is dressed up into button cell and surveys its charging and discharging capacity and high rate performance, charge and discharge is carried out under different multiplying
Electricity, first discharge specific capacity are shown in Table 2.
The experiment condition and result of 2 embodiment 2 of table
Embodiment 3：
The mixing that TDBAC (being 1: 20 with other substance integral molar quantity ratios) is dissolved in alcohol and water (volume ratio 8: 1) is molten
In liquid, stirring at normal temperature 3h obtains I liquid；Vanadic anhydride and oxalic acid are added in (according to 2 times of additions of theoretical amount) in I liquid, room temperature stirs
2h is mixed, obtains II liquid；Sodium fluoride, ammonium dihydrogen phosphate are added in II liquid, stirring at normal temperature 8h, 80 DEG C of dryings for 24 hours, obtain carbon-coated
NaVPO4F presomas；Then 750 DEG C are heated in argon gas atmosphere, constant temperature 4h is to get the porous NaVPO of 3D4F/C composite materials.
The product of gained is dressed up into button cell and surveys its charging and discharging capacity and high rate performance, charge and discharge are carried out under different multiplying,
Charge-discharge property under 0.1C, 0.5C, 1C, 2C and 5C multiplying power is respectively 120mAhg-1、114mAh·g-1、
104mAh·g-1、93mAh·g-1、72mAh·g-1。
Embodiment 4：
CTAB (being 1: 20 with other substance integral molar quantity ratios) is dissolved in the mixed solution of alcohol and water (volume ratio 8: 1)
In, stirring at normal temperature 3h obtains I liquid；Vanadic anhydride and glucose are added in (according to 2 times of additions of theoretical amount) in I liquid, room temperature stirs
2h is mixed, obtains II liquid；Sodium fluoride, ammonium dihydrogen phosphate are added in II liquid, stirring at normal temperature 8h, 80 DEG C of dryings for 24 hours, obtain carbon-coated
NaVPO4F presomas；Then 750 DEG C are heated in argon gas atmosphere, constant temperature 4h is to get the porous NaVPO of 3D4F/C composite materials.
The product of gained is dressed up into button cell and surveys its charging and discharging capacity and high rate performance, charge and discharge are carried out under different multiplying,
Charge-discharge property under 0.1C, 0.5C, 1C, 2C and 5C multiplying power is respectively 118mAhg-1、110mAh·g-1、
99mAh·g-1、89mAh·g-1、70mAh·g-1。
As can be seen that obtained NaVPO from Fig. 4-5,7-84F/C composite material patterns are uniform, in 3D cellulars.It is former
Reason such as preceding analysis, the surface active agent ion that cationic surfactant ionizes out are assembled in the solution, form specific shape
Micella, one end of hydrophilic group is inside, while attracts the anionic group in solution by electrostatic interaction, and hydrophobic group mutually interconnects
It connects.When in solution pentavalent vanadium be reduced into trivalent vanadium and combined with phosphate anion generation precipitation after, limited in growth course
It makes in the micella surrounded in cationic surfactant, and grown as template, so as to prepare the uniform 3D of pattern
Porous sodium-ion battery positive material NaVPO4F/C composite materials.It is also due to form above-mentioned appearance structure, obtain
NaVPO4Specific discharge capacity is up to 108mAh/g under F/C material 1C multiplying powers, and the specific discharge capacity under 5C discharge-rates remains to keep
For 79mAh/g, only 80% conservation rate can be reached, after recycling 100 times, more than 90%, material has excellent capacity retention ratio
Good chemical property, this is that material similar at present is not achieved.
Claims (9)
1. a kind of porous NaVPO of 3D4F/C composite materials, which is characterized in that raw material includes cationic surfactant, vanadium source, goes back
Former agent, sodium source, phosphorus source and Fluorine source.
2. composite material according to claim 1, preparation method include the following steps：
A certain amount of cationic surfactant is dissolved in the mixed solution of alcohol and water, 1 ~ 4h of stirring at normal temperature obtains I liquid；It will
Vanadium source and a certain amount of reducing agent are added in I liquid, and 1 ~ 4h of stirring at normal temperature obtains II liquid；Sodium source, phosphorus source and Fluorine source are added in into II liquid
In, stirring at normal temperature 6 ~ for 24 hours, 60-100 DEG C of 10 ~ 48h of drying obtains carbon-coated NaVPO4F presomas；Then non-oxidizable
700 ~ 800 DEG C are heated in atmosphere, constant temperature 2-12h is to get the porous NaVPO of 3D4F/C composite materials.
3. composite material according to claim 1 or 2, the reducing agent dosage is reduced into the required reason of trivalent vanadium for vanadium
By 1 ~ 5 times of mole.
4. composite material according to claim 1 or 2, the cationic surfactant are with other substance total moles ratios
0.01~0.1。
5. composite material according to claim 1 or 2, the alcohol is 12 ~ 3 with water volume ratio.
6. composite material according to claim 1 or 2, the sodium source, vanadium source, phosphorus source and Fluorine source are according to sodium, vanadium, phosphorus, fluorine
The molar ratio of element is 1-2:1-2:1-2:1-2.
7. composite material according to claim 1 or 2, the cationic surfactant is DTAC, DTAB, CTAB,
One or more of CTAC, TDBAC.
8. composite material according to claim 1 or 2, the Fluorine source is one in sodium fluoride, vanadium trifluoride or ammonium fluoride
Kind or it is several, the sodium source is sodium hydroxide, sodium fluoride, sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium metavanadate, just
One or more of sodium vanadate and sodium dihydrogen phosphate, the vanadium source is vanadic anhydride, ammonium metavanadate, three vanadium oxides, carbonic acid
One or more of vanadium, vanadium trifluoride, preferably vanadic anhydride, ammonium metavanadate, phosphorus source for phosphoric acid, ammonium dihydrogen phosphate,
One or more of diammonium hydrogen phosphate, sodium dihydrogen phosphate, triammonium phosphate and ammonium phosphate.
9. composite material according to claim 1 or 2, the reducing agent is ethanedioic acid, adipic acid, malonic acid, oxalic acid, first
One or more of aldehyde, n-butyric acie, anti-sepsis acid, citric acid, sucrose, glucose and vitamin C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110289411A (en) * | 2019-07-02 | 2019-09-27 | 中南大学 | A kind of fluorinated phosphate zirconium manganese sodium/carbon composite, positive electrode, anode and sodium-ion battery and preparation method thereof |
| CN112216823A (en) * | 2019-07-10 | 2021-01-12 | 上海交通大学 | Vanadium sodium fluorophosphate coated positive electrode material, sodium ion battery and preparation method and application of sodium vanadium fluorophosphate coated positive electrode material and sodium ion battery |
| CN114824250A (en) * | 2022-01-17 | 2022-07-29 | 常州大学 | Multifunctional additive synchronously modified carbon-coated sodium vanadium fluorophosphate composite material, and preparation method and application thereof |
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| CN114824250B (en) * | 2022-01-17 | 2024-05-03 | 常州大学 | Multifunctional additive synchronous modified carbon-coated vanadium sodium fluorophosphate composite material, preparation method and application thereof |
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