CN108231430B - Polyvanadate organic-inorganic hybrid material nano-microsphere and preparation method thereof - Google Patents
Polyvanadate organic-inorganic hybrid material nano-microsphere and preparation method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 11
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
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- 239000007772 electrode material Substances 0.000 claims description 18
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
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- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 150000003681 vanadium Chemical class 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 238000010277 constant-current charging Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 10
- 238000000967 suction filtration Methods 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
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- 150000002739 metals Chemical class 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 14
- 239000013077 target material Substances 0.000 description 13
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- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000013385 inorganic framework Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000013112 mixed metal metal-organic framework Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical class [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- Y02E60/13—Energy storage using capacitors
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- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention relates to a polyvanadate organic-inorganic hybrid material nano-microsphere and a preparation method thereof, and the specific preparation method comprises the steps of reacting vanadium-containing salt or oxide, nickel salt, 4' -bipyridine and a mixed organic solvent at the temperature of 120 ℃ and 170 ℃ in a closed reaction kettle, and then carrying out suction filtration, washing and drying to obtain the organic-inorganic hybrid nano-material containing the dissimilar metals. The method is simple and low in cost, and the obtained nano material has high crystallinity, nano oblate shape and high electrochemical activity, has high specific capacitance and charge-discharge stability, and can be applied to the field of electrochemical capacitors.
Description
Technical Field
The invention relates to the field of novel electrode materials, in particular to a polyvanadate organic-inorganic hybrid material nano microsphere and a preparation method thereof.
Background
The rapid consumption of fossil fuels causes severe energy and environmental problems in the world, and further promotes the development and utilization of new energy. In recent years, new electric energy storage devices such as lithium ion batteries, super capacitors, and the like, which can stably utilize them and convert them into a portable stored electric energy form, have been greatly promoted. The super capacitor is distinguished from the rechargeable battery by the characteristics of high power density, rapid charge and discharge capacity, ultra-long cycle stability and the like, and is paid extensive scientific research attention.
Although research and development progress of electrode materials of the super capacitor is remarkable, the electrode materials commonly used at present, such as carbon, metal oxide, metal sulfide and the like, have various defects that (1) the active components with lower specific surface area and porosity are inhibited from directly contacting with an electrolyte, so that the capabilities of electron transfer and ion mass transfer are weakened, and the energy density and the power density of the electrode materials are difficult to improve; (2) the utilization rate of the components of the electrode material is low, and the active elements in the block body cannot fully generate oxidation-reduction reaction in the rapid charging and discharging process, so that the multiplying power characteristic is poor. Therefore, how to construct an electrode material with high specific surface area and rich active sites and effectively improve the utilization rate of active components has important scientific value and practical significance for developing a novel super capacitor energy storage device.
Organic-inorganic framework compounds (MOFs, also called organic-inorganic hybrid materials) are materials with a porous network framework structure formed by coordination of metal ions and organic ligands. Compared with the traditional porous material, the MOFs has the advantages of various structures, high porosity, large specific surface area, adjustable pore volume, easy functionalization of pore surface and the like, and has potential application prospects in the fields of gas storage, electrochemistry, separation, catalysis, sensing and the like. As a new class of porous crystalline materials, MOFs have unique performance advantages in supercapacitor applications due to their large specific surface area, adjustable pore sizes, easily exposed electrochemically active elements, and adjustable structural properties. On one hand, holes or channels which can be cut by MOFs are beneficial to rapid transfer and diffusion of ions in the charge and discharge process of the super capacitor; on the other hand, MOFs belong to crystalline materials, the structure is highly ordered, active sites are uniformly dispersed, the exposed active sites are favorable for participating in the energy conversion process, and the improvement of the electrochemical energy storage performance can be effectively realized finally.
The dissimilar metal MOFs material has potential application prospect in the electrochemical field due to high redox activity, the nanocrystallization of the MOFs material is a key technology for realizing practical application, the dissimilar metal MOFs material of the nano-microsphere is not reported in documents at present, and the vanadium-nickel mixed metal MOFs nano-microsphere prepared by the simple method has high electrical activity and can be used as a new generation of excellent electrochemical capacitor electrode material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nano-scale polyvanadate organic-inorganic hybrid material with simple process, low preparation cost, high crystallinity of a target product and better electrochemical performance and a preparation method thereof. The specific scheme is as follows: a polyvanadate organic-inorganic hybrid material nano-microsphere is characterized in that: the material is oblate and has the size of 200-300 nm; the molecular formula of the material is [ Ni ]2(4,4’-bipy)3(H2O)2V4O12]·2.5H2O。
Further, the organic-inorganic hybrid material nano-microsphere of poly vanadate is characterized in that: the microstructure of the material contains a mesoporous structure, and the aperture of the mesoporous structure is 0.5-2.5 nm.
Further, the polyvanadate organic-inorganic hybrid material nano-microsphereThe method is characterized in that: when the material is used as a supercapacitor electrode material for constant current charging and discharging, KOH is used as electrolyte, and the current density is 1A.g-1The specific capacitance is 1300F.g-1。
Further, the preparation method of the polyvanadate organic-inorganic hybrid material nano-microsphere comprises the following steps:
the method comprises the following steps: mixing vanadium salt, nickel salt and 4, 4' -bipyridine according to a certain proportion, dissolving the mixture in a mixed solvent, and stirring for a certain time;
step two: and transferring the mixed solution into a closed reaction kettle with a polytetrafluoroethylene inner container, reacting for a plurality of times, naturally cooling to room temperature, filtering solids in the reaction kettle, respectively cleaning with ethanol and distilled water, drying, and grinding to obtain the target nano microsphere material.
Further, the preparation method of the polyvanadate organic-inorganic hybrid material nano-microsphere comprises the following specific steps:
the method comprises the following steps: mixing the components in a molar ratio of 0.8-1.2: 0.6-1.3: 0.6-1.0: 1150-1600 vanadium salt, nickel salt, 4' -bipyridine and mixed solvent are stirred for 30-60 minutes;
step two: and transferring the mixed solution into a sealed reaction kettle with a polytetrafluoroethylene inner container, reacting at the temperature of 180 ℃ for 8-18 hours, naturally cooling to room temperature, filtering solids in the reaction kettle, respectively cleaning with ethanol and distilled water, drying, and grinding to obtain the target nano microsphere material.
Further, the preparation method of the polyvanadate organic-inorganic hybrid material nano-microsphere is characterized by comprising the following steps: the mixed solvent is a mixture of two of ethanol, methanol and acetonitrile.
Further, the preparation method of the polyvanadate organic-inorganic hybrid material nano-microsphere is characterized by comprising the following steps: the mixed solvent is ethanol: the volume ratio of methanol is 1: 1 or 1: 2 or 2: 1; or the volume ratio of the mixed solvent of methanol and acetonitrile is 1: 1 or 1: 2 or 2: 1.
further, the preparation method of the polyvanadate organic-inorganic hybrid material nano-microsphere is characterized by comprising the following steps: the vanadium salt can be one of sodium metavanadate, ammonium metavanadate and vanadyl sulfate;
further, the preparation method of the polyvanadate organic-inorganic hybrid material nano-microsphere is characterized by comprising the following steps: the nickel salt can be one of nickel acetate, nickel nitrate, nickel sulfate or nickel chloride;
further, the preparation method of the polyvanadate organic-inorganic hybrid material nano-microsphere is characterized by comprising the following steps: the reaction kettle is a high-pressure reaction kettle or a hydrothermal reaction kettle.
The invention has the technical advantages that:
1. the preparation process is simple and can be carried out by one-step solvothermal synthesis; the required instruments and equipment are low in cost, and only one common electric heating oven and one high-pressure reaction kettle (hydrothermal reaction kettle) are needed;
2. the electrode material prepared by the process has high crystallinity, a nano oblate structure in the shape of 200-300nm, meets the standard of nano materials, and is suitable for application in many new energy industries;
3. the prepared material contains a mesoporous structure in the microcosmic aspect, the aperture is 0.5-2.5nm, and the nano structure and the small-sized mesoporous structure of the particles are beneficial to the transmission of electrolyte on the surface of the material and the migration of ions in pores, so that the material is an excellent electrochemical capacitor electrode material;
4. the prepared material contains dissimilar metal structural units (vanadium-oxygen clusters and nickel ions), has high redox activity, has high specific capacitance when being used as a super capacitor electrode material, and is expected to be used as a new generation of electricity storage electrode material.
Drawings
FIG. 1 is an XRD diffraction pattern of the prepared material.
FIG. 2 is a schematic diagram of a scanning electron micrograph of the prepared material.
Fig. 3 is a graph showing N2 adsorption and desorption curves and a pore size distribution of the prepared material.
FIG. 4 is a constant current charging and discharging curve diagram of the prepared material as the electrode material of the super capacitor and the specific capacitance under different current densities.
Detailed Description
Example 1: mixing sodium metavanadate, nickel acetate and 4, 4 '-bipyridyl and dissolving the mixture in a mixed solvent (volume ratio is 1: 2) of ethanol and acetonitrile, wherein the mass ratio of the sodium metavanadate to the nickel acetate to the 4, 4' -bipyridyl to the mixed solvent is 0.8: 0.6: 0.6: 1150, then stirred at room temperature (28 degrees) for 40 minutes; and (3) taking 80 ml of the mixed solution, transferring the mixed solution into a closed high-pressure reaction kettle with a polytetrafluoroethylene inner container of 100 ml for reaction at 165 ℃, naturally cooling to room temperature after 12 hours of reaction, carrying out suction filtration on solid matters in the high-pressure reaction kettle, then washing 3 times by using ethanol and distilled water respectively, drying and grinding to obtain the target material I.
Example 2: mixing ammonium metavanadate, nickel nitrate and 4, 4 '-bipyridyl and dissolving the mixture in a mixed solvent (volume ratio is 1: 2) of ethanol and acetonitrile, wherein the amount ratio of the ammonium metavanadate to the nickel nitrate to the 4, 4' -bipyridyl to the mixed solvent is 0.95: 1.15: 1.0: 1500, then stirred at room temperature (28 degrees) for 60 minutes; and (3) taking 80 ml of the mixed solution, transferring the mixed solution into a closed high-pressure reaction kettle with a polytetrafluoroethylene inner container of 100 ml for reaction at the temperature of 170 ℃, naturally cooling to room temperature after 8 hours of reaction, carrying out suction filtration on solid matters in the high-pressure reaction kettle, cleaning for 3 times by using ethanol and distilled water respectively, drying and grinding to obtain the target material II.
Example 3: mixing vanadyl sulfate, nickel sulfate and 4, 4 '-bipyridyl and dissolving in a mixed solvent (volume ratio is 1: 1) of ethanol and methanol, wherein the amount ratio of ammonium metavanadate to nickel sulfate to 4, 4' -bipyridyl to the mixed solvent is 1.15: 1.3: 0.95: 1600 and then stirred at room temperature (28 ℃ C.) for 30 minutes; and (3) taking 80 ml of the mixed solution, transferring the mixed solution into a closed high-pressure reaction kettle with a polytetrafluoroethylene inner container of 100 ml for reaction at the temperature of 130 ℃, naturally cooling to room temperature after 18 hours of reaction, carrying out suction filtration on solid matters in the high-pressure reaction kettle, cleaning for 3 times by using ethanol and distilled water respectively, drying and grinding to obtain the target material III.
Example 4: mixing ammonium metavanadate, nickel acetate and 4, 4 '-bipyridyl and dissolving the mixture in a mixed solvent (volume ratio is 1: 1) of methanol and acetonitrile, wherein the mass ratio of the ammonium metavanadate to the nickel acetate to the 4, 4' -bipyridyl to the mixed solvent is 1.2: 1.1: 0.85: 1400, then stirred at room temperature (28 degrees) for 50 minutes; and (3) taking 80 ml of the mixed solution, transferring the mixed solution into a closed high-pressure reaction kettle with a polytetrafluoroethylene inner container of 100 ml for reaction at the temperature of 120 ℃, naturally cooling to room temperature after 12 hours of reaction, carrying out suction filtration on solid matters in the high-pressure reaction kettle, then respectively cleaning 3 times by using ethanol and distilled water, drying and grinding to obtain the target material IV.
Example 5: mixing ammonium metavanadate, nickel chloride and 4, 4 '-bipyridyl and dissolving the mixture in a mixed solvent (the volume ratio is 2: 1) of ethanol and methanol, wherein the amount ratio of the ammonium metavanadate to the nickel chloride to the 4, 4' -bipyridyl to the mixed solvent is 1.15: 1.2: 0.75: 1350, then stirred at room temperature (28 deg.) for 45 minutes; and (3) taking 80 ml of the mixed solution, transferring the mixed solution into a closed high-pressure reaction kettle with a polytetrafluoroethylene inner container of 100 ml for reaction at the temperature of 150 ℃, naturally cooling to room temperature after reacting for 15 hours, carrying out suction filtration on solid matters in the high-pressure reaction kettle, then respectively cleaning 3 times by using ethanol and distilled water, drying and grinding to obtain the target material V.
Example 6: mixing ammonium metavanadate, nickel acetate and 4, 4 '-bipyridyl and dissolving the mixture in a mixed solvent (volume ratio is 1: 2) of methanol and acetonitrile, wherein the mass ratio of the ammonium metavanadate to the mixed solvent to the nickel acetate to the 4, 4' -bipyridyl to the mixed solvent is 0.9: 0.65: 0.85: 1250 and then stirred at room temperature (28 degrees) for 60 minutes; and (3) taking 80 ml of the mixed solution, transferring the mixed solution into a closed hydrothermal reaction kettle with a polytetrafluoroethylene inner container for reaction at the temperature of 165 ℃, naturally cooling to room temperature after 16 hours of reaction, carrying out suction filtration on solids in the hydrothermal reaction kettle, cleaning for 3 times by using ethanol and distilled water respectively, drying and grinding to obtain the target material six.
The target materials I to VI in examples 1 to 6 were mixed uniformly to obtain mixed target materials, and four mixed target materials were taken out for the following observation and experiment:
firstly, taking a part of mixed target material to make an XRD diffraction pattern, as shown in figure 1, the prepared MOF (V, Ni) has high crystallinity, the corresponding diffraction peak position is consistent with a standard spectrogram, and the molecular formula of the synthesized material is confirmed to be
[Ni2(4, 4’-bipy)3(H2O)2V4O12]·2.5H2O (4, 4 '-bipy is 4, 4' -bipyridine) (CCDC No. 169926)
Secondly, taking a part of the mixed target material for scanning by an electron microscope, as shown in figure 2, and showing a schematic diagram of a scanning electron microscope photo, wherein the shape of most of the material is oblate spheroids and is uniformly dispersed as seen from a low resolution diagram-figure a; from the high resolution plots, plots b, c, d, it can be seen that the oblate spheroid size is approximately 200-300 nm;
thirdly, taking a part of the mixed target material as N2The adsorption and desorption curves and the pore size distribution diagram, as can be seen from fig. 3, the microstructure of the material contains a mesoporous structure, the pore size of the mesoporous structure is 0.5-2.5nm, and the nano structure and the small-sized mesoporous structure of the particles are beneficial to the transmission of electrolyte on the surface of the material and the migration of ions in pores, so that the material is an excellent electrode material of the supercapacitor;
taking a part of the mixed target material as the electrode material of the supercapacitor, and taking KOH as an electrolyte in the figure 4, wherein the constant current charging and discharging curve chart (a) of the electrode material of the supercapacitor and the specific capacitance (b) under different current densities of the electrode material of the supercapacitor are shown, and the current density is 1A.g-1The specific capacitance is 1300F.g-1。
Claims (8)
1. A polyvanadate organic-inorganic hybrid material nano-microsphere is characterized in that: the material is oblate and has the size of 200-300 nm; the molecular formula of the material is [ Ni ]2(4,4’-bipy)3(H2O)2V4O12]·2.5H2O。
2. The organic-inorganic hybrid polyvanadate nano-microsphere according to claim 1, wherein: the microstructure of the material contains a mesoporous structure, and the aperture of the mesoporous structure is 0.5-2.5 nm.
3. The poly-vanadate organic material as defined in claim 1The inorganic hybrid material nano-microsphere is characterized in that: when the material is used as a supercapacitor electrode material for constant current charging and discharging, KOH is used as electrolyte, and the current density is 1A.g-1The specific capacitance is 1300F.g-1。
4. The organic-inorganic hybrid polyvanadate nano-microsphere according to any one of claims 1 to 3, which is prepared by the following steps:
the method comprises the following steps: mixing the components in a molar ratio of 0.8-1.2: 0.6-1.3: 0.6-1.0: 1150-1600 vanadium salt, nickel salt, 4' -bipyridine and mixed solvent are stirred for 30-60 minutes;
step two: transferring the mixed solution into a sealed reaction kettle with a polytetrafluoroethylene inner container, reacting at the temperature of 180 ℃ for 8-18 hours at 120 ℃, naturally cooling to room temperature, filtering solids in the reaction kettle, respectively cleaning with ethanol and distilled water, drying, and grinding to obtain the target nano microsphere material;
the mixed solvent is a mixture of two of ethanol, methanol and acetonitrile.
5. The organic-inorganic hybrid polyvanadate nano-microsphere according to claim 4, wherein the preparation method comprises the following steps: the mixed solvent is ethanol: the volume ratio of methanol is 1: 1 or 1: 2 or 2: 1; or the volume ratio of the mixed solvent of methanol and acetonitrile is 1: 1 or 1: 2 or 2: 1.
6. the organic-inorganic hybrid polyvanadate nano-microsphere according to claim 4, wherein the preparation method comprises the following steps: the vanadium salt can be one of sodium metavanadate, ammonium metavanadate and vanadyl sulfate.
7. The organic-inorganic hybrid polyvanadate nano-microsphere according to claim 4, wherein the preparation method comprises the following steps: the nickel salt can be one of nickel acetate, nickel nitrate, nickel sulfate or nickel chloride.
8. The organic-inorganic hybrid polyvanadate nano-microsphere according to claim 4, wherein the preparation method comprises the following steps: the reaction kettle is a high-pressure reaction kettle or a hydrothermal reaction kettle.
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