CN112209443A - Method for preparing M-phase vanadium dioxide by single ultrasonic atomization microwave method - Google Patents
Method for preparing M-phase vanadium dioxide by single ultrasonic atomization microwave method Download PDFInfo
- Publication number
- CN112209443A CN112209443A CN202011112471.3A CN202011112471A CN112209443A CN 112209443 A CN112209443 A CN 112209443A CN 202011112471 A CN202011112471 A CN 202011112471A CN 112209443 A CN112209443 A CN 112209443A
- Authority
- CN
- China
- Prior art keywords
- microwave
- vanadium dioxide
- preparing
- ultrasonic atomization
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 73
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 41
- 238000000889 atomisation Methods 0.000 title claims abstract description 40
- 230000027311 M phase Effects 0.000 title claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000012716 precipitator Substances 0.000 claims abstract description 22
- 150000003681 vanadium Chemical class 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 230000005587 bubbling Effects 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 description 12
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 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
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 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 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011858 nanopowder 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
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening 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
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Images
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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of preparation of vanadium dioxide powder, and particularly relates to a method for preparing M-phase vanadium dioxide by a single ultrasonic atomization microwave method. The technical scheme adopted by the invention for solving the technical problems is to provide a method for preparing M-phase vanadium dioxide by a single ultrasonic atomization microwave method. The method comprises the following steps: and (2) introducing fog drops formed by ultrasonic atomization of the vanadium salt solution into a uniform precipitator solution containing a surfactant in a bubbling manner to react to obtain a suspension, aging, carrying out solid-liquid separation to obtain a precursor precipitate, washing the precursor precipitate, carrying out solid-liquid separation to obtain a precursor, and carrying out microwave drying, grinding and microwave calcination on the precursor to obtain the M-phase vanadium dioxide. The nano-scale vanadium dioxide powder prepared by the method has good dispersibility and uniformity, short preparation time in the whole process and good application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of vanadium dioxide powder, and particularly relates to a method for preparing M-phase vanadium dioxide by a single ultrasonic atomization microwave method.
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 the like. Wherein VO2(M) is the most studied phase at present, and 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 reported at present2The powder preparation methods include a sol-gel method, a hydrothermal method, a precipitation method and the like, and for the sol-gel method, the raw material cost is high, 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, this method requires high pressure resistance for the equipment and also consumes much energy, thus being disadvantageous for industrial production. The precipitation method has low requirements on raw materials and equipment, is easy to industrially popularize, and can not be realized due to overhigh local concentration of the precipitating agent in the adding process of the precipitating agentThe uniformity of the micro-composition, thereby causing the agglomeration of the product or the uneven particle appearance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing M-phase vanadium dioxide by a single ultrasonic atomization microwave method, which has short preparation time and can ensure that the vanadium dioxide has uniform particle size.
The technical scheme adopted by the invention for solving the technical problems is to provide a method for preparing M-phase vanadium dioxide by a single ultrasonic atomization microwave method. The method comprises the following steps: and (2) introducing fog drops formed by ultrasonic atomization of the vanadium salt solution into a uniform precipitator solution containing a surfactant in a bubbling manner to react to obtain a suspension, aging, carrying out solid-liquid separation to obtain a precursor precipitate, washing the precursor precipitate, carrying out solid-liquid separation to obtain a precursor, and carrying out microwave drying, grinding and microwave calcination on the precursor to obtain the M-phase vanadium dioxide.
In the method for preparing the M-phase vanadium dioxide by the single ultrasonic atomization microwave method, the vanadium salt solution is prepared by dissolving tetravalent vanadium salt in deionized water, and the concentration of the solution is 0.1-0.5 moL/L.
Further, the purity of the tetravalent vanadium salt is more than or equal to 99.0 percent.
Further, the vanadium salt is at least one of vanadyl sulfate, vanadyl oxalate or vanadyl dichloride.
In the method for preparing the M-phase vanadium dioxide by the single ultrasonic atomization microwave method, the surfactant is any one of PEG with the molecular weight of 400-6000, Tween 80, PVP, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, sodium dodecyl sulfonate or sodium dodecyl benzene sulfonate.
In the method for preparing the M-phase vanadium dioxide by the single ultrasonic atomization microwave method, the uniform precipitator solution is prepared by dissolving a precipitator in deionized water to prepare a solution with the concentration of 0.1-1 moL/L, adding 0.5-1 wt% of a surfactant, and performing ultrasonic treatment for 15-30 min.
Further, the uniform precipitator is at least one of ammonia water, sodium hydroxide, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate or sodium carbonate.
In the method for preparing the M-phase vanadium dioxide by the single ultrasonic atomization microwave method, an ultrasonic atomizer is adopted for atomization, wherein the ultrasonic frequency of the ultrasonic atomizer is 1.7-3 MHz.
Further, continuously stirring in the reaction process, and simultaneously controlling the temperature to be 30-60 ℃; the reaction time is 30-120 min.
Further, the aging time is 0.5-12 h.
Further, the solid-liquid separation mode is centrifugation, and the rotation speed of the centrifugation is 5000-11000 rpm.
In the method for preparing the M-phase vanadium dioxide by the single ultrasonic atomization microwave method, the precursor precipitate is washed for 3 times by using deionized water, then washed for 2 times by using absolute ethyl alcohol, and ultrasonic dispersion is adopted for 15-30 min in each washing process.
In the method for preparing the M-phase vanadium dioxide by the single ultrasonic atomization microwave method, the precursor is placed in a microwave atmosphere furnace for microwave drying, inert gas is used for protection, and the microwave frequency is controlled to be 2.45 GHz; the temperature is 70-100 ℃; the time is 5-15 min.
Further, in the microwave drying process, the inert gas adopted is N2Or Ar.
In the method for preparing the M-phase vanadium dioxide by the single ultrasonic atomization microwave method, the microwave calcination is to place the precursor dried and ground by microwaves into the microwave atmosphere furnace again, and the inert gas is used for protection, wherein the temperature is 450-500 ℃; the time is 30-60 min.
Further, in the microwave calcination process, the inert gas adopted is N2Or Ar.
The invention has the beneficial effects that:
the invention introduces fog drops formed by ultrasonic atomization of the vanadium salt solution into the uniform precipitator solution containing the surfactant in a bubbling mode to react to generate precursor precipitates, thereby strengthening the mass transfer process, realizing micro or mesoscopic uniform mixing and achieving the effective control of the growth of precursor crystals. The invention adopts the uniform precipitator and ultrasonic atomization to avoid the phenomenon of uneven local concentration in the solution caused by using a direct precipitator, so that monodisperse and high-purity nano vanadium dioxide powder can be obtained, and the particle size of the prepared M-phase vanadium dioxide is 20-200 nm. The method of the invention combines auxiliary methods such as microwave and the like, effectively shortens the reaction time required by preparing the nano vanadium dioxide powder, and can obviously improve the synthesis efficiency and the crystallinity. The nano-scale vanadium dioxide powder prepared by the method has good dispersibility and uniformity, has superiority and competitiveness in the aspects of low-cost manufacture of high-quality nano-powder and industrialization potential compared with the prior art, and has wide application prospect.
Drawings
FIG. 1 shows VO prepared in example 1 of the present invention2X-ray diffraction pattern (XRD) of the powder.
FIG. 2 shows VO prepared in example 1 of the present invention2Scanning Electron Micrographs (SEM) of the powder.
Detailed Description
Aiming at the problems in the prior art, the invention provides a method for preparing M-phase vanadium dioxide by a single ultrasonic atomization microwave method, and the method has the advantages of short preparation time, high efficiency and large-scale production, and can well control the properties of the powder such as particle size, morphology, crystallinity and the like.
Specifically, the invention provides a method for preparing M-phase vanadium dioxide by a single ultrasonic atomization microwave method, which comprises the following steps:
and (2) introducing fog drops formed by ultrasonic atomization of the vanadium salt solution into a uniform precipitator solution containing a surfactant in a bubbling manner to react to obtain a suspension, aging, carrying out solid-liquid separation to obtain a precursor precipitate, washing the precursor precipitate, carrying out solid-liquid separation to obtain a precursor, and carrying out microwave drying, grinding and microwave calcination on the precursor to obtain the M-phase vanadium dioxide.
In the invention, an ultrasonic atomizer is utilized to atomize a tetravalent vanadium salt solution with a certain concentration into micron fog drops, the fog drops are introduced into a uniform precipitator solution containing 0.5-1 wt% of a surfactant with the concentration of 0.1-1 moL/L in a bubbling manner through a carrier gas, the reaction process is continuously stirred, the temperature is controlled to be 30-60 ℃, precursor precipitate is generated, the precursor precipitate is washed, and the precursor after solid-liquid separation is subjected to microwave drying, grinding and microwave calcination to obtain the nano vanadium dioxide particles.
The invention utilizes ultrasonic cavitation effect to convert tetravalent vanadium salt solution into micro reaction liquid drops, simultaneously improves the contact nonuniformity of the vanadium salt solution and a precipitator during reaction in a bubbling mode, increases the reaction contact area, improves the reaction uniformity, ensures that the nucleation speed in a reaction system is extremely high, generates explosive nucleation, consumes most ions due to the generation of a large amount of crystal nuclei, greatly reduces the degree of over-saturation required by further growth of the crystal nuclei, correspondingly reduces the growth rate, simultaneously improves the system dispersibility under the steric effect of a surfactant, and finally obtains precursor precipitate with small and uniform particle size. The subsequent integration of ultrasonic dispersion-microwave drying/calcining technology, the ultrasonic cavitation effect is utilized to generate shock waves with shearing force in the reaction and washing processes, the agglomeration structure of the powder is destroyed, the characteristics of high microwave heating speed and uniform heating are utilized in the drying and calcining processes, the agglomeration in the precursor heat treatment process can be effectively prevented, and finally the monodisperse nano vanadium dioxide with uniform granularity is obtained.
The present invention will be described in further detail below with reference to specific examples.
Example 1
Step 1: dissolving 0.5moL of sodium hydroxide in deionized water to prepare 1000mL of solution with the concentration of 0.5moL/L, adding 0.5 wt% of surfactant, and performing ultrasonic treatment for 15-30 min to obtain a uniform precipitator solution;
step 2: dissolving vanadyl oxalate in deionized water to prepare 1000mL of 0.25moL/L solution, and performing ultrasonic dispersion for 15-30 min to obtain a vanadium salt solution;
and step 3: putting the vanadium salt solution into a 3MHz ultrasonic atomization device for atomization, introducing atomized reaction liquid drops into 250mL of uniform precipitator solution in a bubbling manner for reaction at the reaction temperature of 60 ℃, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining suspension after full reaction, and obtaining precursor precipitate through centrifugal separation at the rotation speed of 10000 rpm;
and 4, step 4: washing the precursor precipitate with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and in the washing and alcohol washing processes, carrying out ultrasonic dispersion after uniformly stirring the precursor suspension, wherein the duration of each time is 15-30 min, so as to finally obtain a precursor;
and 5: placing the precursor in a microwave atmosphere furnace, and obtaining high-purity N2Protection, microwave frequency is 2.45GHz, temperature is controlled to be 80 ℃, time is 8min, drying is carried out to obtain VO (OH)2Solid, grinding for 30 min;
step 6: the dried and ground precursor is placed in a microwave atmosphere furnace again for calcination, and the high-purity N is obtained2Protecting, controlling the temperature at 450 ℃ for 1h to obtain blue-black M-phase VO2Powder particles of D50The particle size is 80 nm.
Example 2
Step 1: dissolving 0.4moL of sodium carbonate in deionized water to prepare 1000ml of solution with the concentration of 0.4moL/L, adding 0.8 wt% of surfactant, and performing ultrasonic treatment for 15-30 min to obtain uniform precipitator solution;
step 2: dissolving vanadyl sulfate in deionized water to prepare 1000mL of 0.2moL/L solution, and performing ultrasonic dispersion for 15-30 min to obtain a vanadium salt solution;
and step 3: putting the vanadium salt solution into a 3MHz ultrasonic atomization device for atomization, introducing atomized reaction liquid drops into 250mL of uniform precipitator solution in a bubbling manner for reaction at the reaction temperature of 45 ℃, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining suspension after full reaction, and obtaining precursor precipitate through centrifugal separation at the rotation speed of 10000 rpm;
and 4, step 4: washing the precursor precipitate with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and in the washing and alcohol washing processes, carrying out ultrasonic dispersion after uniformly stirring the precursor suspension, wherein the duration of each time is 15-30 min, so as to finally obtain a precursor;
and 5: placing the precursor in a microwave atmosphere furnace, and obtaining high-purity N2Protection, microwave frequency is 2.45GHz, temperature is controlled at 70 ℃ for 10min, and drying is carried out to obtain VO (OH)2Solid, grinding for 30 min;
step 6: drying and grinding the precursor againCalcining in microwave oven to obtain high-purity N2Protecting, controlling the temperature at 500 ℃ for 1h to obtain blue-black M-phase VO2Powder particles of D50The particle size was 136 nm.
Example 3
Step 1: dissolving 0.2moL of ammonium bicarbonate in deionized water to prepare 1000mL of 0.2moL/L solution, adding 1 wt% of surfactant, and performing ultrasonic treatment for 15-30 min to obtain a uniform precipitator solution;
step 2: dissolving vanadyl oxalate in deionized water to prepare 1000mL of 0.1moL/L solution, and performing ultrasonic dispersion for 15-30 min to obtain a vanadium salt solution;
and step 3: putting the vanadium salt solution into a 3MHz ultrasonic atomization device for atomization, introducing the atomized reaction liquid drops into 500mL of uniform precipitator solution in a bubbling manner for reaction at the reaction temperature of 35 ℃, continuously performing ultrasonic and mechanical stirring in the reaction process, obtaining suspension after full reaction, and obtaining precursor precipitate by centrifugal separation at the rotation speed of 10000 rpm;
and 4, step 4: washing the precursor precipitate with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, and in the washing and alcohol washing processes, carrying out ultrasonic dispersion after uniformly stirring the precursor suspension, wherein the duration of each time is 15-30 min, so as to finally obtain a precursor;
and 5: placing the precursor in a microwave atmosphere furnace, and obtaining high-purity N2Protection, microwave frequency is 2.45GHz, temperature is controlled at 90 ℃ for 8min, and drying is carried out to obtain VO (OH)2Solid, grinding for 30 min;
step 6: the dried and ground precursor is placed in a microwave atmosphere furnace again for calcination, and the high-purity N is obtained2Protecting, controlling the temperature at 500 ℃ for 0.5h to obtain blue-black M-phase VO2Powder particles of D50The particle size was 150 nm.
Claims (10)
1. The method for preparing the M-phase vanadium dioxide by the single ultrasonic atomization microwave method is characterized by comprising the following steps: the method comprises the following steps: and (2) introducing fog drops formed by ultrasonic atomization of the vanadium salt solution into a uniform precipitator solution containing a surfactant in a bubbling manner to react to obtain a suspension, aging, carrying out solid-liquid separation to obtain a precursor precipitate, washing the precursor precipitate, carrying out solid-liquid separation to obtain a precursor, and carrying out microwave drying, grinding and microwave calcination on the precursor to obtain the M-phase vanadium dioxide.
2. The method for preparing M-phase vanadium dioxide by using the single ultrasonic atomization microwave method according to claim 1, wherein the method comprises the following steps: the vanadium salt solution is prepared by dissolving tetravalent vanadium salt in deionized water, and the concentration of the solution is 0.1-0.5 moL/L.
3. The method for preparing M-phase vanadium dioxide by the single ultrasonic atomization microwave method according to claim 1 or 2, characterized in that: the surfactant is any one of PEG with the molecular weight of 400-6000, Tween 80, PVP, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
4. The method for preparing M-phase vanadium dioxide by using the single ultrasonic atomization microwave method according to any one of claims 1 to 3, which is characterized by comprising the following steps: the vanadium salt is at least one of vanadyl sulfate, vanadyl oxalate or vanadyl dichloride.
5. The method for preparing M-phase vanadium dioxide by using the single ultrasonic atomization microwave method according to any one of claims 1 to 4, which is characterized by comprising the following steps: the uniform precipitator solution is prepared by dissolving a precipitator in deionized water to prepare a solution with the concentration of 0.1-1 moL/L, adding 0.5-1 wt% of a surfactant, and carrying out ultrasonic treatment.
6. The method for preparing M-phase vanadium dioxide by using the single ultrasonic atomization microwave method according to any one of claims 1 to 5, wherein the method comprises the following steps: the uniform precipitator is at least one of ammonia water, sodium hydroxide, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate or sodium carbonate.
7. The method for preparing M-phase vanadium dioxide by using the single ultrasonic atomization microwave method according to any one of claims 1 to 6, which is characterized by comprising the following steps: in the step of introducing fog drops formed by atomizing a vanadium salt solution into a uniform precipitator solution containing a surfactant in a bubbling mode for reaction to obtain a suspension, at least one of the following conditions is met:
an ultrasonic atomizer is adopted for atomization, wherein the ultrasonic frequency of the ultrasonic atomizer is 1.7-3 MHz;
continuously stirring in the reaction process, and simultaneously controlling the temperature to be 30-60 ℃; the reaction time is 30-120 min;
the aging time is 0.5-12 h;
the solid-liquid separation mode is centrifugation, and the rotation speed of the centrifugation is 5000-11000 rpm.
8. The method for preparing M-phase vanadium dioxide by using the single ultrasonic atomization microwave method according to any one of claims 1 to 7, which is characterized by comprising the following steps: washing the precursor precipitate for 3 times by using deionized water, then washing for 2 times by using absolute ethyl alcohol, and dispersing for 15-30 min by using ultrasonic in each washing process.
9. The method for preparing M-phase vanadium dioxide by using the single ultrasonic atomization microwave method according to any one of claims 1 to 8, which is characterized by comprising the following steps: the microwave drying is to place the precursor in a microwave atmosphere furnace, protect with inert gas, and control the microwave frequency to be 2.45 GHz; the temperature is 70-100 ℃; the time is 5-15 min.
10. The method for preparing M-phase vanadium dioxide by using the single ultrasonic atomization microwave method according to any one of claims 1 to 9, which is characterized by comprising the following steps: the microwave calcination is to place the precursor subjected to microwave drying and grinding in the microwave atmosphere furnace again, and under the protection of inert gas, the temperature is 450-500 ℃; the time is 30-60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011112471.3A CN112209443A (en) | 2020-10-16 | 2020-10-16 | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization microwave method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011112471.3A CN112209443A (en) | 2020-10-16 | 2020-10-16 | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization microwave method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112209443A true CN112209443A (en) | 2021-01-12 |
Family
ID=74055580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011112471.3A Pending CN112209443A (en) | 2020-10-16 | 2020-10-16 | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization microwave method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112209443A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116002754A (en) * | 2022-12-13 | 2023-04-25 | 大连融科储能集团股份有限公司 | High-purity small-grain vanadium oxide and preparation method and application thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5427763A (en) * | 1994-04-15 | 1995-06-27 | Mcdonnel Douglas Corp. | Method for making vanadium dioxide powders |
| CN101239703A (en) * | 2008-03-10 | 2008-08-13 | 江苏大学 | A kind of method for preparing monodisperse spherical nano metal oxide powder |
| CN101760735A (en) * | 2008-12-31 | 2010-06-30 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide precursor liquid and method for preparing thin-film material by using the same |
| CN101830510A (en) * | 2010-05-18 | 2010-09-15 | 中国科学院上海硅酸盐研究所 | Preparation method of rutile phase vanadium dioxide nanowire and application |
| CN104071843A (en) * | 2013-03-30 | 2014-10-01 | 中国科学院合肥物质科学研究院 | Preparation method of monodispersed M-phase vanadium dioxide nanoparticles |
| WO2016100967A1 (en) * | 2014-12-19 | 2016-06-23 | Dimien Llc | Vanadium oxide compositions and systems and methods for creating them |
| CN105819508A (en) * | 2016-03-15 | 2016-08-03 | 中国科学院广州能源研究所 | A method for preparing VO2(M) nanopowder and film by spray pyrolysis |
| CN106395901A (en) * | 2016-10-20 | 2017-02-15 | 中国人民解放军国防科学技术大学 | Monoclinic phase vanadium dioxide nanowire and preparation method and application thereof |
| WO2017065451A1 (en) * | 2015-10-12 | 2017-04-20 | 나노에스디 주식회사 | Vanadium-based hollow particles |
| US20170174526A1 (en) * | 2014-04-18 | 2017-06-22 | The Research Foundation For The State University Of New York | Composite nanomaterials and micromaterials, films of same, and methods of making and uses of same |
| JP2017132677A (en) * | 2016-01-30 | 2017-08-03 | 日本化学工業株式会社 | Method for producing vanadium dioxide |
| CN109399711A (en) * | 2018-11-23 | 2019-03-01 | 法尔胜泓昇集团有限公司 | A kind of preparation method of rutile phase hypovanadic oxide nano-powder |
| CN110203972A (en) * | 2019-06-13 | 2019-09-06 | 湖北大学 | The preparation method of phase-M vanadium dioxide nanometre powder |
| CN110255617A (en) * | 2019-06-28 | 2019-09-20 | 东莞深圳清华大学研究院创新中心 | A kind of preparation method of vanadium dioxide nano powder |
| CN110627122A (en) * | 2019-10-24 | 2019-12-31 | 成都先进金属材料产业技术研究院有限公司 | Preparation of VO by solid phase method2Method for phase change materials |
-
2020
- 2020-10-16 CN CN202011112471.3A patent/CN112209443A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5427763A (en) * | 1994-04-15 | 1995-06-27 | Mcdonnel Douglas Corp. | Method for making vanadium dioxide powders |
| CN101239703A (en) * | 2008-03-10 | 2008-08-13 | 江苏大学 | A kind of method for preparing monodisperse spherical nano metal oxide powder |
| CN101760735A (en) * | 2008-12-31 | 2010-06-30 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide precursor liquid and method for preparing thin-film material by using the same |
| CN101830510A (en) * | 2010-05-18 | 2010-09-15 | 中国科学院上海硅酸盐研究所 | Preparation method of rutile phase vanadium dioxide nanowire and application |
| CN104071843A (en) * | 2013-03-30 | 2014-10-01 | 中国科学院合肥物质科学研究院 | Preparation method of monodispersed M-phase vanadium dioxide nanoparticles |
| US20170174526A1 (en) * | 2014-04-18 | 2017-06-22 | The Research Foundation For The State University Of New York | Composite nanomaterials and micromaterials, films of same, and methods of making and uses of same |
| WO2016100967A1 (en) * | 2014-12-19 | 2016-06-23 | Dimien Llc | Vanadium oxide compositions and systems and methods for creating them |
| WO2017065451A1 (en) * | 2015-10-12 | 2017-04-20 | 나노에스디 주식회사 | Vanadium-based hollow particles |
| JP2017132677A (en) * | 2016-01-30 | 2017-08-03 | 日本化学工業株式会社 | Method for producing vanadium dioxide |
| CN105819508A (en) * | 2016-03-15 | 2016-08-03 | 中国科学院广州能源研究所 | A method for preparing VO2(M) nanopowder and film by spray pyrolysis |
| CN106395901A (en) * | 2016-10-20 | 2017-02-15 | 中国人民解放军国防科学技术大学 | Monoclinic phase vanadium dioxide nanowire and preparation method and application thereof |
| CN109399711A (en) * | 2018-11-23 | 2019-03-01 | 法尔胜泓昇集团有限公司 | A kind of preparation method of rutile phase hypovanadic oxide nano-powder |
| CN110203972A (en) * | 2019-06-13 | 2019-09-06 | 湖北大学 | The preparation method of phase-M vanadium dioxide nanometre powder |
| CN110255617A (en) * | 2019-06-28 | 2019-09-20 | 东莞深圳清华大学研究院创新中心 | A kind of preparation method of vanadium dioxide nano powder |
| CN110627122A (en) * | 2019-10-24 | 2019-12-31 | 成都先进金属材料产业技术研究院有限公司 | Preparation of VO by solid phase method2Method for phase change materials |
Non-Patent Citations (4)
| Title |
|---|
| A. EL HAIMEUR ET AL.: ""Optical, Magnetic, and Electronic Properties of Nanostructured VO2 Thin Films Grown by Spray Pyrolysis: DFT First Principle Study"", 《J SUPERCOND NOV MAGN》 * |
| 刘强 等: ""超声雾化反应法制备CeO2纳米粉体"", 《中国稀土学报》 * |
| 毛红艳 主编: "《化学实验员简明手册 实验室基础篇》", 30 June 2007, 中国纺织出版社 * |
| 邵美苓等: ""雾滴微反应器法制备纳米氧化铝粉体"", 《机械工程材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116002754A (en) * | 2022-12-13 | 2023-04-25 | 大连融科储能集团股份有限公司 | High-purity small-grain vanadium oxide and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112209440A (en) | Process for preparing M-phase vanadium dioxide nano powder | |
| CN101234750B (en) | Method of preparing superfine micro-particle and nano granule | |
| CN109019656B (en) | Production method of nanometer rare earth oxide powder | |
| CN112174207B (en) | Method for directly preparing M-phase vanadium dioxide nano powder by ultrasonic spray pyrolysis | |
| CN109205655B (en) | Preparation method of nano gadolinium oxide with particle size of 80-100nm | |
| CN102786085B (en) | Method for preparing rutile type titanium dioxide nanorod microsphere | |
| KR20080080350A (en) | Method for producing metal oxide nanoparticles with controlled properties, and nanoparticles and preparations prepared by the method | |
| CN102515268B (en) | Preparation method of high-dispersion titanium dioxide nanopowder | |
| CN110615476A (en) | M-phase VO prepared by using failed vanadium battery positive electrolyte2Method (2) | |
| JP5233007B2 (en) | Paint for transparent conductive material and method for producing transparent conductive film | |
| CN112209443A (en) | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization microwave method | |
| CN100546915C (en) | A kind of preparation method of anatase titanium dioxide nanopowder | |
| CN112266019A (en) | Method for preparing M-phase vanadium dioxide by single ultrasonic atomization homogeneous precipitation method | |
| CN112158883A (en) | Process for preparing vanadium dioxide nano powder | |
| CN112209442B (en) | Method for preparing M-phase vanadium dioxide nano powder by salt-assisted ultrasonic pyrolysis method | |
| CN105970323B (en) | A kind of antistatic powder and preparation method thereof | |
| CN108767232A (en) | A kind of method for coating of anode material for lithium-ion batteries | |
| CN101734720B (en) | Preparation method of vanadium dioxide ultrafine powder | |
| CN109529951B (en) | Synthesis method of small-particle-size stably-dispersed nano titanium dioxide | |
| CN107010939A (en) | A kind of preparation method of high densification Al-Doped ZnO target | |
| CN101239738A (en) | A kind of preparation method of titanium dioxide nanotube | |
| CN113353971B (en) | Preparation method of spherical nanoscale high-dispersion ITO powder | |
| CN116986625A (en) | Preparation method of in-situ precipitation self-dispersion indium oxide powder | |
| CN115676884A (en) | Method for preparing bismuth vanadate nano powder based on ultrasonic atomization microwave and powder | |
| CN114014362A (en) | M-phase vanadium dioxide powder based on freeze drying and carbothermic reduction and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210112 |