CN114538523A - Iron vanadate material and preparation method and application thereof - Google Patents
Iron vanadate material and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 41
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 35
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 19
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 229910003206 NH4VO3 Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C01P2004/60—Particles characterised by their size
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
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Abstract
The invention discloses an iron vanadate material and a preparation method and application thereof, and belongs to the technical field of batteries. The preparation method of the material comprises the following steps: (1) adding ammonium metavanadate into water, and stirring and dissolving to obtain a solution A; (2) adding ferric nitrate into water, and stirring and dissolving to obtain a solution B; (3) pouring the solution B into the solution A, and continuously stirring to form a uniform suspension solution; (4) carrying out hydrothermal reaction on the suspension solution obtained in the step (3) to obtain an iron vanadate precursor; (5) and (5) calcining the iron vanadate precursor obtained in the step (4) in an air atmosphere, and naturally cooling to obtain the iron vanadate material. The preparation method is simple to operate, low in cost, controllable in reaction and suitable for industrial production. The iron vanadate material synthesized by the invention can be used as a lithium/sodium ion battery cathode material and a zinc ion battery anode material at the same time.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an iron vanadate material, and a preparation method and application thereof.
Background
At present, lithium ion batteries are widely applied to the fields of portable electronic equipment, electric automobiles, smart power grids and the like. However, with the development of electric vehicles and large energy storage power stations, higher requirements are put on lithium ion batteries. The current commercial graphite negative electrode has a limited theoretical specific capacity, which makes it difficult to meet the requirements of a new generation of high-performance lithium ion battery. In recent years, the more binary transition metal oxides have been used as electrode materialsMore attention has been paid to the fact that, due to the coexistence of two different transition metal elements, very high specific capacities are generally obtained. In addition, binary transition metal oxides generally have higher conductivity and better cycling stability than single transition metal oxides due to the synergistic effect of electron transfer between cations and relatively low activation energy. In view of the multiple valence states of vanadium and iron and the rich source of iron, iron vanadate materials are expected to be used as lithium ion battery negative electrode materials. Fe2V4O13The material is an iron vanadate material with a horseshoe-shaped chain structure, and the quadrangular and hexagonal channels of the material are beneficial to the transmission of lithium ions, so that the material is expected to realize high electrochemical performance.
Sodium ion batteries are considered one of the most promising alternatives to lithium ion batteries because of their abundant sodium resources, and electrochemical reaction processes similar to those of lithium ion batteries. However, the radius of sodium ions is larger than that of lithium ions, and most of electrode materials suitable for lithium ion batteries are not suitable for sodium ion batteries. And Fe2V4O13Has large channels and is promising as the electrode material of the sodium ion battery.
Aqueous zinc ion batteries are also promising alternatives to lithium ion batteries due to their abundant raw materials and environmental friendliness. At present, vanadium-based materials are widely used as the anode materials of aqueous zinc ion batteries, but Fe2V4O13Has not been studied as a positive electrode material for an aqueous zinc-ion battery.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of an iron vanadate material.
The invention also aims to provide the iron vanadate material prepared by the method.
The invention further aims to provide application of the iron vanadate material in the fields of lithium ion batteries, sodium ion batteries and zinc ion batteries.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a ferrovanadate material comprises the following steps:
(1) mixing ammonium metavanadate (NH)4VO3) Adding the mixture into water, and stirring and dissolving to obtain a solution A;
(2) mixing ferric nitrate (Fe (NO)3)3·9H2O) adding the mixture into water, and stirring and dissolving to obtain a solution B;
(3) pouring the solution B into the solution A, and continuously stirring to form a uniform suspension solution;
(4) carrying out hydrothermal reaction on the suspension solution obtained in the step (3) to obtain an iron vanadate precursor;
(5) calcining the iron vanadate precursor obtained in the step (4) in air atmosphere, and naturally cooling to obtain an iron vanadate material, namely Fe2V4O13。
Preferably, the molar ratio of vanadium to iron in the ammonium metavanadate to the iron nitrate is 2: 1.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 100-200 ℃ and the time is 1-12 hours.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 180 ℃ and the time is 3 hours.
Preferably, in the step (4), after the hydrothermal reaction of the suspension solution, the suspension solution is cooled to room temperature, and then is subjected to centrifugation, drying and grinding in sequence.
Preferably, the calcining temperature in the step (5) is 300-800 ℃, and the calcining time is 2-12 hours.
An iron vanadate material prepared by the preparation method of any one of the above.
The iron vanadate material is applied to preparation of a lithium ion battery cathode material.
The iron vanadate material is applied to preparation of a sodium ion battery cathode material.
The iron vanadate material is applied to preparation of a zinc ion battery anode material.
Compared with the prior art, the invention has the following advantages:
(1) the invention adopts hydrothermal combined calcinationThe method of burning treatment synthesizes pure-phase Fe2V4O13The preparation method has the advantages of simple operation, low cost and controllable reaction, and is suitable for industrial production.
(2) Fe synthesized by the invention2V4O13The material can be simultaneously used as a negative electrode material of a lithium/sodium ion battery and a positive electrode material of a zinc ion battery, and the material is tried to be applied as the negative electrode material of the lithium/sodium ion battery and the positive electrode material of the zinc ion battery for the first time.
(3) Fe synthesized by the invention2V4O13The material has wide application, not only can be used as an electrode material in the field of energy storage, but also can be used in the fields of catalysis, refrigeration and the like.
Drawings
FIG. 1 is Fe in example 1 of the present invention2V4O13X-ray diffraction pattern of (a).
FIG. 2 is Fe in example 1 of the present invention2V4O13Scanning electron microscope pictures.
FIG. 3 is Fe in example 1 of the present invention2V4O13The cycle performance curve chart of the lithium ion battery cathode is shown.
FIG. 4 is Fe in example 1 of the present invention2V4O13And the obtained picture is taken as a scanning electron microscope picture after the lithium ion battery cathode is cycled for 80 times.
FIG. 5 shows Fe in example 1 of the present invention2V4O13And the obtained picture is taken as a scanning electron microscope picture after the lithium ion battery cathode is cycled for 500 times.
FIG. 6 is Fe in example 1 of the present invention2V4O13And taking the curve chart of the charge and discharge of the first three circles of the negative electrode of the sodium-ion battery.
FIG. 7 shows Fe in example 1 of the present invention2V4O13And taking the curve chart of the charge and discharge of the first three circles of the positive electrode of the zinc ion battery.
FIG. 8 shows Fe in example 2 of the present invention2V4O13X-ray diffraction pattern of (a).
FIG. 9 shows Fe in example 2 of the present invention2V4O13Scanning electron microscope pictures.
FIG. 10 shows Fe in example 2 of the present invention2V4O13The cycle performance curve diagram of the lithium ion battery cathode is shown.
FIG. 11 shows Fe in example 2 of the present invention2V4O13And taking the curve chart of the charge and discharge of the first three circles of the negative electrode of the sodium-ion battery.
FIG. 12 shows Fe in example 2 of the present invention2V4O13And taking the curve chart of the charging and discharging of the first three circles of the positive electrode of the zinc ion battery.
FIG. 13 is Fe in example 3 of the present invention2V4O13X-ray diffraction pattern of (a).
FIG. 14 is Fe in example 3 of the present invention2V4O13The cycle performance curve chart of the lithium ion battery cathode is shown.
Detailed Description
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The practice of the present invention will be further illustrated, but is not limited, by the following examples and the accompanying drawings.
Example 1
Adding 4mmol NH4VO3Adding 20ml of deionized water, placing the mixture on a magnetic stirrer, and uniformly stirring the mixture to fully dissolve the mixture (solution A); 2mmol of Fe (NO)3)3·9H2Adding O into 20ml of deionized water, placing the mixture on a magnetic stirrer, and uniformly stirring the mixture to fully dissolve the O (solution B); slowly pouring the solution B into the solution A, and stirring the solution A under the condition of uninterrupted magnetic force to form uniform suspension solution; and transferring the obtained suspension solution to a high-pressure reaction kettle for hydrothermal reaction at 180 ℃ for 3 hours, cooling to room temperature, centrifuging, drying and grinding to obtain iron vanadate precursor powder. Calcining the iron vanadate precursor powder material for 2h at 500 ℃ in air atmosphere, and naturally cooling to obtain the iron vanadate material, namely Fe2V4O13。
The X-ray diffraction pattern of the product obtained in this example is shown in FIG. 1. As can be seen from FIG. 1, pure-phase monoclinic Fe was synthesized by this method2V4O13A material. The absence of impurity peaks in the spectrogram indicates that the product has high purity, narrow and sharp diffraction peaks and good crystallinity. The scanning electron micrograph of the product is shown in FIG. 2, and it can be seen that Fe2V4O13Is composed of a plurality of large irregularly-shaped particles with the particle size of between a few microns and tens of microns. And these microparticles are composed of a large number of nanoparticles, which are relatively loose among them.
Manufacturing an electrode plate of the lithium ion battery: fe prepared in this example2V4O13The electrode plate is prepared by fully mixing and grinding a conductive agent Super P and a binding agent sodium alginate in deionized water according to the ratio of 7:2:1 to obtain uniform slurry, coating the slurry on a current collector copper foil, naturally volatilizing a surface water solvent, and finally drying in a vacuum oven at 90 ℃ overnight.
Manufacturing an electrode plate of the sodium-ion battery: fe prepared in this example2V4O13The electrode plate is prepared by fully mixing and grinding a conductive agent Super P and a binder PVDF in NMP (1-methyl-2 pyrrolidone) according to the ratio of 7:2:1 to obtain uniform slurry, coating the slurry on a current collector copper foil, then copying under an infrared lamp for 30 minutes to dry a surface solvent, and finally completely drying in a vacuum oven at 90 ℃ for one night.
Manufacturing an electrode plate of the zinc ion battery: fe prepared in this example2V4O13Fully mixing and grinding a conductive agent Super P and a binder PVDF in NMP (1-methyl-2 pyrrolidone) according to the ratio of 7:2:1 to obtain uniform slurry, coating the slurry on a current collector titanium foil, then copying for 30 minutes under an infrared lamp to bake a surface solvent, and finally completely drying in a vacuum oven at 90 ℃ for one night to obtain an electrode plate;
assembling the lithium ion battery: mixing the obtained Fe2V4O13The pole piece is a working electrode, and the lithium piece isCounter electrode, 1M LiPF6EC (EC) of (C) DEC (EMC) (1:1:1 vol.%) is electrolyte, Celgard2320 is diaphragm, and the diaphragm is assembled into a CR2032 type button cell in a high-purity argon glove box.
Assembling the sodium-ion battery: mixing the obtained Fe2V4O13The pole piece is a working electrode, the sodium piece is a counter electrode, and 1M NaClO4A CR2032 type coin cell was assembled in a high purity argon glove box with electrolyte (solvents EC: DMC (1:1 vol.%) and 5 wt.% FEC) and glass fiber separator.
Assembling the zinc ion battery: mixing the obtained Fe2V4O13The CR2032 type button cell is assembled in the air by taking the pole piece as a working electrode, the zinc sheet as a counter electrode, 2M zinc sulfate as electrolyte and glass fiber as a diaphragm.
And (3) testing the battery: the button cell prepared above was tested in the wuhan blue-electricity system with a room temperature constant at 25 ℃.
Fe of the present example2V4O13When the lithium ion battery cathode material is used in a voltage range of 0.01-3V and the current density is 2A/g, the cycle is performed for 500 times, and the cycle performance is shown in figure 3. As can be seen from FIG. 3, the first charging specific capacity is about 1048mAh/g, the first coulombic efficiency is 75.9%, and such high specific capacity and coulombic efficiency are mainly due to the high valence state of the metal element and Fe2V4O13The specific structure of (1). With the circulation, the specific capacity is continuously reduced, and is continuously increased after about 80 times of circulation, and finally, the specific capacity tends to be stable. After 500 cycles, the specific capacity of the battery is stabilized at 850 mAh/g. Fe prepared in this example2V4O13The lithium ion battery cathode material has high specific capacity even under high current density and is stable for a long time, and is a very potential lithium ion battery cathode material. Fe of the present example2V4O13The scanning electron micrographs of the lithium ion battery cathode material after 80 cycles and 500 cycles are respectively shown in fig. 4 and fig. 5. As can be seen from FIG. 4, Fe after 80 cycles2V4O13Electrode surface and Fe in FIG. 22V4O13The powder is totally different, which should have occurredThe structure is recombined. And large blocks exist on the surface, and cracks exist among the blocks, so that the specific capacity is reduced correspondingly. It can be seen from the electrode after 500 cycles of fig. 5 that the surface cracks are significantly reduced and the grains are also smaller, indicating Fe in the process2V4O13The bulk is crushed, which helps to shorten the diffusion path of lithium ions, thereby increasing the specific capacity (activation process).
Fe of the present example2V4O13The charge-discharge curve chart of the first three circles is shown in figure 6 when the sodium ion battery cathode material is in a voltage range of 0.01-3V and the current density is 100 mA/g. The first charging specific capacity is about 446mAh/g, which indicates that Fe2V4O13Is feasible as the negative electrode material of the sodium-ion battery.
Fe of the present example2V4O13When the zinc ion battery anode material is used in a voltage range of 0.2-1.6V and the current density is 50mA/g, the first three-circle charge-discharge curve chart is shown in figure 7. The first charging specific capacity is about 349mAh/g, which indicates that Fe2V4O13Is feasible as the positive electrode material of the zinc ion battery.
Example 2
Adding 4mmol NH4VO3Adding 20ml of deionized water, placing the mixture on a magnetic stirrer, and uniformly stirring the mixture to fully dissolve the mixture (solution A); 2mmol of Fe (NO)3)3·9H2Adding O into 20ml of deionized water, placing the mixture on a magnetic stirrer, and uniformly stirring the mixture to fully dissolve the O (solution B); slowly pouring the solution B into the solution A, and stirring the solution A under the condition of uninterrupted magnetic force to form uniform suspension solution; and transferring the obtained suspension solution to a high-pressure reaction kettle for hydrothermal reaction at 180 ℃ for 3 hours, cooling to room temperature, centrifuging, drying and grinding to obtain iron vanadate precursor powder. Calcining the iron vanadate precursor powder material for 12h at 300 ℃ in air atmosphere, and naturally cooling to obtain the iron vanadate material, namely Fe2V4O13。
The X-ray diffraction pattern of the product obtained in this example is shown in FIG. 8. From FIG. 8, it can be seen thatMonoclinic Fe synthesized by the method2V4O13The material is amorphous. The scanning electron micrograph of the product is shown in FIG. 9, and it can be seen that Fe2V4O13Consists of many nanoparticles, which are relatively bulky, which facilitates lithium ion transport.
Manufacturing an electrode plate of the lithium ion battery: fe prepared in this example2V4O13The electrode plate is prepared by fully mixing and grinding a conductive agent Super P and a binding agent sodium alginate in deionized water according to the ratio of 7:2:1 to obtain uniform slurry, coating the slurry on a current collector copper foil, naturally volatilizing a surface water solvent, and finally drying in a vacuum oven at 90 ℃ overnight.
Manufacturing an electrode plate of the sodium-ion battery: fe prepared in this example2V4O13The electrode plate is prepared by fully mixing and grinding a conductive agent Super P and a binder PVDF in NMP (1-methyl-2 pyrrolidone) according to the ratio of 7:2:1 to obtain uniform slurry, coating the slurry on a current collector copper foil, then copying under an infrared lamp for 30 minutes to dry a surface solvent, and finally completely drying in a vacuum oven at 90 ℃ for one night.
Manufacturing an electrode plate of the zinc ion battery: fe prepared in this example2V4O13Fully mixing and grinding a conductive agent Super P and a binder PVDF in NMP (1-methyl-2 pyrrolidone) according to the ratio of 7:2:1 to obtain uniform slurry, coating the slurry on a current collector titanium foil, then copying for 30 minutes under an infrared lamp to bake a surface solvent, and finally completely drying in a vacuum oven at 90 ℃ for one night to obtain an electrode plate;
assembling the lithium ion battery: mixing the obtained Fe2V4O13The pole piece is a working electrode, the lithium piece is a counter electrode, and 1M LiPF6EC (EC) of (C) DEC (EMC) (1:1:1 vol.%) is electrolyte, Celgard2320 is diaphragm, and the diaphragm is assembled into a CR2032 type button cell in a high-purity argon glove box.
Assembling the sodium-ion battery: mixing the obtained Fe2V4O13The pole piece is a working electrode, the sodium piece is a counter electrode, and 1M NaClO4A CR2032 type coin cell was assembled in a high purity argon glove box with electrolyte (solvents EC: DMC (1:1 vol.%) and 5 wt.% FEC) and glass fiber separator.
Assembling the zinc ion battery: mixing the obtained Fe2V4O13The CR2032 type button cell is assembled in the air by taking the pole piece as a working electrode, the zinc piece as a counter electrode, 3M zinc trifluoromethanesulfonate as electrolyte and glass fiber as a diaphragm.
And (3) testing the battery: the button cell prepared above was tested in the wuhan blue-electricity system with a room temperature constant at 25 ℃.
Fe of the present example2V4O13When the material is used as a negative electrode material of a lithium ion battery, the voltage is in a range of 0.01-3V, the current density is 100mA/g, the cycle is 200 times, and the cycle performance is shown in figure 10. As can be seen from FIG. 10, the first charge specific capacity is about 1049mAh/g, and as the cycle proceeds, the specific capacity decreases and then increases continuously, and after 200 cycles, the specific capacity is about 1639mAh/g and tends to increase continuously.
Fe of the present example2V4O13The charge-discharge curve of the first three circles is shown in figure 11 when the sodium ion battery cathode material is in a voltage range of 0.01-3V and the current density is 100 mA/g. The first charging specific capacity is about 485mAh/g, which shows that Fe2V4O13Is a very potential sodium ion battery cathode material.
Fe of the present example2V4O13When the zinc ion battery anode material is used in a voltage range of 0.2-1.6V and the current density is 50mA/g, the first three-circle charge-discharge curve chart is shown in figure 12. The first charging specific capacity is about 400mAh/g, which shows that Fe2V4O13Is a very potential positive electrode material of a zinc ion battery.
Example 3
Adding 4mmol NH4VO3Adding 20ml of deionized water, placing the mixture on a magnetic stirrer, and uniformly stirring the mixture to fully dissolve the mixture (solution A); 2mmol of Fe (NO)3)3·9H2Adding O into 20ml deionized water, placing on a magnetic stirrer, and uniformly stirring to fully stirDissolution (solution B); slowly pouring the solution B into the solution A, and stirring the solution A under the condition of uninterrupted magnetic force to form uniform suspension solution; and transferring the obtained suspension solution to a high-pressure reaction kettle for hydrothermal reaction at 180 ℃ for 3 hours, cooling to room temperature, centrifuging, drying and grinding to obtain iron vanadate precursor powder. Calcining the iron vanadate precursor powder material for 6h at 800 ℃ in air atmosphere, and naturally cooling to obtain the iron vanadate material, namely Fe2V4O13。
The X-ray diffraction pattern of the product obtained in this example is shown in FIG. 13. As can be seen from FIG. 13, pure-phase monoclinic Fe was synthesized by this method2V4O13A material. The spectrogram has no impurity peak, which indicates that the product has high purity, and the diffraction peak is narrow and sharp, which indicates that the crystallinity is good.
Manufacturing an electrode plate of the lithium ion battery: fe prepared in this example2V4O13The electrode plate is prepared by fully mixing and grinding a conductive agent Super P and a binder PVDF in NMP (1-methyl-2 pyrrolidone) according to the ratio of 7:2:1 to obtain uniform slurry, coating the slurry on a current collector copper foil, then copying under an infrared lamp for 30 minutes to dry a surface solvent, and finally completely drying in a vacuum oven at 90 ℃ for one night.
Assembling the lithium ion battery: mixing the obtained Fe2V4O13The pole piece is a working electrode, the lithium piece is a counter electrode, and 1M LiPF6EC (EC) of (C) DEC (EMC) (1:1:1 vol.%) is electrolyte, Celgard2320 is diaphragm, and the diaphragm is assembled into a CR2032 type button cell in a high-purity argon glove box.
And (3) testing the battery: the button cell prepared above was tested in the wuhan blue-electricity system with a room temperature constant at 25 ℃.
Fe of the present example2V4O13When the lithium ion battery cathode material is used in a voltage range of 0.01-3V and the current density is 100mA/g, the cycle is performed for 200 times, and the cycle performance is shown in FIG. 14. As can be seen from fig. 14, the first charging specific capacity is about 920mAh/g, and as the cycle proceeds, the specific capacity decreases, increases and stabilizes. Through 200 cyclesThen, the specific capacity is about 1004 mAh/g.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the disclosure.
Claims (10)
1. The preparation method of the iron vanadate material is characterized by comprising the following steps of:
(1) adding ammonium metavanadate into water, and stirring and dissolving to obtain a solution A;
(2) adding ferric nitrate into water, and stirring and dissolving to obtain a solution B;
(3) pouring the solution B into the solution A, and continuously stirring to form a uniform suspension solution;
(4) carrying out hydrothermal reaction on the suspension solution obtained in the step (3) to obtain an iron vanadate precursor;
(5) calcining the iron vanadate precursor obtained in the step (4) in air atmosphere, and naturally cooling to obtain an iron vanadate material, namely Fe2V4O13。
2. The method of claim 1, wherein the molar ratio of vanadium to iron in the ammonium metavanadate to iron nitrate is 2: 1.
3. The preparation method according to claim 2, wherein the hydrothermal reaction in the step (4) is carried out at a temperature of 100 to 200 ℃ for 1 to 12 hours.
4. The method according to claim 3, wherein the hydrothermal reaction in step (4) is carried out at 180 ℃ for 3 hours.
5. The method according to any one of claims 1 to 4, wherein in the step (4), the suspension is subjected to hydrothermal reaction, then cooled to room temperature, and then subjected to centrifugation, drying and grinding in this order.
6. The method according to any one of claims 1 to 4, wherein the calcination in step (5) is carried out at a temperature of 300 ℃ to 800 ℃ for 2 to 12 hours.
7. An iron vanadate material prepared by the preparation method according to any one of claims 1 to 6.
8. The use of an iron vanadate material according to claim 7 for preparing a lithium ion battery negative electrode material.
9. The use of an iron vanadate material according to claim 7 for preparing a negative electrode material of a sodium ion battery.
10. The use of an iron vanadate material according to claim 7 for preparing a positive electrode material of a zinc ion battery.
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