CN109133171B - VO with spherical porous morphology and different diameter sizes2And method for preparing the same - Google Patents
VO with spherical porous morphology and different diameter sizes2And method for preparing the same Download PDFInfo
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- CN109133171B CN109133171B CN201811328714.XA CN201811328714A CN109133171B CN 109133171 B CN109133171 B CN 109133171B CN 201811328714 A CN201811328714 A CN 201811328714A CN 109133171 B CN109133171 B CN 109133171B
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- C01P2004/30—Particle morphology extending in three dimensions
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Abstract
The invention relates to a VO with spherical porous morphology and different diameters2And a preparation method thereof, belonging to the technical field of micro-nano functional material preparation. The first step of the preparation method is to mix ammonium metavanadate, hydroxylamine hydrochloride and glycol as raw materials, and the mixed solution is stirred differentlyPreparing precursors VEG with different diameters by a hydrothermal method during stirring; the second step is to calcine the precursor VEG for 3 to 4 hours at 480 to 500 ℃ in nitrogen atmosphere to prepare spherical and porous VO2The morphology of (2). The method controls the diameter size of the spherical product through different stirring time, has the characteristics of simple operation, convenient synthesis, good repeatability, low-temperature energy conservation and the like, is easy to control the appearance, uniform in size and high in purity of the product, and is well applied as an anode material in a lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of micro-nano functional material preparation. In particular to a method for preparing spherical and porous VO with different diameter sizes2A method for new morphologies.
Background
Vanadium oxide, as a rich resource, has a plurality of oxidation states, and its excellent properties make it widely used in the fields of catalysis, batteries, magnetism, adsorption, etc. Vanadium oxides have their unique physical and chemical properties and thus have wide applications, for example, as catalysts, chemical sensors, electrode materials for high-density lithium batteries, and in various optical and electronic devices. In recent years, research on vanadium oxide micro-nano materials is widely concerned by people, and microstructures such as dimensions, sizes and appearances of vanadium oxides have great influence on optical, electric, magnetic, catalytic and other properties of devices. The preparation of the micro-nano material with fine particles, uniform size, uniform appearance and high dispersity by adopting a simple and industrialized synthesis method is a precondition for preparing high-performance material devices. There are many methods for preparing vanadium oxide nanomaterials, such as hydrothermal (solvothermal) method, sol-gel method, redox method, etc.
VO at present2The shapes of the nano-belt and the nano-film are the same, and the shape of the spherical porous surface is not reported. Preparation of VO by reduction of ammonium polyvanadate with hydrogen, as is known at present2However, hydrogen is easy to explode when meeting open fire, and the hydrogen is utilized to reduce ammonium polyvanadate to prepare VO2The method of (2) is costly.
According to the method, ammonium metavanadate, hydroxylamine hydrochloride and ethylene glycol are used as raw materials, precursor VEG (ethylene glycol vanadate) with different diameters can be prepared at a lower hydrothermal temperature (160-170 ℃) and a shorter time (10-15 hours), the diameter of the precursor VEG is increased along with the increase of the stirring time of a mixed solution, and the spherical diameter of the precursor VEG is distributed between 1-11 microns. Then calcining the prepared spherical precursors VEG with different diameters under the nitrogen atmosphere condition to prepare micro-nano spherical and porous VO with different diameters2New appearance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing spherical and porous VO with different diameters and sizes2A preparation method of a new appearance. And spherical and porous VO with different diameter sizes is prepared2A new morphology which is similar to the appearance of a plurality of small spheres stacked into a big sphere.
VO with spherical porous appearances of different diameter sizes2The specific technical scheme is as follows.
VO with spherical porous morphology and different diameter sizes2Is characterized by consisting of VO2The nano particles are stacked into spherical porous shapes with different diameter sizes; the diameter of the sphere is in the range of 1 to 11 μm.
The VO2Having a monoclinic phase.
VO with spherical porous shapes and different diameter sizes2The specific technical scheme of the preparation method is as follows.
VO with spherical porous morphology and different diameter sizes2The preparation method comprises preparing a precursor of ethyl vanadateDiol esters (VEG) and preparation of VO2Two steps; it is characterized in that the preparation method is characterized in that,
the preparation method of the precursor ethylene glycol vanadate comprises the steps of mixing ammonium metavanadate and ethylene glycol, and then adding hydroxylamine hydrochloride to obtain a mixed solution, wherein the molar ratio of the ammonium metavanadate to the hydroxylamine hydrochloride is 2: 3-3.1, and the molar ratio of the ammonium metavanadate to the ethylene glycol is 1: 715-718; stirring the mixed solution at 1000-1500 rpm for 0.5-8 hours, transferring the mixed solution into a polytetrafluoroethylene lining of a reaction kettle, and reacting at 160-170 ℃ for 10-35 hours; carrying out solid-liquid separation to obtain a mauve precipitate, carrying out centrifugal washing, and carrying out low-temperature freeze drying to obtain a precursor ethylene glycol Vanadate (VEG);
the preparation of VO2Calcining a precursor ethylene glycol Vanadate (VEG) for 3-4 hours at 480-500 ℃ in a nitrogen atmosphere to prepare spherical and porous VO2The morphology of (2).
The density of the ethylene glycol is 1.111-1.115 g/ml.
The mixture was transferred to the reactor teflon liner at a fill ratio (i.e., the ratio of the mixed solution to the volume of the reactor teflon liner) of 80%.
The centrifugal washing is to carry out centrifugal washing on the mauve precipitate for 5 times by using deionized water and absolute ethyl alcohol; the low-temperature freeze drying is to freeze the precipitate after centrifugal washing by liquid nitrogen and then to dry the precipitate for 24 hours at low temperature by a low-temperature freeze dryer.
The calcination can be carried out by heating to 480-500 ℃ at a heating rate of 2 ℃/min.
The size of the spherical diameter of the precursor VEG can be increased along with the increase of the stirring time of the mixed solution in a certain time, and the size distribution of the spherical diameter of the precursor is 1-11 mu m. Then preparing spherical porous VO with different diameter sizes by calcining precursor VEG with different diameter sizes in nitrogen atmosphere at certain temperature2New appearance. Calcined spherical porous VO2The diameter size is substantially the same as the spherical diameter size of the precursor before calcination (1 to 11 μm).
The invention has the beneficial effects that:
1. the product obtained by the invention can be prepared into various productsThe size of the spherical diameter of the precursor VEG is adjusted by controlling the stirring time of the mixed solution, and then VO with spherical shapes with different diameters and sizes and a porous structure can be prepared by calcining the precursor VEG with different diameters and sizes in a nitrogen atmosphere2New morphology, VO2Is monoclinic phase, and the product has uniform size and high purity.
2. The raw material proportion of ammonium metavanadate, hydroxylamine hydrochloride and glycol required by the preparation of the precursor is different from that of the prior art, and the size of the sphere can be controlled by changing the stirring time of the mixed solution, and the method has the advantages of simple and convenient operation, easy synthesis, good repeatability, low temperature and energy conservation.
Drawings
FIG. 1 is an XRD pattern of a spherical precursor VEG (ethylene glycol vanadate) obtained in example 1.
FIG. 2 is an SEM image of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 1.
FIG. 3 is an XRD pattern of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 2.
FIG. 4 is an SEM image of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 2.
FIG. 5 is an XRD pattern of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 3.
FIG. 6 is an SEM image of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 3.
FIG. 7 is an XRD pattern of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 4.
FIG. 8 is an SEM image of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 4.
FIG. 9 is an XRD pattern of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 5.
FIG. 10 is an SEM image of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 5.
FIG. 11 is an XRD pattern of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 6.
FIG. 12 is an SEM photograph of the spherical precursor VEG (ethylene glycol vanadate) obtained in example 6.
FIG. 13 shows VO, a product obtained in example 72XRD pattern of (a).
FIG. 14 shows VO as a product obtained in example 72SEM image of (d).
FIG. 15 shows VO as a product obtained in example 82SEM image of (d).
Detailed Description
The invention will be further illustrated with reference to specific examples. Mainly explaining the influence of the stirring time of the mixed solution on the spherical diameter size of the precursor. Specifically, examples 1-6 explore the effect of the stirring time of the mixed solution on the diameter size of the precursor VEG.
Example 1
0.5849g of ammonium metavanadate is dissolved in a 200ml ethylene glycol beaker, yellow floccule can be obtained after the ammonium metavanadate and the ethylene glycol are fully mixed, then 0.5212g of hydroxylammonium hydrochloride is added into the beaker and placed on a magnetic stirrer to be stirred, the rotating speed is set to be 1000 r/min, the mixture is stirred for 30min at normal temperature and normal pressure, and the yellow floccule gradually turns into white to obtain a white flocculent precursor. The solution after even mixing is transferred to a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining (the filling ratio is 80 percent), and the solution is placed in a heating furnace with intelligently controllable temperature for heating, and the reaction conditions are as follows: the reaction temperature is 160 ℃, the reaction time is 15 hours, and the hydrothermal product is obtained after natural cooling. And (3) performing centrifugal separation on the hydrothermal product to obtain mauve precipitate, performing centrifugal washing on the mauve precipitate for 5 times by using deionized water and absolute ethyl alcohol, freezing the centrifugally washed precipitate by using liquid nitrogen, and performing low-temperature drying on the precipitate for 24 hours by using a low-temperature freeze dryer to obtain grey-black powder.
The XRD spectrum of the gray black powder is shown in fig. 1, and the analytical XRD spectrum shows that the prepared gray black powder product is a precursor VEG (ethylene glycol vanadate) and has a good crystal structure. The prepared precursor VEG was morphologically observed using a Magellan type 400 field emission scanning electron microscope, as shown in fig. 2. As can be seen from FIG. 2, the diameter size distribution of the prepared precursor VEG is 1-3 μm.
Example 2
The same procedure as in example 1 was followed, except that the solution after uniform mixing was subjected to hydrothermal reaction in a reaction vessel for 25 hours, and the other conditions were not changed.
The XRD spectrum of the obtained gray black powder is shown in fig. 3, and the analytical XRD spectrum shows that the prepared gray black powder product is a precursor VEG (ethylene glycol vanadate) and has a good crystal structure. The prepared precursor VEG was morphologically observed using a Magellan type 400 field emission scanning electron microscope, as shown in fig. 4. As can be seen from FIG. 4, the diameter size of the prepared precursor VEG is also distributed in the range of 1-3 μm.
Example 3
The same procedure as in example 1 was followed, except that the hydrothermal reaction time of the uniformly mixed solution in the reaction vessel was 35 hours, and the other conditions were not changed.
The XRD spectrum of the obtained gray black powder is shown in fig. 5, and the analytical XRD spectrum shows that the prepared gray black powder product is a precursor VEG (ethylene glycol vanadate) and has a good crystal structure. The prepared precursor VEG was morphologically observed using a Magellan type 400 field emission scanning electron microscope, as shown in fig. 6. As can be seen from FIG. 6, the diameter size of the prepared precursor VEG is also distributed in 1-3 μm.
From examples 1 to 3, it can be seen that, when only the hydrothermal reaction time is changed without changing other variables, the hydrothermal reaction time is within the range of 10 to 35 hours, and the diameter size of the precursor VEG is not affected substantially.
Example 4
The stirring time of example 1 was modified to 2h, and the other conditions were not changed.
The XRD spectrum of the prepared gray black powder is shown in fig. 7, and the analytical XRD spectrum shows that the prepared gray black powder product is a precursor VEG (ethylene glycol vanadate) and has a good crystal structure. The prepared precursor VEG was morphologically observed using a Magellan type 400 field emission scanning electron microscope, as shown in fig. 8. As can be seen from FIG. 8, the diameter size distribution of the prepared precursor VEG is 3-5 μm.
Example 5
The stirring time of example 1 was modified to 4h, and the other conditions were not changed.
The XRD spectrum of the prepared gray black powder is shown in fig. 9, and the analytical XRD spectrum shows that the prepared gray black powder product is a precursor VEG (ethylene glycol vanadate) and has a good crystal structure. The prepared precursor VEG was morphologically observed using a Magellan type 400 field emission scanning electron microscope, as shown in fig. 10. As can be seen from FIG. 10, the diameter size distribution of the prepared precursor VEG is 6-10 μm.
Example 6
The stirring time of example 1 was modified to 8h, and the other conditions were not changed.
The XRD spectrum of the obtained gray black powder is shown in fig. 11, and the analytical XRD spectrum shows that the prepared gray black powder product is a precursor VEG (ethylene glycol vanadate) and has a good crystal structure. The prepared precursor VEG was morphologically observed using a Magellan type 400 field emission scanning electron microscope, as shown in fig. 12. As can be seen from FIG. 12, the diameter size distribution of the prepared precursor VEG is 7-11 μm.
Experiments have shown that varying the stirring time of the mixed solution, with other variables controlled, affects the diameter size of the precursor, in particular: the diameter size of the precursor VEG increases with increasing stirring time.
Example 7
A sample of the precursor VEG (ethylene glycol vanadate) prepared as in example 1 was calcined in a tube furnace. Calcining conditions are as follows: in N2Calcining under the condition of flow-down, heating rate is 2 ℃/min, calcining temperature is 480 ℃, calcining time is 4 hours, and spherical porous VO can be obtained2。
The XRD spectrum is shown in FIG. 13, and the analytic XRD spectrum shows that the prepared sample has good crystal structure, and the product is VO2. The prepared sample is observed by a Magellan400 type field emission scanning electron microscope. As can be seen from FIG. 14, VO was prepared2Is spherical, and the prepared VO2The spherical morphology of the precursor VEG is substantially preserved.
Example 8
A sample of the precursor VEG (ethylene glycol vanadate) prepared as in example 1 was calcined in a tube furnace. Calcining conditions are as follows: in N2Calcining under the condition of flow-down, heating rate is 2 ℃/min, calcining temperature is 500 ℃, calcining time is 3 hours, and spherical porous VO can be obtained2。
The XRD spectrum of the sample is the same as that of example 5, and the analytic XRD spectrum shows that the prepared sample is VO with good crystal structure2. The prepared sample is observed by a Magellan400 type field emission scanning electron microscope. As can be seen from FIG. 15, VO was prepared2Is spherical, and the prepared VO2The spherical morphology of the precursor VEG is substantially preserved.
Experiments show that the spherical and porous VO prepared after calcination2Spherical and porous VO after calcination with the spherical diameter of the precursor VEG retained2The morphology is similar to that of a plurality of small spheres (VO)2Nanoparticles of (b) are stacked into one large sphere and the calcined VO is2The product has high purity.
Claims (5)
1. VO with spherical porous morphology and different diameter sizes2The VO with the spherical porous morphology and different diameter sizes2From VO2The nano particles are stacked into spherical porous shapes with different diameter sizes; the diameter of the sphere is in the range of 1-11 mu m; preparing precursor ethylene glycol vanadate and preparing VO2Two steps; it is characterized in that the preparation method is characterized in that,
the preparation method of the precursor ethylene glycol vanadate comprises the steps of mixing ammonium metavanadate and ethylene glycol, and then adding hydroxylamine hydrochloride to obtain a mixed solution, wherein the molar ratio of the ammonium metavanadate to the hydroxylamine hydrochloride is 2: 3-3.1, and the molar ratio of the ammonium metavanadate to the ethylene glycol is 1: 715-718; stirring the mixed solution at 1000-1500 rpm for 0.5-8 hours, transferring the mixed solution into a polytetrafluoroethylene lining of a reaction kettle, and reacting at 160-170 ℃ for 10-35 hours; carrying out solid-liquid separation to obtain a mauve precipitate, carrying out centrifugal washing, and carrying out low-temperature freeze drying to obtain a precursor of ethylene glycol vanadate;
the preparation of VO2Calcining a precursor ethylene glycol vanadate at 480-500 ℃ for 3-4 hours in a nitrogen atmosphere to prepare spherical and porous VO2The morphology of (2).
2. Spherical porous-morphology VO with different diameter sizes according to claim 12The preparation method is characterized in that the density of the ethylene glycol is 1.111-1.115 g/ml.
3. Spherical porous-morphology VO with different diameter sizes according to claim 12The method for preparing (1) is characterized in that the polytetrafluoroethylene lining is transferred into a reaction kettle, and the filling ratio is 80% by volume.
4. Spherical porous-morphology VO with different diameter sizes according to claim 12The preparation method is characterized in that the centrifugal washing is to carry out centrifugal washing on the mauve sediment for 5 times by using deionized water and absolute ethyl alcohol; the low-temperature freeze drying is to freeze the precipitate after centrifugal washing by liquid nitrogen and then to dry the precipitate for 24 hours at low temperature by a low-temperature freeze dryer.
5. VO with spherical porous morphology of different diameter sizes according to claim 1, 2, 3 or 42The preparation method is characterized in that the temperature is raised to 480-500 ℃ at the temperature raising rate of 2 ℃/min.
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| CN110205803B (en) * | 2019-05-30 | 2020-11-03 | 四川大学 | Preparation method of multi-valence vanadium oxide flexible electrode |
| CN112266018A (en) * | 2020-10-16 | 2021-01-26 | 成都先进金属材料产业技术研究院有限公司 | Method for preparing nano vanadium dioxide by reverse hydrolysis precipitation |
| CN114349042A (en) * | 2022-01-05 | 2022-04-15 | 中国科学技术大学 | Rutile phase doped metal oxide, stable defect-free rutile phase metal oxide and preparation method thereof |
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| CN102795968B (en) * | 2012-09-12 | 2014-07-09 | 西南大学 | Preparation method of vanadyl ethylene glycol and method for preparing M-phase vanadium dioxide powder from vanadyl ethylene glycol |
| CN103633309A (en) * | 2013-12-13 | 2014-03-12 | 黑龙江大学 | Preparation method of core-shell structure vanadium trioxide microspheres |
| CN104176778B (en) * | 2014-08-11 | 2016-01-06 | 武汉理工大学 | A kind of classifying porous barium oxide microballoon and its preparation method and application |
| CN108298582A (en) * | 2018-03-28 | 2018-07-20 | 西安交通大学 | One kind is by VO2The preparation method of hollow ball and film that nanoscale twins surround |
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