CN112209440A - Process for preparing M-phase vanadium dioxide nano powder - Google Patents
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- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 33
- 230000027311 M phase Effects 0.000 title claims abstract description 29
- 239000011858 nanopowder Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000003681 vanadium Chemical class 0.000 claims abstract description 28
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000012266 salt solution Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 51
- 238000005406 washing Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 18
- 239000012716 precipitator Substances 0.000 claims description 18
- 238000000889 atomisation Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 12
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 12
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 12
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 230000008859 change Effects 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QKDGGEBMABOMMW-UHFFFAOYSA-I [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] QKDGGEBMABOMMW-UHFFFAOYSA-I 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a process method, in particular discloses a process method for preparing M-phase vanadium dioxide nano powder, and belongs to the technical field of metallurgical production processes. The preparation method for preparing the M-phase vanadium dioxide nano powder has the advantages of short preparation time, high preparation efficiency, energy conservation and uniform appearance and narrow distribution. 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; followed by the reaction of VO (OH)2The precursor is prepared into the nano vanadium dioxide particles through microwave drying, grinding and calcining.
Description
Technical Field
The invention relates to a process method, in particular to a process method for preparing M-phase vanadium dioxide nano powder, belonging to the technical field of metallurgical production processes.
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.
VO that has been reported2The powder preparation method includes sol-gel method, hydrothermal method, precipitation method, etc., for example, in chinese patent with application publication No. CN201110320919, V with purity higher than 99.9% is used2O5Powder and KReO with purity higher than 99.0%4Preparing gel powder from the powder by sol-gel method, mixing with C powder, and introducing N into the mixed powder2Reduced to obtain Re-doped VO2And (3) powder. For another example, in chinese patent application publication No. CN201810064752, vanadyl sulfate is first synthesized, vanadyl sulfate solution is titrated with sodium hydroxide solution to prepare vanadium hydroxide oxide, and meanwhile, based on the special structure of the reaction kettle and the use of an oxidant capable of volatilizing oxidizing gas, hydrothermal reaction is performed in a specific oxidizing atmosphere,the reaction solution is basic vanadium oxide solution, and M-phase vanadium dioxide nano powder is prepared by reacting for 72 hours at 260 ℃. However, the sol-gel method has expensive raw material cost, some organic matters are harmful to human bodies, the phenomena of shrinkage and agglomeration can occur during heat treatment at high temperature, the process is difficult to amplify, and the industrial application is very difficult. The powder prepared by the hydrothermal method has the advantages of complete crystal grain development, small grain size, uniform distribution, small agglomeration degree and high activity in the calcining process. However, the disadvantages are that the equipment is required to be resistant to high pressure and the energy consumption is large, thus being not beneficial to industrial production. For the precipitation method, the requirements on raw materials and equipment are low, and the industrial popularization is easy, however, in the adding process of the precipitating agent, the uniformity of microscopic composition can not be realized due to the overhigh local concentration of the precipitating agent, so that the product is agglomerated or the particle appearance is not uniform.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method for preparing the M-phase vanadium dioxide nano powder has the advantages of short preparation time, high preparation efficiency, energy conservation and uniform appearance and narrow distribution.
The technical scheme adopted for solving the technical problems is as follows: a process for preparing M-phase vanadium dioxide nano-powder includes respectively atomizing alkaline precipitant and quadrivalent vanadium salt solution containing surfactant to obtain fog drops less than 10 microns by ultrasonic atomizer, contacting the two atomized drops in reactor in ultrasonic water bath, and reacting to obtain VO (OH)2Precipitating, and collecting the precipitate VO (OH) obtained by the reaction with ethanol2And washed to obtain VO (OH)2A precursor; followed by the reaction of VO (OH)2The precursor is prepared into the nano vanadium dioxide particles through microwave drying, grinding and calcining.
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.
The preferred mode of the above scheme is to collect and wash the obtained VO (OH)2The 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.
Further, the microwave drying of the precursor is carried out as follows,
placing the precursor in a microwave atmosphere furnace, controlling the microwave frequency to be 2.45GHz and the protection of inert gas, controlling the temperature to be 70-100 ℃ and the time to be 5-15 min, and drying to obtain VO (OH)2Solid, grind for 30 min.
In a preferred embodiment of the above aspect, the calcination of the milled precursor is carried out by the following steps,
the dried and ground precursor is placed in a microwave atmosphere furnace again for calcination, the temperature is controlled to be 450-550 ℃ under the protection of inert gas, the time is 30 min-1 h, and the blue-black M-phase VO is obtained2The powder has a particle size of 50 to 200 nm.
Further, the inert gas may be N2Or Ar.
The invention has the beneficial effects that: the technological method provided by the application utilizes an ultrasonic atomizer to atomize tetravalent vanadium salt solution with certain concentration and containing a surfactant and alkaline precipitator with certain concentration into fog drops with the diameter of several micrometers, and the two atomized drops are placed in a reactor in an ultrasonic water bath for contact reaction to generate VO (OH)2Precipitation, reaction to precipitate VO (OH)2Collecting by using ethanol; collecting the washed VO (OH)2 to be dried/ground/calcined into nano vanadium dioxide particles by microwave. The basic principle is that the ultrasonic cavitation effect is fully utilized to convert a vanadium source and a precipitator into micro reaction liquid drops for contact reaction, so that the degree of supersaturation of the reaction is highly homogenized, explosive nucleation is generated, meanwhile, the system dispersibility is improved under the steric effect of a surfactant, and finally precursor precipitate with small and uniform particle size is obtained. The method has the advantages of short preparation time and high preparation efficiencyAnd the energy is saved, and the nano vanadium dioxide with uniform appearance and narrow distribution can be prepared.
Detailed Description
In order to solve the technical problems in the prior art, the invention provides a process method for preparing M-phase vanadium dioxide nano-powder, which has the advantages of short preparation time, high preparation efficiency, energy conservation and uniform appearance and narrow distribution. 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; followed by the reaction of VO (OH)2The precursor is prepared into the nano vanadium dioxide particles through microwave drying, grinding and calcining. The technological method provided by the application utilizes an ultrasonic atomizer to atomize tetravalent vanadium salt solution with certain concentration and containing a surfactant and alkaline precipitator with certain concentration into fog drops with the diameter of several micrometers, and the two atomized drops are placed in a reactor in an ultrasonic water bath for contact reaction to generate VO (OH)2Precipitation, reaction to precipitate VO (OH)2Collecting by using ethanol; collecting washed VO (OH)2And drying/grinding/calcining by microwave to obtain the nano vanadium dioxide particles. The basic principle is that the ultrasonic cavitation effect is fully utilized to convert a vanadium source and a precipitator into micro reaction liquid drops for contact reaction, so that the degree of supersaturation of the reaction is highly homogenized, explosive nucleation is generated, meanwhile, the system dispersibility is improved under the steric effect of a surfactant, and finally precursor precipitate with small and uniform particle size is obtained.
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. 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 performing ultrasonic dispersion for 15-30 min to complete preparation of a precipitator solution; 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. Meanwhile, VO (OH) obtained by collecting and washing in the present application2The precursor is prepared by washing the precipitate obtained by the 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 process, the precursor suspension is uniformly stirred and then subjected to the next washing processAnd carrying out ultrasonic dispersion, wherein the duration of each time is 15-30 min. The microwave drying of the precursor is carried out according to the following steps, the precursor is placed in a microwave atmosphere furnace, the microwave frequency is 2.45GHz, the inert gas is used for protection, the temperature is controlled to be 70-100 ℃, the time is 5-15 min, and drying is carried out to obtain VO (OH)2Solid, grind for 30 min.
Further, the method comprises the following steps of placing the dried and ground precursor in a microwave atmosphere furnace again for calcination under the protection of inert gas, controlling the temperature to be 450-550 ℃ and the time to be 30 min-1 h to obtain the blue-black M-phase VO2The powder has a particle size of 50 to 200 nm. In this case, the inert gas may be N2Or Ar.
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 invention utilizes the microwave and other external field auxiliary methods, has the characteristics of high speed, high efficiency, energy saving, high quality and the like, does not generate overheating phenomenon, and has short preparation time and high efficiency.
3. The invention effectively integrates the technologies of ultrasonic wave, microwave and the like, can greatly shorten the reaction time required by preparing the nano vanadium dioxide powder, 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 double ultrasonic atomization technology of the application introduces two-phase reaction liquid simultaneously under the ultrasonic atomization environment to form a fog droplet micro-reactor, limits the reaction in the fog droplets, integrates the microwave drying/pyrolysis technology to effectively avoid the defects, and efficiently prepares the monodisperse vanadium dioxide nano powder with uniform particle size. The prior art has no report of preparing M-phase vanadium dioxide powder by adopting a double ultrasonic atomization-microwave drying/pyrolysis mode.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Aiming at the problems in the prior art, the invention provides a method for preparing M-phase vanadium dioxide nano powder based on a double ultrasonic atomization-microwave technology, which has the advantages of short preparation time, high efficiency, large-scale production and the like, and can well control the properties of the powder such as particle size, morphology, crystallinity and the like.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method for preparing M-phase vanadium dioxide nano powder based on a double ultrasonic atomization-microwave technology comprises the following steps:
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.
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. The vanadium salt can be one of the following: vanadyl sulfate; vanadyl oxalate; one or more of vanadyl dichloride. 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).
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.
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.
Microwave drying: placing the precursor obtained in the fourth step in a microwave atmosphere furnace, controlling the microwave frequency to be 2.45GHz and the protection of inert gas, controlling the temperature to be 70-100 ℃ and the time to be 5-15 min, and drying to obtain VO (OH)2Solid, grind for 30 min.
Microwave calcination: the precursor dried and ground in the fifth step is placed in a microwave atmosphere furnace again for calcination, the temperature is controlled to be 450-550 ℃ under the protection of inert gas, the time is 30 min-1 h, and the blue-black M-phase VO is obtained2The powder has a particle size of 50 to 200 nm. The inert gas may be N2 or Ar.
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 0.1mol/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;
step 5, placing the precursor d in a microwave atmosphere furnace, controlling the microwave frequency to be 2.45GHz and the protection of high-purity N2, controlling the temperature to be 80 ℃ and the time to be 8min, drying to obtain VO (OH)2 solid, and grinding for 30 min;
and 6, putting the dried and ground precursor into a microwave atmosphere furnace again for calcination, protecting by high-purity N2, controlling the temperature at 450 ℃ for 1h, and obtaining blue-black M-phase VO2 powder with the D50 particle size of 80 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;
step 5, placing the precursor d in a microwave atmosphere furnace, controlling the microwave frequency to be 2.45GHz and the protection of high-purity N2, controlling the temperature to be 70 ℃ and the time to be 10min, drying to obtain VO (OH)2 solid, and grinding for 30 min;
and 6, putting the dried and ground precursor into a microwave atmosphere furnace again for calcination, protecting by high-purity N2, controlling the temperature at 500 ℃ for 1h, and obtaining blue-black M-phase VO2 powder with the D50 particle size of 136 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;
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 12 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;
step 5, placing the precursor d in a microwave atmosphere furnace, controlling the microwave frequency to be 2.45GHz and the protection of high-purity N2, controlling the temperature to be 80 ℃ and the time to be 8min, drying to obtain VO (OH)2 solid, and grinding for 30 min;
and 6, putting the dried and ground precursor into a microwave atmosphere furnace again for calcination, protecting by high-purity N2, controlling the temperature at 550 ℃ for 0.5h, and obtaining blue-black M-phase VO2 powder with the D50 particle size of 150 nm.
Claims (10)
1. A process method for preparing M-phase vanadium dioxide nano powder is characterized by comprising 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; followed by the reaction of VO (OH)2The precursor is prepared into the nano vanadium dioxide particles through microwave drying, grinding and calcining.
2. The process method for preparing the M-phase vanadium dioxide nano powder according to claim 1, which is characterized in that: 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, centrifuging to obtain a precipitate, wherein the centrifugal rotating speed is 5000-11000 rpm.
3. The process method for preparing the M-phase vanadium dioxide nano powder according to claim 1, which is characterized in that: 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 the M-phase vanadium dioxide nano powder according to claim 3, which is characterized in that: 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 the M-phase vanadium dioxide nano powder according to claim 1, which is characterized in that: 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 the M-phase vanadium dioxide nano powder according to claim 5, which is characterized in that: 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 the M-phase vanadium dioxide nano powder according to the claim 1, 2, 3, 4, 5 or 6, which is 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 the M-phase vanadium dioxide nano powder according to the claim 1, 2, 3, 4, 5 or 6, which is characterized in that: the microwave drying of the precursor is carried out according to the following steps,
placing the precursor in a microwave atmosphere furnace, controlling the microwave frequency to be 2.45GHz and the protection of inert gas, controlling the temperature to be 70-100 ℃ and the time to be 5-15 min, and drying to obtain VO (OH)2Solid, grind for 30 min.
9. The process method for preparing the M-phase vanadium dioxide nano powder according to claim 8, which is characterized in that: the calcination of the milled precursor is carried out as follows,
the dried and ground precursor is placed in a microwave atmosphere furnace again for calcination, the temperature is controlled to be 450-550 ℃ under the protection of inert gas, the time is 30 min-1 h, and the blue-black M-phase VO is obtained2The powder has a particle size of 50 to 200 nm.
10. The process method for preparing the M-phase vanadium dioxide nano powder according to claim 9, which is characterized in that: the inert gas may be N2Or Ar.
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