CN103872324A - Preparation method of petaloid lithium ion battery negative electrode material VPO4 - Google Patents
Preparation method of petaloid lithium ion battery negative electrode material VPO4 Download PDFInfo
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- CN103872324A CN103872324A CN201410120043.3A CN201410120043A CN103872324A CN 103872324 A CN103872324 A CN 103872324A CN 201410120043 A CN201410120043 A CN 201410120043A CN 103872324 A CN103872324 A CN 103872324A
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- Prior art keywords
- lithium ion
- ion battery
- vpo
- battery negative
- vanadium
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000007773 negative electrode material Substances 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000012002 vanadium phosphate Substances 0.000 claims abstract description 14
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 4
- 239000000203 mixture Substances 0.000 abstract 3
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 1
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for preparing a petaloid lithium ion battery negative electrode material vanadium phosphate (VPO4) by a liquid phase method, which belongs to the technical field of a lithium ion battery. The method is characterized by preparing the lithium ion battery negative electrode material VPO4 by the liquid phase method and comprises the specific steps of dissolving a vanadium source, a phosphorus source and a reducing agent in the molar ratio of 1:1:2 into water, adjusting the pH value to be 7, and stirring the mixture to obtain a homogenous solution, sol or turbid liquid; transferring the obtained homogenous solution, sol or turbid liquid into a polytetrafluoroethylene tank, placing the mixture into a pyrolysis tank, heating the mixture in a drying box to 280 DEG C for reacting for 30h to obtain an amorphous vanadium phosphate precursor; and grinding and tabletting the amorphous vanadium phosphate precursor, sintering the amorphous precursor in a tubular sintering furnace at the temperature of 725 DEG C under the non-oxidation atmosphere for 6h, and cooling the precursor to the room temperature to obtain the vanadium phosphate product. The microstructure of the prepared negative electrode material VPO4 is in the shape of petaloid microsphere formed by stacking nano-sheets, the material is unique in shape, and the electrochemical performance is excellent.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, specifically a kind of a kind of petal-shaped lithium ion battery negative material of Liquid preparation methods VPO that adopts
4method.Belong to technical field of lithium ion.
Background technology
Along with the arrival in electronic information epoch, for meeting the energy demand of growing various mobile devices, the trend that the development life-span is long, specific power is large, cost is low, free of contamination high-performance secondary lithium battery has become current research.Lithium ion battery negative material is the key components of lithium ion battery, in commercialization at present, main application is graphite cathode, but no matter be that native graphite or its theoretical specific capacity of Delanium are all 372mAh/g, along with the exploitation of some height ratio capacity positive electrodes, the graphite with lower specific capacity can not meet the demand of positive electrode already as negative pole.Therefore, the negative material of research and development height ratio capacity has very large potential value.
In numerous alternative negative materials, VPO
4pass through PO
4 3-the deintercalation that polyanion is lithium ion provides stable 3D frame structure, has alleviated the excessive problem of material volume irreversible change in charge and discharge process, and VPO
4there is higher specific capacity (550mAh/g) and China's vanadium resource abundant, raw material wide material sources, with low cost.Therefore, VPO
4it is a lithium ion battery negative material with very large potential value.
At present, as negative pole VPO
4preparation mainly by the method for collosol and gel, but its synthetic VPO
4microscopic appearance wayward, be unfavorable for Physical Processing performance, and inhomogenous microscopic appearance also has larger impact to the chemical property of material.Exploring new synthetic method is to improve VPO
4an effective way of negative material chemical property and Physical Processing performance.The present invention has synthesized the stacking microspheroidal VPO of nanometer sheet by liquid phase method
4negative material, the material electrochemical performance excellence of synthesized, and also the second particle of microspheroidal is conducive to improve the Physical Processing performance of material.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing Liquid preparation methods petal-shaped lithium ion battery negative material vanadium phosphate, to improve lithium ion battery negative material vanadium phosphate chemical property and Physical Processing performance.
Technical scheme of the present invention is as follows:
(1) vanadium source, phosphorus source are mixed with the mol ratio of vanadium ion, phosphate anion at 1: 1, add the organic carbon source of 2 times of lithium source molal quantitys as reactant feed simultaneously, concentration of metal ions is controlled at 0.001-2mol/L.
(2) above-mentioned solution is placed in to 20-100 DEG C of thermostat water bath and stirs 4H, form solution, colloidal sol or suspension-turbid liquid;
(3) above-mentioned solution, colloidal sol or suspension-turbid liquid are regulated to PH to 1-14;
(4) above-mentioned solution, colloidal sol or suspension-turbid liquid are moved in polytetrafluoroethyltank tank, are placed in pyrolytic tank and add thermal response 1-72H in 100-350 DEG C;
(5) above-mentioned reactor product is taken out, filter 40-150 DEG C of oven dry of vacuum and obtain amorphous state VPO
4presoma;
(6) by above-mentioned amorphous state presoma VPO
4be placed in pipe type sintering furnace, 300-900 DEG C of sintering 0.1-20H under nonoxidizing atmosphere, cool to room temperature obtains petal-shaped VPO
4;
Further, the vanadium source described in step (1) is vanadic oxide, ammonium metavanadate, ammonium vanadate, vanadium trioxide, oxalic acid vanadyl one;
Further, the phosphorus source described in step (1) is the one in ammonium dihydrogen phosphate, phosphorus hydrogen two ammoniums, ammonium phosphate, phosphoric acid, pyrophosphoric acid;
Further, the reducing agent described in step (1) is the one in tartaric acid, citric acid, oxalic acid, ethanedioic acid, adipic acid, malonic acid, ascorbic acid;
Further, in step (6), the nonoxidizing atmosphere of sintering is the one in argon gas, nitrogen, hydrogen, helium, carbon monoxide;
Advantage of the present invention:
The present invention utilizes solwution method to prepare petal-shaped lithium ion battery negative material VPO
4.Preparing negative pole utmost point material is by the sheet VPO with nano thickness
4the stacking microspheroidal VPO that forms
4its laminated structure has the abundant infiltration that higher specific area is conducive to electrolyte, being connected of lamella, shorten ion transfer path, be conducive to the transmission of lithium ion, the stacking microballoon forming of nanometer sheet is conducive to lithium ion in the embedding of all directions and deviates from, and material high rate performance is improved significantly, and second particle using microspheroidal as material is conducive to improve the Physical Processing performance of material, especially the tap density of material is greatly improved.The petal-like negative pole utmost point of the stacking microspheroidal forming of the nanometer sheet material VPO that the present invention is synthetic
4there is the chemical property of good excellence.
Brief description of the drawings
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, for explaining the present invention, is not construed as limiting the invention together with embodiments of the present invention.In the accompanying drawings:
Fig. 1 is the XRD figure of No. 3 samples in embodiment 1;
Fig. 2 is the SEM diffraction pattern of No. 3 sample presomas in embodiment 1;
Fig. 3 is 0.1C, the 1C discharge curve first of No. 3 samples in embodiment 1;
Embodiment
Embodiment 1
Take vanadic oxide 0.91g, diammonium hydrogen phosphate 1.15g, citric acid 1.4g, is dissolved in the deionized water of 80mL, and in 80 DEG C of water-baths, mechanical agitation, to forming homogeneous blue solution, regulates PH=7; Then gone to and in polytetrafluoroethyltank tank, be placed in 280 DEG C of pyrolytic tanks and add thermal response 30h, be cooled to room temperature and take out and filter, by filtration product 80 DEG C of oven dry in vacuum drying oven.Oven dry powder is fully ground in agate mortar, be then placed in sintering furnace, under argon gas atmosphere, in 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C sintering 6h, be then naturally cooled to room temperature and obtain vanadium phosphate.Products obtained therefrom wherein obtains pure phase VPO at 600 DEG C, 700 DEG C through XRD analysis
4, at other temperature, products obtained therefrom has VPO
4h
2o or V
2o
5dephasign.Detect by SEM, the microscopic appearance of 1,2, No. 3 resulting materials is the stacking microballoon of nanometer sheet.Obtained product is assembled into experiment button cell and surveys its charging and discharging capacity and cycle performance, carry out charge-discharge test under 0.1C, 1C, its first discharge specific capacity is in table 1.
The experiment condition of table 1 experimental example 1 and experimental result
Embodiment 2
Take vanadic oxide 1.82g, diammonium hydrogen phosphate 2.3g, citric acid 2.8g, is dissolved in the deionized water of 80mL, and in 80 DEG C of water-baths, mechanical agitation, to forming homogeneous green solution, regulates PH=7; Then gone to and in polytetrafluoroethyltank tank, be placed in 280 DEG C of pyrolytic tanks and add thermal response 30h, be cooled to room temperature and take out and filter, by filtration product 80 DEG C of oven dry in vacuum drying oven.Oven dry powder is fully ground in agate mortar, be then placed in sintering furnace, under argon gas atmosphere, in 700 DEG C of sintering 2h, 4h, 8h, 10h, is then naturally cooled to room temperature and obtains vanadium phosphate.Products obtained therefrom is all pure phase VPO through XRD analysis
4, detect by SEM, the microscopic appearance of 1, No. 2 resulting materials is the stacking microballoon of nanometer sheet, 3, No. 4 resulting materials without special appearance.Obtained product is assembled into experiment button cell and surveys its charging and discharging capacity and cycle performance, carry out charge-discharge test under 0.1C, 1C, its first discharge specific capacity is in table 2.
The experiment condition of table 2 experimental example 2 and experimental result
Embodiment 3
Take ammonium metavanadate 1.17g, diammonium hydrogen phosphate 1.15g, citric acid 1.4g, is dissolved in the deionized water of 80mL, and in 80 DEG C of water-baths, mechanical agitation, to forming homogeneous green solution, regulates PH=7; Then gone to and in polytetrafluoroethyltank tank, be placed in 150 DEG C of pyrolytic tanks, 200 DEG C, 250 DEG C, 300 DEG C and add thermal response 30h, be cooled to room temperature and take out and filter, by filtration product 80 DEG C of oven dry in vacuum drying oven.Oven dry powder is fully ground in agate mortar, be then placed in sintering furnace, under argon gas atmosphere, in 700 DEG C of sintering 6h, be then naturally cooled to room temperature and obtain vanadium phosphate.Products obtained therefrom, through XRD analysis, only has sample 3 to obtain pure phase VPO
4.Detect by SEM, the microscopic appearance of 1,2, No. 3 resulting materials is nano-sheet structure.Obtained product is assembled into experiment button cell and surveys its charging and discharging capacity and cycle performance, carry out charge-discharge test under 0.1C, 1C, its first discharge specific capacity and circulation are in table 3.
The experiment condition of table 3 experimental example 3 and experimental result
Embodiment 4
Take vanadic oxide 0.91g, diammonium hydrogen phosphate 1.15g, citric acid 1.4g, is dissolved in the deionized water of 80mL, and in 80 DEG C of water-baths, mechanical agitation, to forming homogeneous blue solution, regulates PH=7; Then gone to and in polytetrafluoroethyltank tank, be placed in 280 DEG C of pyrolytic tanks and add thermal response 5h, 10h, 20h, 40h, be cooled to room temperature and take out and filter, by filtration product 80 DEG C of oven dry in vacuum drying oven.Oven dry powder is fully ground in agate mortar, be then placed in sintering furnace, under argon gas atmosphere, in 700 DEG C of sintering 6h, be then naturally cooled to room temperature and obtain vanadium phosphate.Products obtained therefrom, through XRD analysis, only has sample 2 to obtain pure phase VPO
4.Detect by SEM, the microscopic appearance of 1,2, No. 3 resulting materials is nano-sheet.Obtained product is assembled into experiment button cell and surveys its charging and discharging capacity and cycle performance, carry out charge-discharge test under 0.1C, 1C, its first discharge specific capacity and circulation are in table 4
The experiment condition of table 4 experimental example 4 and experimental result
Claims (6)
1. a preparation method for petal-shaped lithium ion battery negative material vanadium phosphate, is characterized in that comprising the following steps:
(1) vanadium source, phosphorus source are mixed with the mol ratio of vanadium ion, phosphate anion at 1: 1, add the organic carbon source of 2 times of lithium source molal quantitys as reactant feed simultaneously, concentration of metal ions is controlled at 0.001-2mol/L;
(2) above-mentioned solution is placed in to 20-100 DEG C of thermostat water bath and stirs 4H, form solution, colloidal sol or suspension-turbid liquid;
(3) above-mentioned solution, colloidal sol or suspension-turbid liquid are regulated to PH to 1-14;
(4) above-mentioned solution, colloidal sol or suspension-turbid liquid are moved in polytetrafluoroethyltank tank, are placed in pyrolytic tank and add thermal response 1-72H in 100-350 DEG C;
(5) above-mentioned reactor product is taken out, filter, vacuum 40-150 DEG C of oven dry obtains amorphous state VPO
4presoma;
(6) by above-mentioned amorphous state presoma VPO
4be placed in pipe type sintering furnace, 300-900 DEG C of sintering 0.1-20H under nonoxidizing atmosphere, cool to room temperature obtains petal-shaped VPO
4.
2. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method, it is characterized in that: vanadium source, phosphorus source are mixed by mole proportioning with reducing agent at 1: 1: 2, and vanadium metal ion concentration is controlled at 0.001-2mol L
-1between.
3. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method, it is characterized in that: in step (1), described vanadium source is the one in vanadic oxide, ammonium metavanadate, ammonium vanadate, vanadium trioxide, oxalic acid vanadyl.
4. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method, it is characterized in that: in step (1), described phosphorus source is the one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, pyrophosphoric acid.
5. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method it is characterized in that:, in step (1), described reducing agent is the one in tartaric acid, citric acid, oxalic acid, ethanedioic acid, adipic acid, malonic acid, ascorbic acid.
6. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method it is characterized in that: the one in argon gas that the nonoxidizing atmosphere of sintering is, nitrogen, hydrogen, helium, carbon monoxide.
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