CN112158883A - Process for preparing vanadium dioxide nano powder - Google Patents
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Abstract
The invention discloses a process method, in particular discloses a process method for preparing vanadium dioxide nano powder, and belongs to the technical field of metallurgical production process manufacturing. The preparation method has the advantages of short preparation time, high preparation efficiency, energy conservation, uniform appearance and high system dispersibility. The process method comprises respectively atomizing alkaline precipitant and tetravalent vanadium salt solution containing surfactant into fog drops below 10 μm by ultrasonic atomizer, and placing the two atomized drops in a reactor in ultrasonic water bath for contact and reaction to generate VO (OH)2Precipitating, and collecting the precipitate VO (OH) obtained by the reaction with ethanol2And washed to obtain VO (OH)2A precursor; collecting and washing the obtained VO (OH)2Precursor and deionized waterDispersing the mixture into suspension by sound, and finally carrying out hydrothermal crystallization treatment on the suspension to obtain the nano vanadium dioxide with uniform granularity and dispersed monomers.
Description
Technical Field
The invention relates to a process method, in particular to a process method for preparing vanadium dioxide nano powder, belonging to the technical field of metallurgical production process manufacturing.
Background
Vanadium dioxide (VO)2) Is a vanadium oxide with VO which is most reported and most widely applied at present2(A)、VO2(B)、VO2(C)、VO2(D)、VO2(M)、VO2(R)、VO2(T) and VO2(P) and other isomers of various homologies, wherein VO2(M) is currently the most studied phase. It has been proved that light, heat, electricity, stress, etc. can induce VO2(M) undergoes a phase transition accompanied by a large change in characteristics such as crystal structure, resistivity, and optical properties. When the phase change occurs, the crystal structure of the material is changed from monoclinic phase to tetragonal rutile phase, the resistivity is changed to be abrupt change of more than 3 orders of magnitude, and the semiconductor before the phase change is changed into metal; in terms of optical performance, the high transmittance of infrared light before and after the phase change is changed into high reflection. Due to VO2The phase change material has unique phase change property and excellent performance, and is applied to intelligent glass, optical storage, laser radiation protective films, lithium battery electrodes and the like in recent years. In addition, VO2But also can be widely applied to other aspects, such as antistatic coatings, nonlinear and linear resistance materials, high-sensitivity temperature sensors, adjustable microwave switch devices, infrared modulation materials and the like. In summary, VO as a functional material2Has higher potential application value and wide application prospect, and has great research and development values.
The existing preparation methods of the M-phase vanadium dioxide powder comprise the following steps: a method for preparing pure-phase VO powder with adjustable phase-change temperature by one-step hydrothermal method is disclosed in Chinese patent CN108975401A, firstly preparing a precursor by an oxalic acid precipitation method, and then carrying out hydrothermal treatment on the precursor to obtain pure-phase vanadium dioxide powder; the other method is a method for preparing vanadium dioxide powder by a hydrothermal-assisted uniform precipitation method disclosed in Chinese patent CN103880080A, wherein a precursor precipitate is prepared by the uniform precipitation method, and M-phase vanadium dioxide powder is prepared by hydrothermal reaction; a precursor treatment process of treating a tetravalent vanadium ion aqueous solution by using an alkaline reagent to obtain a suspension is also disclosed in Chinese patent CN102120614A, and then M-phase vanadium dioxide powder is prepared by using a hydrothermal method; the fourth method is a method for preparing doped vanadium dioxide powder by a hydrothermal method disclosed in U.S. Pat. No. 4, 20150251948. However, it is difficult to obtain a monodisperse, high-purity, and sufficiently small particle size nano-powder with high yield and high efficiency by these methods.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method has the advantages of short preparation time, high preparation efficiency, energy conservation, uniform appearance and high system dispersibility.
The technical scheme adopted for solving the technical problems is as follows: a process for preparing vanadium dioxide nano-powder includes atomizing alkaline precipitant and quadrivalent vanadium salt solution containing surfactant to fog drops less than 10 microns by ultrasonic atomizer, putting two atomized drops in reactor in ultrasonic water bath for contact and reaction to generate VO (OH)2Precipitating, and collecting the precipitate VO (OH) obtained by the reaction with ethanol2And washed to obtain VO (OH)2A precursor; collecting and washing the obtained VO (OH)2And ultrasonically dispersing the precursor and deionized water into a suspension, and finally carrying out hydrothermal crystallization treatment on the suspension to obtain the nano vanadium dioxide with uniform granularity and dispersed monomers.
Further, the atomization of the alkaline precipitant and the tetravalent vanadium salt solution and the reaction and precipitation in the reactor are carried out as follows,
firstly, respectively placing a vanadium salt solution and a precipitator solution in an ultrasonic atomizer with ultrasonic frequency of 1.7-3 MHz for atomization to generate fog drops, guiding the fog drops into a reactor filled with absolute ethyl alcohol through carrier gas, placing the reactor in ultrasonic water bath equipment, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining a suspension after full reaction, aging for 0.5-12 h, and centrifuging to obtain a precipitate, wherein the centrifugal rotating speed is 5000-11000 rpm.
The preferable mode of the scheme is that the precipitant solution is prepared before being atomized, and the preparation process comprises the following steps,
dissolving a precipitator in deionized water to prepare a solution of 0.2-1 mol/L, and performing ultrasonic dispersion for 15-30 min to complete the preparation of the precipitator solution.
Further, the precipitant solution may be one or more of ammonia, sodium hydroxide, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate and sodium carbonate.
The preferable mode of the above scheme is that the tetravalent vanadium salt solution containing the surfactant needs to be prepared before the tetravalent vanadium salt solution is atomized, and the preparation process comprises the following steps,
dissolving a tetravalent vanadium salt with the purity of more than or equal to 99.0% in deionized water to prepare a solution with the concentration of 0.1-0.5 mol/L, adding 0.5-1 wt% of a surfactant, and performing ultrasonic dispersion for 15-30 min; and slowly dripping the qualified precipitant solution into the prepared vanadyl sulfate solution, and filtering and separating out a clarified solution for later use after a small amount of precipitate appears.
Further, the tetravalent vanadium salt can be one or more of vanadyl sulfate, vanadyl oxalate and vanadyl dichloride; the surfactant can be one of PEG with molecular weight of 400-6000, Tween 80, PVP, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
In a preferred embodiment of the above-described process, the collecting and washing of the obtained VO (OH)2 precursor is carried out in the following steps,
washing the precipitate obtained by the reaction with deionized water for three times, then washing with absolute ethyl alcohol for two times, finally separating to obtain a precursor,
and in the washing and alcohol washing processes, the precursor suspension is uniformly stirred and then subjected to ultrasonic dispersion, wherein the duration of each time is 15-30 min.
Furthermore, the hydrothermal crystallization of the precursor for preparing the suspension is carried out according to the following steps,
transferring the suspension containing the precursor into a hydrothermal kettle, preparing vanadium dioxide powder through hydrothermal reaction,
wherein the temperature of the hydrothermal reaction is controlled to be 80-400 ℃; the hydrothermal reaction time is controlled to be 2-240 hours; the filling ratio of the hydrothermal reaction is controlled to be 20-90%.
In the preferable mode of the scheme, the temperature of the hydrothermal reaction is 200-350, the time of the hydrothermal reaction is 4-120 hours, and the filling ratio of the hydrothermal reaction is 30-80%.
Furthermore, the temperature of the hydrothermal reaction is 240-300 ℃, the time of the hydrothermal reaction is 4-48 hours, and the filling ratio of the hydrothermal reaction is 50-80%.
The invention has the beneficial effects that: the process method provided by the application comprises two steps of preparing a precursor by ultrasonic atomization and hydrothermal crystallization, wherein during preparation, an ultrasonic atomizer is used for atomizing a tetravalent vanadium salt solution with a certain concentration and containing a surfactant and an alkaline precipitator with a certain concentration into fog drops with the diameter of several micrometers, and then the two atomized liquid drops are placed in a reactor in an ultrasonic water bath for contact reaction to generate VO (OH)2Precipitating and collecting the VO (OH) with ethanol2Reaction and precipitation; the collected and washed VO (OH)2And ultrasonically dispersing the vanadium dioxide and deionized water into suspension, and finally performing hydrothermal crystallization to obtain the nano vanadium dioxide with uniform granularity and dispersed monomers. The basic principle is that a vanadium source and a precipitator are converted into micro reaction liquid drops by utilizing an ultrasonic cavitation effect and are in contact reaction, so that the reaction supersaturation degree is highly homogenized, explosive nucleation is generated, meanwhile, the system dispersibility is improved under the steric effect of a surfactant, precursor precipitates with small and uniform particle sizes are finally obtained, meanwhile, the hydrothermal crystallization process of a hydrothermal technology is integrated, the agglomeration of the precursor in the heat treatment process can be effectively prevented, and finally, the nano vanadium dioxide with uniform particle sizes and monodispersity is obtained. The method has the advantages of short preparation time, high preparation efficiency, energy conservation and capability of preparing the nano vanadium dioxide with uniform appearance and high system dispersibility.
Detailed Description
In order to solve the technical problems in the prior art, the method provided by the invention has the advantages of short preparation time, high preparation efficiency, energy saving, uniform appearance and high system dispersibility, and can be used for preparing vanadium dichloride nano-particlesA powder process method. The process method comprises respectively atomizing alkaline precipitant and tetravalent vanadium salt solution containing surfactant into fog drops below 10 μm by ultrasonic atomizer, and placing the two atomized drops in a reactor in ultrasonic water bath for contact and reaction to generate VO (OH)2Precipitating, and collecting the precipitate VO (OH) obtained by the reaction with ethanol2And washed to obtain VO (OH)2A precursor; collecting and washing the obtained VO (OH)2And ultrasonically dispersing the precursor and deionized water into a suspension, and finally carrying out hydrothermal crystallization treatment on the suspension to obtain the nano vanadium dioxide with uniform granularity and dispersed monomers. The process method provided by the application comprises two steps of preparing a precursor by ultrasonic atomization and hydrothermal crystallization, wherein during preparation, an ultrasonic atomizer is used for atomizing a tetravalent vanadium salt solution with a certain concentration and containing a surfactant and an alkaline precipitator with a certain concentration into fog drops with the diameter of several micrometers, and then the two atomized liquid drops are placed in a reactor in an ultrasonic water bath for contact reaction to generate VO (OH)2Precipitating and collecting the VO (OH) with ethanol2Reaction and precipitation; the collected and washed VO (OH)2And ultrasonically dispersing the vanadium dioxide and deionized water into suspension, and finally performing hydrothermal crystallization to obtain the nano vanadium dioxide with uniform granularity and dispersed monomers. The basic principle is that a vanadium source and a precipitator are converted into micro reaction liquid drops by utilizing an ultrasonic cavitation effect and are in contact reaction, so that the reaction supersaturation degree is highly homogenized, explosive nucleation is generated, meanwhile, the system dispersibility is improved under the steric effect of a surfactant, precursor precipitates with small and uniform particle sizes are finally obtained, meanwhile, the hydrothermal crystallization process of a hydrothermal technology is integrated, the agglomeration of the precursor in the heat treatment process can be effectively prevented, and finally, the nano vanadium dioxide with uniform particle sizes and monodispersity is obtained. The method has the advantages of short preparation time, high preparation efficiency, energy conservation and capability of preparing the nano vanadium dioxide with uniform appearance and high system dispersibility.
In the above embodiment, in order to maximize the production efficiency and obtain the powder with the most uniform particle size, the atomization of the alkaline precipitant and the tetravalent vanadium salt solution and the reaction and precipitation in the reactor of the present application are performed as follows,
firstly, respectively placing a vanadium salt solution and a precipitator solution in an ultrasonic atomizer with ultrasonic frequency of 1.7-3 MHz for atomization to generate fog drops, guiding the fog drops into a reactor filled with absolute ethyl alcohol through carrier gas, placing the reactor in ultrasonic water bath equipment, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining a suspension after full reaction, aging for 0.5-12 h, and centrifuging to obtain a precipitate, wherein the centrifugal rotating speed is 5000-11000 rpm.
Correspondingly, the precipitator solution needs to be prepared before the precipitator solution is atomized, and the preparation process comprises the steps of dissolving the precipitator in deionized water to prepare a solution of 0.2-1 mol/L, and performing ultrasonic dispersion for 15-30 min to complete the preparation of the precipitator solution. In this case, the precipitant solution may be one or more of ammonia, sodium hydroxide, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, and sodium carbonate. The preparation method comprises the steps of firstly preparing a tetravalent vanadium salt solution containing a surfactant before atomizing the tetravalent vanadium salt solution, wherein the preparation process comprises the steps of dissolving tetravalent vanadium salt with the purity of more than or equal to 99.0% in deionized water to prepare a solution with the concentration of 0.1-0.5 mol/L, adding 0.5-1 wt% of the surfactant, and carrying out ultrasonic dispersion for 15-30 min; and slowly dripping the qualified precipitant solution into the prepared vanadyl sulfate solution, and filtering and separating out a clarified solution for later use after a small amount of precipitate appears. In this case, the tetravalent vanadium salt may be one or more of vanadyl sulfate, vanadyl oxalate and vanadyl dichloride; the surfactant can be one of PEG with molecular weight of 400-6000, Tween 80, PVP, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
Further, the VO (OH)2 precursor collected and washed in the method is prepared by the following steps of washing precipitates obtained by reaction with deionized water for three times, washing with absolute ethyl alcohol for two times, and finally separating to obtain the precursor, wherein in each washing and alcohol washing process, the precursor suspension is uniformly stirred and then subjected to ultrasonic dispersion, and the duration of each washing is 15-30 min. The hydrothermal crystallization of the precursor for preparing the suspension is carried out according to the following steps, the suspension containing the precursor is transferred to a hydrothermal kettle, and the vanadium dioxide powder is prepared through hydrothermal reaction, wherein the temperature of the hydrothermal reaction is controlled between 80 and 400 ℃; the hydrothermal reaction time is controlled to be 2-240 hours; the filling ratio of the hydrothermal reaction is controlled to be 20-90%. In this case, the temperature of the hydrothermal reaction is preferably 200 to 350, the time of the hydrothermal reaction is preferably 4 to 120 hours, and the packing ratio of the hydrothermal reaction is preferably 30 to 80%. Further, the temperature of the hydrothermal reaction is 240-300 ℃, the time of the hydrothermal reaction is 4-48 hours, and the filling ratio of the hydrothermal reaction is 50-80%.
In summary, the above process provided by the present application also has the following advantages,
1. the invention ultrasonically atomizes the vanadium source and the precipitator, strengthens the mass transfer process, realizes the micro or mesoscopic uniform mixing and achieves the effective control of the growth of the precursor crystal.
2. The method for preparing the vanadium dioxide powder has the advantages of simple and convenient operation, low cost, easy control, full reaction, good product crystallization and good dispersibility in water and a dispersing agent;
3. the invention effectively integrates the technologies of ultrasonic wave, hydrothermal and the like, and can obviously improve the synthesis efficiency and the crystallinity; the obtained nano-scale vanadium dioxide has good dispersibility and uniformity, and can be widely applied to various fields such as film materials and the like as a nano material.
The invention prepares the M-phase vanadium dioxide nano powder based on a hydrothermal auxiliary-ultrasonic atomization method, and can prepare the nano powder with uniform appearance, narrow distribution and good dispersibility. Compared with the prior art, the method has advantages and competitiveness in the aspects of manufacturing high-quality nano powder and industrialization potential, and has wide application prospect.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In view of the problems of the prior art, the present invention aims to provide a method for preparing a monodisperse high-purity vanadium dioxide powder with high yield. Before hydrothermal reaction, the precursor is prepared by adopting double ultrasonic spraying, the advantages of a double ultrasonic atomization method and a hydrothermal method can be combined, the hydrothermal reaction can be carried out more easily, and the prepared vanadium dioxide powder is fine in particles, uniform in integral distribution and good in crystallinity.
The specific operation steps are as follows:
1. preparation of a precipitant solution: dissolving a precipitator in deionized water to prepare a solution of 0.2-1 mol/L, and performing ultrasonic dispersion for 15-30 min; the precipitant may be one of the following: ammonia water; sodium hydroxide; ammonium bicarbonate; ammonium carbonate; sodium bicarbonate; one or more of sodium carbonate.
2. Preparing a vanadium salt solution: dissolving tetravalent vanadium salt (the purity is more than or equal to 99.0%) in deionized water to prepare a solution of 0.1-0.5 mol/L, adding 0.5-1 wt% of surfactant, and performing ultrasonic dispersion for 15-30 min; slowly dripping the precipitant solution obtained in the step one into the prepared vanadyl sulfate solution, and filtering and separating clear liquid for later use when a small amount of precipitate appears. Wherein the vanadium salt may be one of the following: vanadyl sulfate; vanadyl oxalate; tetravalent vanadium sources such as vanadyl dichloride and the like. The surfactant may be one of the following: PEG (molecular weight 400-; tween 80; PVP; cetyl trimethylammonium bromide (CTAB); sodium Dodecyl Sulfate (SDS); sodium dodecyl sulfate; sodium Dodecylbenzenesulfonate (SDBS).
3. Double ultrasonic atomization precipitation: firstly, respectively placing a vanadium salt solution and a precipitator solution in an ultrasonic atomizer with ultrasonic frequency of 1.7-3 MHz for atomization to generate fog drops, guiding the fog drops into a reactor filled with absolute ethyl alcohol through carrier gas, placing the reactor in ultrasonic water bath equipment, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining a suspension after full reaction, aging for 0.5-12 h, centrifuging to obtain a precipitate, wherein the centrifugal rotating speed is 5000-11000 rpm.
4. Precursor washing and centrifugal separation: washing the precipitate obtained in the third step with deionized water for three times, washing with absolute ethyl alcohol for two times, and in the washing and alcohol washing processes, carrying out ultrasonic dispersion after uniformly stirring the precursor suspension for 15-30 min each time; and carrying out centrifugal separation after each water washing and alcohol washing process to finally obtain the precursor.
5. Hydrothermal crystallization: and (4) preparing the precursor obtained in the fourth step into a suspension, transferring the suspension to a hydrothermal kettle, and preparing vanadium dioxide powder through hydrothermal reaction. The hydrothermal reaction temperature may be 180 to 400 ℃, preferably 200 to 350 ℃, and more preferably 240 to 300 ℃. The hydrothermal reaction time is 2 to 240 hours, preferably 4 to 120 hours, and more preferably 4 to 48 hours. The filling ratio of the hydrothermal reaction may be 20 to 90%, preferably 30 to 80%, and more preferably 50 to 80%.
Example one
Step 1, dissolving 0.2mol of sodium hydroxide in deionized water, and performing ultrasonic dispersion for 15-30 min to prepare 1000ml of solution a with the concentration of 0.2 mol/L;
step 2, dissolving vanadyl sulfate in deionized water to prepare 1000ml of solution with the concentration of 0.1mol/l, adding 5g of PEG-6000, and performing ultrasonic dispersion for 15-30 min to obtain solution b;
step 3, respectively putting the solutions a and b in a 3MHz ultrasonic atomization device for atomization, then dropping the atomized reaction liquid into a reactor for mixing reaction, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining a suspension after full reaction, and then obtaining a precipitate c through centrifugal separation at the rotation speed of 10000 rpm;
step 4, washing the precipitate c with deionized water for three times, washing with absolute ethyl alcohol for two times, and in the washing and alcohol washing processes, carrying out ultrasonic dispersion after uniformly stirring the precursor suspension for 15-30 min each time to finally obtain a precursor d;
and 5, preparing the precursor obtained in the fourth step into 150ml of suspension, then putting the mixed solution into a 200ml hydrothermal kettle, carrying out hydrothermal reaction at 260 ℃ for 24 hours, naturally cooling to room temperature, centrifuging, washing and drying to obtain blue-black M-phase VO2 granular powder, wherein the D50 particle size is 70 nm.
Example two
Step 1, dissolving 0.4mol of sodium hydroxide in deionized water, and performing ultrasonic dispersion for 15-30 min to prepare 1000ml of solution a with the concentration of 0.4 mol/L;
step 2, dissolving vanadyl sulfate in deionized water to prepare 1000ml of 0.2mol/l solution, adding 10g of PEG-2000, and performing ultrasonic dispersion for 15-30 min to obtain a solution b;
step 3, respectively putting the solutions a and b in a 3MHz ultrasonic atomization device for atomization, then introducing the atomized reaction liquid drops into a reactor for mixing reaction, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining a suspension after full reaction, aging for 6 hours, and then obtaining a precipitate c through centrifugal separation at the rotation speed of 10000 rpm;
step 4, washing the precipitate c with deionized water for three times, washing with absolute ethyl alcohol for two times, and in the washing and alcohol washing processes, carrying out ultrasonic dispersion after uniformly stirring the precursor suspension for 15-30 min each time to finally obtain a precursor d;
and 5, preparing the precursor obtained in the fourth step into 100ml of suspension, then putting the mixed solution into a 200ml hydrothermal kettle, carrying out hydrothermal reaction for 24 hours at 240 ℃, naturally cooling to room temperature, and carrying out centrifugal washing and drying to obtain blue-black M-phase VO2 particle powder, wherein the D50 particle size is 110 nm.
EXAMPLE III
Step 1, dissolving 0.2mol of ammonium bicarbonate in deionized water, and performing ultrasonic dispersion for 15-30 min to prepare 1000ml of solution a with the concentration of 0.2 mol/L;
step 2, dissolving vanadyl oxalate in deionized water to prepare 1000ml of solution with the concentration of 0.1mol/l, adding 10g of CTBA, and performing ultrasonic dispersion for 15-30 min to obtain solution b;
and 3, respectively putting the solutions a and b into a 3MHz ultrasonic atomization device for atomization, then introducing the atomized reaction liquid drops into a reactor for mixing reaction, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining a suspension after full reaction, aging for 12 hours, and then obtaining a precipitate c through centrifugal separation at the rotation speed of 10000 rpm. (ii) a
Step 4, washing the precipitate c with deionized water for three times, washing with absolute ethyl alcohol for two times, and in the washing and alcohol washing processes, carrying out ultrasonic dispersion after uniformly stirring the precursor suspension for 15-30 min each time to finally obtain a precursor d;
and 5, preparing the precursor obtained in the fourth step into 150ml of suspension, then putting the mixed solution into a 200ml hydrothermal kettle, carrying out hydrothermal reaction for 24 hours at 300 ℃, naturally cooling to room temperature, and carrying out centrifugal washing and drying to obtain blue-black M-phase VO2 particle powder, wherein the D50 particle size is 90 nm.
Claims (10)
1. AThe technological process of preparing nanometer vanadium dioxide powder includes the following steps: the process method comprises respectively atomizing alkaline precipitant and tetravalent vanadium salt solution containing surfactant into fog drops below 10 μm by ultrasonic atomizer, and placing the two atomized drops in a reactor in ultrasonic water bath for contact and reaction to generate VO (OH)2Precipitating, and collecting the precipitate VO (OH) obtained by the reaction with ethanol2And washed to obtain VO (OH)2A precursor; collecting and washing the obtained VO (OH)2And ultrasonically dispersing the precursor and deionized water into a suspension, and finally carrying out hydrothermal crystallization treatment on the suspension to obtain the nano vanadium dioxide with uniform granularity and dispersed monomers.
2. The process method for preparing vanadium dioxide nanopowder according to claim 1, wherein: the atomization of the alkaline precipitant and the tetravalent vanadium salt solution and the reaction and precipitation in the reactor are carried out as follows,
firstly, respectively placing a vanadium salt solution and a precipitator solution in an ultrasonic atomizer with ultrasonic frequency of 1.7-3 MHz for atomization to generate fog drops, guiding the fog drops into a reactor filled with absolute ethyl alcohol through carrier gas, placing the reactor in ultrasonic water bath equipment, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining a suspension after full reaction, aging for 0.5-12 h, and centrifuging to obtain a precipitate, wherein the centrifugal rotating speed is 5000-11000 rpm.
3. The process method for preparing vanadium dioxide nanopowder according to claim 1, wherein: the precipitant solution is prepared before atomizing the precipitant solution, the preparation process comprises,
dissolving a precipitator in deionized water to prepare a solution of 0.2-1 mol/L, and performing ultrasonic dispersion for 15-30 min to complete the preparation of the precipitator solution.
4. The process method for preparing vanadium dioxide nanopowder according to claim 3, wherein: the precipitant solution may be one or more of ammonia, sodium hydroxide, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate and sodium carbonate.
5. The process method for preparing vanadium dioxide nanopowder according to claim 1, wherein: before the quadrivalent vanadium salt solution containing the surfactant is atomized, the quadrivalent vanadium salt solution needs to be prepared, the preparation process comprises the following steps,
dissolving a tetravalent vanadium salt with the purity of more than or equal to 99.0% in deionized water to prepare a solution with the concentration of 0.1-0.5 mol/L, adding 0.5-1 wt% of a surfactant, and performing ultrasonic dispersion for 15-30 min; and slowly dripping the qualified precipitant solution into the prepared vanadyl sulfate solution, and filtering and separating out a clarified solution for later use after a small amount of precipitate appears.
6. The process method for preparing vanadium dioxide nanopowder according to claim 5, wherein: the tetravalent vanadium salt can be one or more of vanadyl sulfate, vanadyl oxalate and vanadyl dichloride; the surfactant can be one of PEG with molecular weight of 400-6000, Tween 80, PVP, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
7. The process method for preparing vanadium dioxide nanopowder according to claim 1, 2, 3, 4, 5 or 6, characterized in that: collecting and washing the VO (OH) obtained2The precursor is carried out according to the following steps,
washing the precipitate obtained by the reaction with deionized water for three times, then washing with absolute ethyl alcohol for two times, finally separating to obtain a precursor,
and in the washing and alcohol washing processes, the precursor suspension is uniformly stirred and then subjected to ultrasonic dispersion, wherein the duration of each time is 15-30 min.
8. The process method for preparing vanadium dioxide nanopowder according to claim 7, wherein: the hydrothermal crystallization of the precursor for preparing the suspension is carried out according to the following steps,
transferring the suspension containing the precursor into a hydrothermal kettle, preparing vanadium dioxide powder through hydrothermal reaction,
wherein the temperature of the hydrothermal reaction is controlled to be 80-400 ℃; the hydrothermal reaction time is controlled to be 2-240 hours; the filling ratio of the hydrothermal reaction is controlled to be 20-90%.
9. The process method for preparing vanadium dioxide nanopowder according to claim 8, wherein: the temperature of the hydrothermal reaction is 200-350, the time of the hydrothermal reaction is 4-120 hours, and the filling ratio of the hydrothermal reaction is 30-80%.
10. The process method for preparing vanadium dioxide nanopowder according to claim 9, wherein: the temperature of the hydrothermal reaction is 240-300 ℃, the time of the hydrothermal reaction is 4-48 hours, and the filling ratio of the hydrothermal reaction is 50-80%.
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Cited By (2)
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| CN113912116A (en) * | 2021-11-09 | 2022-01-11 | 成都先进金属材料产业技术研究院股份有限公司 | Method for synthesizing superfine M-phase vanadium dioxide nano powder by microwave precipitation method |
| CN116891649A (en) * | 2023-09-11 | 2023-10-17 | 成都先进金属材料产业技术研究院股份有限公司 | Vanadium dioxide composite functional powder, film and preparation method thereof |
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