CN106374104A - Method for preparing sodium fluorine vanadium phosphate material in air atmosphere - Google Patents

Method for preparing sodium fluorine vanadium phosphate material in air atmosphere Download PDF

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Publication number
CN106374104A
CN106374104A CN201610881047.2A CN201610881047A CN106374104A CN 106374104 A CN106374104 A CN 106374104A CN 201610881047 A CN201610881047 A CN 201610881047A CN 106374104 A CN106374104 A CN 106374104A
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vanadium
sodium
source
air atmosphere
prepares
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CN106374104B (en
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冯季军
李烨
刘振江
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University of Jinan
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University of Jinan
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a method for preparing a sodium fluorine vanadium phosphate material in air atmosphere. The method comprises the following steps of enabling a vanadium source, a phosphate source and a carbon source to be mixed, or enabling the vanadium source and the phosphate source to be mixed and grinded; then performing calcining and sintering in argon atmosphere; cooling to the room temperature and grinding to obtain vanadium phosphate; adding the vanadium phosphate, a fluorine source and a sodium source into deionized water separately and performing magnetic stirring, moving the mixture into a high-pressure reaction kettle to be subjected to hydrothermal reaction; next, naturally cooling the reaction kettle to the room temperature, taking the mixture out, and performing water bath drying; taking the product out and carrying out grinding and tabletting, and performing calcining and sintering in the air atmosphere; and then performing furnace cooling to the room temperature and grinding to obtain the product which is sodium fluorine vanadium phosphate. The prepared sodium fluorine vanadium phosphate material is uniform in grain diameter distribution, high in purity, and high in rate capability and cycling performance.

Description

A kind of method that air atmosphere prepares fluorophosphoric acid vanadium sodium material
Technical field
The invention belongs to compound polyanionic material preparing technical field, it is related to a kind of air atmosphere and prepares fluorophosphoric acid vanadium sodium The method of material.
Background technology
Fluorophosphoric acid vanadium sodium is earliest by barker et al. proposition, its crystal structure and fluorophosphoric acid aluminum sodium (α-na3al2(po4)2f3) Similar (masquelier c.; croguennec l. polyanionic (phosphates, silicates, sulfates) frameworks as electrode materials for rechargeable li (or na) Batteries. chem. rev. 2013,113:6552-6591), there is cubic symmetrical structure, its space group isi4/ mmm.It is by [mo4f2] octahedra and [po4] the coplanar three-dimensional net structure of tetrahedron, this three-D space structure be sodium from Son provides embedded and deintercalation passage；There is reversible specific volume well with the sodium-ion battery that fluorophosphoric acid vanadium sodium makees positive electrode Amount, has between 23 DEG C to 60 DEG C and embeds stability well.
Fluorophosphoric acid vanadium sodium can be synthesized by sol-gal process, and fluorophosphoric acid vanadium sodium does positive electrode, and lithium piece does negative pole Material, in little circulation, illustrates the voltage platform of 3.6 v and fabulous capability retention (zhao j. q.; he j. p.; ding x. c.; zhou j. h.; ma y. wu s. c. huang r. m.; a novel sol-gel synthesis route to navpo4f as cathode material for hybrid lithium ion Batteries. j. power sources 2010,195:6854-6859).Fluorophosphoric acid vanadium sodium can also be solid by two steps Phase method synthesizes, and can improve the capacity of fluorophosphoric acid vanadium sodium positive electrode by different amounts of carbon coating, is 5 in carbon coating amount During wt.%, discharge capacity reaches 97.8 mah g first-1(lu y.; zhang s.; li y.; xue l. g.; xu g. j.; zhang x. w. preparation and characterization of carbon-coated navpo4f as cathode material for rechargeable sodium-ion batteries. j. power sources 2014,247:770-777).
But the defect of fluorophosphoric acid vanadium sodium hinders it also could not be used widely so far, is embodied in: (1) material times Rate poor performance, cycle performance is poor；(2) traditional fluorophosphoric acid vanadium sodium preparation method needs high temperature to carry out under argon protection.
In order that fluorophosphoric acid vanadium sodium can put into industrialized production it is necessary to improve by improving preparation method or modification Its chemical property, improves the capability retention after its multiple charge and discharge cycles and the capability retention under big multiplying power discharging.
At present, prepared fluorophosphoric acid vanadium sodium raw material in having been reported, after multiple charge and discharge cycles, its capacity keeps Rate is low, poorly conductive, and under big multiplying power, capability retention is low, and high temperature preparation under traditional argon gas atmosphere, and preparation process needs one Straight-through inert gas shielding, thus be not suitable for industrialization demand.The present invention is successfully prepared for presoma using water-heat process, and Achieve preparation navpo under air atmosphere4f.The material of application the method preparation shows excellent chemical property, 2.0 ~ The potential range interior circulation of 4.5v still has 80 mahg 100 times-1Above specific discharge capacity, and still have 64 mahg under 8c-1 Specific discharge capacity.Have no preparation navpo under any air atmosphere at present both at home and abroad4The relevant report of f.
Content of the invention
It is an object of the invention to provide a kind of air atmosphere prepares the preparation method of fluorophosphoric acid vanadium sodium material.The present invention changes The method preparing fluorophosphoric acid vanadium sodium under traditional high temperature argon atmosphere protection, prepares the forerunner of fluorophosphoric acid vanadium sodium using hydro-thermal method Body, and prepare fluorophosphoric acid vanadium sodium in air atmosphere, the fluorophosphoric acid vanadium sodium material obtained by the preparation method of the present invention, granularity is divided Uniformly, purity is high, has preferable high rate performance and cycle performance for cloth.
Embodiment of the present invention is as follows:
A kind of air atmosphere prepares the preparation method of fluorophosphoric acid vanadium sodium material, specifically comprises the following steps that
1) vanadium source, phosphoric acid root and carbon source are mixed, grind, under an argon atmosphere, through calcinations and sintering, be cooled to room temperature, grind, Obtain vanadium phosphate, vanadium phosphate, Fluorine source and sodium source are added separately in deionized water, obtain mixing molten after being uniformly mixed Liquid；
2) mixed solution of step 1) gained is transferred in teflon-lined stainless steel cauldron, after hydro-thermal reaction It is cooled to room temperature, eliminating water obtains presoma after being dried；
3) by step 2) presoma of gained takes out and grinds, tabletting, and in air atmosphere, through calcinations and sintering, it is cooled to room temperature, grind Target product fluorophosphoric acid vanadium sodium is obtained final product after mill.
It is further preferred that vanadium source described in step (1) be vanadic anhydride, ammonium metavanadate, in Vanadium sesquioxide one Kind, described phosphoric acid root is one of ammonium dihydrogen phosphate, diammonium phosphate, ammonium phosphate, and described carbon source is glucose, Vitamin C One of acid, sucrose, described Fluorine source is one of sodium fluoride, ammonium fluoride, and described sodium source is sodium acetate, sodium carbonate, fluorination At least one in sodium, sodium hydroxide.
It is further preferred that the molar ratio in vanadium source, phosphoric acid root and carbon source described in step (1) is 1:1:1 or vanadium source Molar ratio with phosphoric acid root is 1:1.
It is further preferred that calcining heat described in step (1) is 600 ~ 800 DEG C, calcination time 4 ~ 10h.
It is further preferred that the molar ratio of intermediate product vanadium phosphate, Fluorine source and sodium source is 1:1:1 described in step (1).
It is further preferred that the temperature of hydro-thermal reaction described in step (2) is 180 ~ 250 DEG C, the time of hydro-thermal reaction is 24~56h.
It is further preferred that the eliminating water drying mode of gained mixture adds for water-bath after hydro-thermal reaction described in step (2) Thermal evaporation, drying baker one of are dried, are vacuum dried, and temperature for removing water is dried and is 50 ~ 120 DEG C.
It is further preferred that the pressure of precursor powder tabletting base described in step (3) is 1 ~ 10mpa.
It is further preferred that calcining heat described in step (3) is 200 ~ 600 DEG C, calcination time is 2 ~ 10h.
It is further preferred that the type of cooling described in step (3) be programme-control slow cooling, natural cooling, by sample Put in water or one of quenching in liquid nitrogen.
The present invention has the advantages that compared with the prior art
(1) present invention changes the step preparing fluorophosphoric acid vanadium sodium under traditional argon gas atmosphere, by hydro-thermal method, heat under air atmosphere Process is prepared for fluorophosphoric acid vanadium sodium；(2) present invention the material obtaining show excellent chemical property, in 2.0 ~ 4.5v Potential range interior circulation be still not less than 80 mahg 100 times-1Specific discharge capacity, and still have 64 mahg under 8c-1's Specific discharge capacity.
Brief description
In order to be illustrated more clearly that technical scheme, below to required use in the present invention and embodiment description Accompanying drawing do simple introduction.It should be evident that drawings in the following description are only some embodiments of the present invention, for this For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings Accompanying drawing.
Fig. 1 prepares navpo for the present invention4The X-ray diffraction figure of f material sample.
Fig. 2 prepares navpo for the present invention4The scanning electron microscope (SEM) photograph of f material sample.
Fig. 3 prepares navpo for the present invention4The x- X-ray photoelectron spectroscopy X figure of f material sample v element.
Fig. 4 prepares navpo for the present invention4The charge and discharge cycles high rate performance figure of f material sample.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Whole description.
Embodiment 1:
By 0.01mol ammonium dihydrogen phosphate, 0.005mol vanadic anhydride, the mixing of 0.00167mol glucose, grind uniformly, in pipe Under argon gas atmosphere protection in formula stove, 750 DEG C of calcining 8h, then cool to room temperature with the furnace, take out and grind uniformly, obtain in 0.01mol Between product vanadium phosphate, subsequently 0.01mol intermediate product vanadium phosphate, 0.01mol sodium fluoride, 0.01mol sodium acetate are added to In the deionized water of 40ml, magnetic agitation 3h, the mixed solution then being formed is transferred in autoclave, at 200 DEG C Autoclave is subsequently naturally cooled to room temperature by lower reaction 48h, takes out 60 DEG C of drying with water baths of product, by dried product Take out, grind, by pressed powder base under pressure is for 6mpa, more in air atmosphere, 300 DEG C of calcining 5h, in tube furnace Naturally cool to room temperature, grind, obtain product fluorophosphoric acid vanadium sodium；The x- ray powder diffraction pattern of sample referring to Fig. 1, products therefrom Purity is higher, and degree of crystallinity is high；Referring to Fig. 2, products therefrom granule is cube and octahedral shape to the scanning electron microscope (SEM) photograph of sample, and Even particle size is consistent；Referring to Fig. 3, the main of products therefrom vanadium is learnt by x- X-ray photoelectron spectroscopy X and analysis titration Valence state is trivalent；Using the product of gained as positive electrode, in the glove box full of argon, composition tests button-shaped sodium ion Battery, with 0.1c(14.3ma/g) multiplying power carry out charge and discharge cycles between 2.0-4.5v, first discharge capacity be 88.30ma/ G, the discharge capacity under 8c, 16c respectively reaches 53.00,33.20ma/g, has good cycle performance and high rate performance, After heavy-current discharge, return to and remain under small current recover its initial reversible capacity, refer to Fig. 4.
Embodiment 2:
By 0.01mol diammonium phosphate, the mixing of 0.005mol Vanadium sesquioxide, grind uniformly, in tube furnace, argon gas atmosphere is protected Under shield, 600 DEG C of calcining 10h, then cool to room temperature with the furnace, take out and grind uniformly, obtain 0.01mol intermediate product vanadium phosphate, with Afterwards 0.01mol intermediate product vanadium phosphate, 0.01mol ammonium fluoride, 0.01mol sodium carbonate are added in the deionized water of 40ml, Magnetic agitation 1h, the mixed solution then being formed is transferred in autoclave, reacts 51h, subsequently by height at 180 DEG C Pressure reactor naturally cools to room temperature, takes out 50 DEG C of drying with water baths of product, and dried product is taken out, and grinds, in pressure is By pressed powder base under 1mpa, more in air atmosphere, 200 DEG C of calcining 10h, programme-control is slowly decreased to room temperature, grinds, obtain Product fluorophosphoric acid vanadium sodium.
Embodiment 3:
By 0.01mol ammonium phosphate, 0.01mol ammonium metavanadate, the mixing of 0.00167mol glucose, grind uniformly, in tube furnace Under argon gas atmosphere protection, 800 DEG C of calcining 4h, then cool to room temperature with the furnace, take out and grind uniformly, obtain 0.01mol intermediate product 0.01mol intermediate product vanadium phosphate, 0.01mol sodium fluoride, 0.01mol sodium fluoride are subsequently added to going of 40ml by vanadium phosphate In ionized water, magnetic agitation 2h, the mixed solution then being formed is transferred in autoclave, reacts at 250 DEG C Autoclave is subsequently naturally cooled to room temperature by 24h, takes out 60 DEG C of drying with water baths of product, dried product is taken out, grinds Mill, by pressed powder base under pressure is for 8mpa, more in air atmosphere, 600 DEG C of calcining 2h, plunge the sample into quenching-in water Cooling, grinds, obtains product fluorophosphoric acid vanadium sodium.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to invention protection domain Restriction, one of ordinary skill in the art should be understood that, on the basis of technical scheme, those skilled in the art are not required to The various modifications that creative work to be paid can be made or deformation are still within the scope of the present invention.

Claims (10)

1. a kind of air atmosphere prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that specifically comprising the following steps that
1) by the mixing of vanadium source, phosphoric acid root and carbon source or vanadium source and the mixing of phosphoric acid root, grind, under an argon atmosphere, through calcining Sintering, is cooled to room temperature, grinds, obtains vanadium phosphate, vanadium phosphate, Fluorine source and sodium source are added separately in deionized water, stirring Mixed solution is obtained after mix homogeneously；
2) mixed solution of step 1) gained is transferred in teflon-lined stainless steel cauldron, after hydro-thermal reaction It is cooled to room temperature, eliminating water obtains presoma after being dried；
3) by step 2) presoma of gained takes out and grinds, tabletting, and in air atmosphere, through calcinations and sintering, it is cooled to room temperature, grind Target product fluorophosphoric acid vanadium sodium is obtained final product after mill.
2. air atmosphere according to claim 1 prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that step (1) vanadium source described in is one of vanadic anhydride, ammonium metavanadate, Vanadium sesquioxide, and described phosphoric acid root is biphosphate One of ammonium, diammonium phosphate, ammonium phosphate, described carbon source is one of glucose, ascorbic acid, sucrose, described Fluorine source For one of sodium fluoride, ammonium fluoride, described sodium source is sodium acetate, at least one in sodium carbonate, sodium fluoride, sodium hydroxide.
3. air atmosphere according to claim 2 prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that step (1) molar ratio of vanadium source described in, phosphoric acid root and carbon source is the molar ratio of 1:1:1 or vanadium source and phosphoric acid root is 1:1.
4. air atmosphere according to claim 1 prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that step (1) calcining heat described in is 600 ~ 800 DEG C, calcination time 4 ~ 10h.
5. air atmosphere according to claim 1 prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that step (1) molar ratio of intermediate product vanadium phosphate described in, Fluorine source and sodium source is 1:1:1.
6. air atmosphere according to claim 1 prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that step (2) temperature of hydro-thermal reaction described in is 180 ~ 250 DEG C, and the time of hydro-thermal reaction is 24 ~ 56h.
7. air atmosphere according to claim 1 prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that step (2) after hydro-thermal reaction described in, the eliminating water drying mode of gained mixture is that heating in water bath evaporates, drying baker is dried, vacuum drying One of, temperature for removing water is dried and is 50 ~ 120 DEG C.
8. air atmosphere according to claim 1 prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that step (3) pressure of the base of precursor powder tabletting described in is 1 ~ 10mpa.
9. air atmosphere according to claim 1 prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that step (3) calcining heat described in is 200 ~ 600 DEG C, and calcination time is 2 ~ 10h.
10. air atmosphere according to claim 1 prepares the preparation method of fluorophosphoric acid vanadium sodium material it is characterised in that walking Suddenly the type of cooling described in (3) be programme-control slow cooling, natural cooling, plunge the sample in water or in liquid nitrogen quench in A kind of.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109037630A (en) * 2018-07-25 2018-12-18 三峡大学 A kind of phosphorus doping carbon coating Na3V2(PO4)2O2F positive electrode 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
CN112701285A (en) * 2020-12-29 2021-04-23 东北师范大学 Positive electrode material and preparation method and application thereof
CN112850684A (en) * 2019-11-27 2021-05-28 中国科学院大连化学物理研究所 Preparation method and application of lithium vanadium fluorophosphate
CN112864358A (en) * 2019-11-27 2021-05-28 中国科学院大连化学物理研究所 Vanadium-based polyanion compound prepared by one-step method and application thereof
CN114094066A (en) * 2021-10-29 2022-02-25 江苏大学 Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery

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CN101627493A (en) * 2007-03-06 2010-01-13 威伦斯技术公司 Method of making active materials for use in secondary electrochemical cells
US20110052986A1 (en) * 2002-04-04 2011-03-03 Jeremy Barker Sodium Ion Batteries
CN104112858A (en) * 2014-06-26 2014-10-22 西南大学 Preparation method and application of network structure nano NaVPO4F/C composite material and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050238961A1 (en) * 2001-04-06 2005-10-27 Jeremy Barker Sodium ion batteries
US20110052986A1 (en) * 2002-04-04 2011-03-03 Jeremy Barker Sodium Ion Batteries
CN101627493A (en) * 2007-03-06 2010-01-13 威伦斯技术公司 Method of making active materials for use in secondary electrochemical cells
CN104112858A (en) * 2014-06-26 2014-10-22 西南大学 Preparation method and application of network structure nano NaVPO4F/C composite material and application thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109037630A (en) * 2018-07-25 2018-12-18 三峡大学 A kind of phosphorus doping carbon coating Na3V2(PO4)2O2F positive electrode and preparation method thereof
CN109037630B (en) * 2018-07-25 2019-04-30 三峡大学 A kind of phosphorus doping carbon coating Na3V2(PO4)2O2F positive electrode 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
CN112850684A (en) * 2019-11-27 2021-05-28 中国科学院大连化学物理研究所 Preparation method and application of lithium vanadium fluorophosphate
CN112864358A (en) * 2019-11-27 2021-05-28 中国科学院大连化学物理研究所 Vanadium-based polyanion compound prepared by one-step method and application thereof
CN112850684B (en) * 2019-11-27 2022-07-08 中国科学院大连化学物理研究所 Preparation method and application of lithium vanadium fluorophosphate
CN112864358B (en) * 2019-11-27 2023-11-07 中国科学院大连化学物理研究所 Vanadium-based polyanion compound prepared by one-step method and application thereof
CN112490448A (en) * 2020-11-27 2021-03-12 中南大学 Preparation and purification method of (fluoro) vanadium sodium phosphate compound cathode material
CN112701285A (en) * 2020-12-29 2021-04-23 东北师范大学 Positive electrode material and preparation method and application thereof
CN114094066A (en) * 2021-10-29 2022-02-25 江苏大学 Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery

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