CN108878875A - The preparation method of fluorophosphoric acid vanadium sodium - Google Patents
The preparation method of fluorophosphoric acid vanadium sodium Download PDFInfo
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- CN108878875A CN108878875A CN201810626201.0A CN201810626201A CN108878875A CN 108878875 A CN108878875 A CN 108878875A CN 201810626201 A CN201810626201 A CN 201810626201A CN 108878875 A CN108878875 A CN 108878875A
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- fluorophosphoric acid
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation method of fluorophosphoric acid vanadium sodium, using cheap pentavalent inorganic vanadium source, vanadium phosphate intermediate is prepared in lower temperature and in the short period using spray pyrolysis after at normal temperatures and pressures mixing vanadium source, phosphoric acid root and organic reducing agent, solid phase mixing further is carried out with sodium source and Fluorine source, calcines in lower temperature and in the short period the good fluorophosphoric acid vanadium sodium of synthetic crystallization；Gained fluorophosphoric acid vanadium sodium has spherical morphology, and part hollow sphere, partial size is smaller.Spray pyrolysis is used to prepare vanadium phosphate intermediate during the preparation method, process is short, process is simple, production capacity is big, high production efficiency.
Description
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, it particularly relates to a kind of fluorophosphoric acid vanadium sodium
Preparation method, especially a kind of preparation method of spherical fluorophosphoric acid vanadium sodium.
Background technique
Currently, fossil fuel has become the main power supply source of our lives.It is arranged on a large scale using fossil fuel
The carbon dioxide gas put, the main reason for becoming global warming.Therefore, the mankind are sought for other renewable energy, such as wind
Energy, solar energy, nuclear energy power generation.However, the normal operation of power grid needs to continue and stable power supply, all due to solar energy and wind energy
It is highly dependent on the reason in environment, weather, season and place etc., is considered being not suitable for being directly incorporated into power grid.In order to overcome this
Problem, chemical energy storage are given great expectations.Small in size, light weight that lithium-ion electric commercial at present has by it, specific capacity be big,
Have extended cycle life, memory-less effect the advantages that and receive significant attention, market demand is incrementally increasing.However its is higher
Cost is difficult to apply to power grid scale energy storage.The sodium ion and lithium ion for belonging to same main group have similar electrochemical properties,
And sodium resource distribution is extensive, at low cost, safety is good, it is considered to be most has the secondary cell of application prospect, is applied to power grid
The fixed energy storage field of scale.
Polyanionic compound obtains the extensive concern of researcher, the fluorophosphoric acid vanadium sodium of tetragonal crystal system based on structural stability
(NaVPO4It F) is a kind of high voltage (3.7V, 4.2Vv.s.Na), height ratio capacity (143mAh/g) sodium-ion battery positive material.
Its structure is one by PO4Tetrahedron and VO4F2Octahedron is built into the three-dimensional framework of extension, and it is logical to provide sodium ion diffusion transport
Road, sodium ion occupy the crystal positions of two non-equivalences of three-dimensional framework, and the space structure of material is highly stable；The poly- yin of phosphate radical
The high F element of ion complex electronegativity, so that reversible deintercalation sodium voltage platform is in 3.7,4.1V, corresponding V3+/V4+Redox is anti-
It answers, sodium ion transmits good reversibility, and chemical property is good, thermal stability with higher and security performance.
Chinese patent CN107154493A provides a kind of fluorophosphoric acid vanadium sodium salt and its preparation method and application, the fluorophosphoric acid
The molecular formula of vanadium sodium salt is Na3(VOxPO4)2F3-2x, wherein 0≤x≤1, pattern is spherical knitting wool bulk, loose hollow ball or receives
Rice grain aggregate, size is from nanoscale to micron order.This method needs to adjust solution ph and carries out precipitating post-processing,
Complicated for operation, long flow path, high production cost has certain limitation.
Chinese patent CN103594716A provides a kind of activate by collosol and gel and assists the preparation of two step high temperature solid-state methods
Fluorophosphoric acid vanadium sodium positive electrode method.This method is needed by two step pyroreactions, the temperature of synthesis at 650 DEG C or more,
Soaking time is longer, complicated for operation, and production cost is higher.
In above method, do not solved effectively aiming at the problem that fluorine element volatile loss under the high temperature conditions, because
This, the fluorophosphoric acid vanadium sodium of controlledly synthesis high-purity is still more difficult.At present fluorophosphoric acid vanadium sodium preparation method have carbothermic method,
Sol-gal process, hydro-thermal method.These method and processes are relatively complicated, long flow path, synthesis temperature are high, be made material granule reunite it is tight
Weight, fluorine element are easy loss, cause material electrochemical performance poor.
Summary of the invention
For above-mentioned technical problem in the related technology, the present invention proposes a kind of preparation method of fluorophosphoric acid vanadium sodium, passes through
Spray pyrolysis prepares intermediate, then it is ground prepare fluorophosphoric acid vanadium sodium, overcome current battery positive electrode high temperature, generated time long
Limitation, propose it is a kind of under short period and lower temperature obtain uniform particle sizes, morphological rules NaVPO4The preparation side of F
Method.
To realize the above-mentioned technical purpose, the technical proposal of the invention is realized in this way：
On the one hand, the present invention provides a kind of preparation method of fluorophosphoric acid vanadium sodium, includes the following steps：
1) vanadium source, phosphoric acid root are mixed and is dissolved in deionized water according to vanadium, the ratio that P elements molar ratio is 1: 1, added
Enter organic reducing agent, stirs and evenly mixs to obtain mixed liquor；The mixed liquor of preparation is prepared into unformed VPO through spray pyrolysis4；
2) by VPO4Mixed grinding is carried out according to vanadium, sodium, the ratio that fluorine element molar ratio is 1: 1: 1 with sodium source and Fluorine source,
It is placed in non-oxidizing atmosphere and calcines, keep constant temperature, obtain fluorophosphoric acid vanadium sodium.
Further, each substance total concentration range is 0.1~1.0mol/L in the mixed liquor.
Further, the temperature of the spray pyrolysis is 500~700 DEG C, and sample rate is 50~120ml/h, intake
For 2~6L/min.
Further, the organic reducing agent includes ethanedioic acid, adipic acid, malonic acid, oxalic acid, formaldehyde, n-butyric acie, resists and lose
One or more of hematic acid, citric acid or vitamin C.
Further, the vanadium source includes one or more of vanadic anhydride or ammonium metavanadate.
Further, the phosphoric acid root includes phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, tricresyl phosphate
One or more of ammonium or ammonium phosphate.
Further, the sodium source include sodium hydroxide, sodium fluoride, sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, partially
One or more of sodium vanadate, sodium vanadate or sodium dihydrogen phosphate.
Further, the Fluorine source includes one or more of sodium fluoride, vanadium trifluoride or ammonium fluoride.
Further, the mode of the mixed grinding includes mechanical ball mill or underhand polish, and the mixed grinding is in room temperature
0.5~2h of lower progress.Room temperature of the present invention refers to 15~35 DEG C.Preferably 25 DEG C.
Further, the non-oxidizing atmosphere includes hydrogen, nitrogen or argon gas.
Further, the temperature of the calcining is 500~700 DEG C.
Further, the time of the constant temperature is 1~8h.
Further, the organic reducing agent dosage is the 1~5 of the required theoretical molar amount that vanadium is oxidized to trivalent vanadium
Times.
Further, mixed solution is made to carry out at room temperature.Spray pyrolysis also carries out in non-oxidizing atmosphere.
On the other hand, the present invention provides a kind of anode material for lithium-ion batteries, including the method system described through the invention
Standby obtained fluorophosphoric acid vanadium sodium.
On the other hand, the present invention provides a kind of anode, including with anode material for lithium-ion batteries of the present invention
For raw material preparation.
On the other hand, the present invention provides a kind of battery, including anode of the present invention.
Beneficial effects of the present invention：
The present invention provides a kind of preparation method of fluorophosphoric acid vanadium sodium, using cheap pentavalent inorganic vanadium source, in room temperature
It is made in lower temperature and in the short period after mixing vanadium source, phosphoric acid root and organic reducing agent under normal pressure using spray pyrolysis
It is standby to obtain vanadium phosphate intermediate, solid phase mixing further is carried out with sodium source and Fluorine source, is calcined in lower temperature and in the short period
The good fluorophosphoric acid vanadium sodium of synthetic crystallization；Gained fluorophosphoric acid vanadium sodium has spherical morphology, and part hollow sphere, partial size is smaller.
It uses water to dissolve during the preparation method as solvent environmentally protective, is prepared in vanadium phosphate using spray pyrolysis
Mesosome process is short, process is simple, production capacity is big, high production efficiency.
The fluorophosphoric acid vanadium sodium of preparation method preparation has spherical morphology, and particle size is controllable simultaneously and is evenly distributed, and compares table
The advantages that area is big, and product component is uniform.
Compared to the preparation method of current existing fluorophosphoric acid vanadium sodium, synthesis temperature is low, simple process, resulting materials particle not
Easy to reunite, calcination temperature is low, soaking time is short, can effectively solve the problems, such as fluorine element volatilizees.
Spherical shape fluorophosphoric acid vanadium sodium provided by the invention is by the dosage of control vanadium, P elements molar ratio and organic acid with spray
Mist pyrolysis prepares that particle is tiny, the uniform amorphous vanadium phosphate of particle diameter distribution, further through control vanadium, sodium, fluorine element molar ratio,
Grinding, which is sufficiently mixed solid phase, enhances reactivity, then synthesizes the fluorophosphoric acid of specific spherical morphology through low temperature, short time calcining
Vanadium sodium salt solves the problems, such as that fluorine element is easily volatilized so that particle size is controllably evenly distributed simultaneously, reduces synthesis energy consumption.
Fluorophosphoric acid vanadium sodium prepared by the present invention has good chemical property, assembles button cell as electrode material,
Under 0.1C current ratio, specific discharge capacity reaches as high as 135mAhg-1, close to theoretical specific capacity (the theoretical specific volume of material
Measure 143mAhg-1), and good cycling stability.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 be embodiment 1 at different temperatures gained NaVPO4The XRD spectrum of F.
Fig. 2 is gained VPO in embodiment 14SEM spectrum.
Fig. 3 is gained NaVPO in embodiment 14The SEM spectrum of number 1 in F.
Fig. 4 is gained NaVPO in embodiment 14The SEM spectrum of number 2 in F.
Fig. 5 is gained NaVPO in embodiment 14The SEM spectrum of number 3 in F.
Fig. 6 be embodiment 2 under different soaking times gained NaVPO4The XRD spectrum of F.
Fig. 7 is gained NaVPO in embodiment 24The SEM spectrum of number 2 in F.
Fig. 8 is gained NaVPO in embodiment 24The SEM spectrum of number 3 in F.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art's every other embodiment obtained belong to what the present invention protected
Range.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or
Person can the product as made from well known method.
Embodiment 1
It is in molar ratio to be dissolved in ammonium dihydrogen phosphate and ammonium metavanadate in deionized water at 1: 1, then be oxidized to trivalent by vanadium
3 times of addition oxalic acid of the required theoretical molar amount of vanadium, control total concentration are 0.5mol/L, stir 0.5h under normal temperature condition；It will be molten
Liquid carries out spray pyrolysis (sample rate 60ml/h, intake 3L/min) under 600 DEG C, argon atmosphere, collects to obtain phosphoric acid
Vanadium powder；
After collected vanadium phosphate is mixed underhand polish 1h according to molar ratio with sodium fluoride for 1: 1, in argon atmosphere respectively
In 500 DEG C, 550 DEG C, 600 DEG C of heat preservation 4h, the NaVPO of spherical structure is obtained4F.Resulting product is dressed up into button cell and surveys it
Charging and discharging capacity and high rate performance, carry out charge and discharge under different multiplying, and first discharge specific capacity is shown in Table 1.
The experiment condition and result of 1 embodiment 1 of table
Embodiment 2：
It is in molar ratio to be dissolved in ammonium dihydrogen phosphate, ammonium metavanadate in deionized water at 1: 1, then be oxidized to trivalent vanadium by vanadium
Required theoretical molar amount 3 times of addition oxalic acid, control total concentration is 0.5mol/L, stirs 0.5h under normal temperature condition；By solution
Spray pyrolysis (sample rate 100ml/h, intake 2L/min) is carried out under 600 DEG C, argon atmosphere, collects to obtain vanadium phosphate
Powder；
After being 1: 1 mixing machinery grinding 0.5h according to molar ratio by collected vanadium phosphate and sodium fluoride, it is placed in argon atmosphere
Under 550 DEG C respectively keep the temperature 4,6,8h, obtain the NaVPO of spherical structure4F.It resulting product is dressed up into button cell surveys it and fill
Specific discharge capacity and high rate performance, carry out charge and discharge under different multiplying, and first discharge specific capacity is shown in Table 2.
The experiment condition and result of 2 embodiment 2 of table
Embodiment 3：
It is in molar ratio to be dissolved in triammonium phosphate, vanadic anhydride in deionized water at 1: 1, then be oxidized to trivalent vanadium by vanadium
Required theoretical molar amount 1 times of addition adipic acid, control total concentration is 0.1mol/L, stirs 1h under normal temperature condition；By solution
Spray pyrolysis (sample rate 110ml/h, intake 6L/min) is carried out under 500 DEG C, argon atmosphere, collects to obtain vanadium phosphate
Powder；
After collected vanadium phosphate, ammonium fluoride are mixed underhand polish 2h according to molar ratio with sodium acetate for 1: 1: 1, it is placed in nitrogen
In 650 DEG C of heat preservation 2h in gas atmosphere, the NaVP0 of spherical structure is obtained4F.Resulting product is dressed up into button cell and surveys its charge and discharge
Electric specific capacity and high rate performance, specific discharge capacity is respectively 130,123,118,112mAh under 0.1C, 1C, 2C, 5C multiplying power
g-1。
Embodiment 4：
It is in molar ratio to be dissolved in ammonium dihydrogen phosphate, vanadic anhydride in deionized water at 1: 1, then be oxidized to trivalent by vanadium
5 times of addition citric acids of the required theoretical molar amount of vanadium, control total concentration are 1mol/L, stir 1h under normal temperature condition；By solution
Spray pyrolysis (sample rate 80ml/h, intake 4L/min) is carried out under 600 DEG C, argon atmosphere, collects to obtain vanadium phosphate
Powder；
After being 1: 1 mixing machinery grinding 1h according to molar ratio by collected vanadium phosphate and sodium fluoride, it is placed under argon atmosphere
In 700 DEG C of heat preservation 8h, the NaVPO of spherical structure is obtained4F.Resulting product is dressed up into button cell and surveys its charging and discharging capacity
And high rate performance, specific discharge capacity is respectively 128,120,113,104mAhg under 0.1C, 1C, 2C, 5C multiplying power-1。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of fluorophosphoric acid vanadium sodium, which is characterized in that include the following steps：
1）By vanadium source, phosphoric acid root according to vanadium, P elements molar ratio be 1:1 ratio mixing is dissolved in deionized water, and addition has
Machine reducing agent stirs and evenly mixs to obtain mixed liquor；The mixed liquor of preparation is prepared into unformed VPO through spray pyrolysis4；
2）By VPO4It according to vanadium, sodium, fluorine element molar ratio is 1 with sodium source and Fluorine source:1:1 ratio carries out mixed grinding, is placed in
It is calcined in non-oxidizing atmosphere, keeps constant temperature, obtain fluorophosphoric acid vanadium sodium.
2. the preparation method of fluorophosphoric acid vanadium sodium according to claim 1, which is characterized in that each substance is total in the mixed liquor
Concentration range is 0.1 ~ 1.0 mol/L；
The temperature of the spray pyrolysis is 500 ~ 700 DEG C, and sample rate is 50 ~ 120 ml/h, intake is 2 ~ 6 L/min.
3. the preparation method of fluorophosphoric acid vanadium sodium according to claim 1, which is characterized in that the organic reducing agent includes second
One or more of diacid, adipic acid, malonic acid, oxalic acid, formaldehyde, n-butyric acie, anti-sepsis acid, citric acid or vitamin C；Institute
State 1 ~ 5 times that organic reducing agent dosage is the required theoretical molar amount that vanadium is oxidized to trivalent vanadium.
4. the preparation method of fluorophosphoric acid vanadium sodium according to claim 1, which is characterized in that the vanadium source includes five oxidations two
One or more of vanadium or ammonium metavanadate.
5. the preparation method of fluorophosphoric acid vanadium sodium according to claim 1, which is characterized in that the phosphoric acid root includes phosphorus
One or more of acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, triammonium phosphate or ammonium phosphate.
6. the preparation method of fluorophosphoric acid vanadium sodium according to claim 1, which is characterized in that the sodium source includes hydroxide
One of sodium, sodium fluoride, sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium metavanadate, sodium vanadate or sodium dihydrogen phosphate
Or it is several；
The Fluorine source includes one or more of sodium fluoride, vanadium trifluoride or ammonium fluoride.
7. the preparation method of fluorophosphoric acid vanadium sodium according to claim 1, which is characterized in that the non-oxidizing atmosphere includes
Hydrogen, nitrogen or argon gas；The mode of the mixed grinding includes mechanical ball mill or underhand polish, and the mixed grinding is at room temperature
Carry out 0.5 ~ 2h；
The temperature of the calcining is 500 ~ 700 DEG C；
The time of the constant temperature is 1 ~ 8h.
8. a kind of anode material for lithium-ion batteries, including the fluorine phosphorus being prepared by any method of claim 1 ~ 7
Sour vanadium sodium.
9. a kind of anode, including prepared by raw material of anode material for lithium-ion batteries according to any one of claims 8.
10. a kind of battery, including anode as claimed in claim 9.
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| CN110071285A (en) * | 2019-04-18 | 2019-07-30 | 中南大学 | Sodium-ion battery positive material and the preparation method and application thereof |
| CN111446449A (en) * | 2020-03-10 | 2020-07-24 | 西安交通大学 | Multi-electron-transmission vanadium-based oxygen sodium fluophosphate battery material and preparation method thereof |
| CN112018339A (en) * | 2019-05-31 | 2020-12-01 | 中南大学 | Method for preparing sodium ion battery vanadium fluorophosphate/carbon composite positive electrode material from vanadium-containing mineral aggregate and prepared positive electrode material |
| CN112490448A (en) * | 2020-11-27 | 2021-03-12 | 中南大学 | Preparation and purification method of (fluoro) vanadium sodium phosphate compound cathode material |
| CN113517426A (en) * | 2021-06-22 | 2021-10-19 | 广东工业大学 | Sodium vanadium fluorophosphate/reduced graphene oxide composite material and preparation method and application thereof |
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| CN112490448A (en) * | 2020-11-27 | 2021-03-12 | 中南大学 | Preparation and purification method of (fluoro) vanadium sodium phosphate compound cathode material |
| CN113517426A (en) * | 2021-06-22 | 2021-10-19 | 广东工业大学 | Sodium vanadium fluorophosphate/reduced graphene oxide composite material and preparation method and application thereof |
| CN113517426B (en) * | 2021-06-22 | 2023-03-28 | 广东工业大学 | Sodium vanadium fluorophosphate/reduced graphene oxide composite material and preparation method and application thereof |
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