CN108726572B - Preparation method of doped vanadium dioxide nano powder - Google Patents
Preparation method of doped vanadium dioxide nano powder Download PDFInfo
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- CN108726572B CN108726572B CN201810554990.1A CN201810554990A CN108726572B CN 108726572 B CN108726572 B CN 108726572B CN 201810554990 A CN201810554990 A CN 201810554990A CN 108726572 B CN108726572 B CN 108726572B
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Abstract
A preparation method of doped vanadium dioxide nano powder comprises the following steps: according to product V1‑xMxO2(wherein M is one or two of doping elements W or Mo, x is more than or equal to 0 and less than or equal to 0.25) preparation amount and molar ratio of the doping elements and vanadium in the chemical composition formula, weighing W/Mo source reactant and ammonium metavanadate with corresponding mass, weighing solid organic acid and ammonium salt thereof according to 0.5-6 times of the mole number of the metal elements in the product, adding the solid organic acid and the ammonium salt thereof into a ball milling tank of a ball mill for ball milling for 0.5-5 hours, drying the ball milling product in the air at 60-120 ℃ for 0.5-8 hours, calcining the ball milling product in a specific gas atmosphere at 200-800 ℃ for 0.5-6 hours, and cooling to room temperature to obtain the final product. The powder prepared by the method has uniform particles, pure phases, simple equipment, easily obtained raw materials, high yield, short time, low cost, easy mass preparation and good industrial application prospect.
Description
Technical Field
The invention belongs to the field of preparation of nano powder, and relates to a method for preparing monoclinic phase doped vanadium dioxide nano powder in a green, efficient and rapid manner.
Technical Field
The research finds that the monoclinic phase vanadium dioxide is an inorganic thermotropic phase change material, when the temperature reaches 68 ℃, the vanadium dioxide can be converted into a high-temperature rutile phase from a low-temperature monoclinic phase, the metal-semiconductor conversion is shown, meanwhile, the physical properties of optics, magnetism, electricity and the like are changed, in addition, the phase change temperature can be greatly reduced by doping the vanadium dioxide, and the thermotropic phase change characteristic of the vanadium dioxide enables the vanadium dioxide to show wide application prospects in the aspects of intelligent glass, temperature control switches, stealth materials and the like.
At present, there are many methods for preparing monoclinic phase nano vanadium dioxide, such as hydrothermal method, sol-gel method, precipitation pyrolysis method, etc. The hyperhydric tablet is prepared from vanadic anhydride and oxalic acid dihydratePutting the mixture into a reaction kettle, and preserving the heat for 7 days at the temperature of 240 ℃ to obtain monoclinic phase vanadium dioxide (A)J. Phys. Chem. C 2008, 112, 18810–18814). Although pure-phase monodisperse nano vanadium dioxide can be obtained by the method, the preparation method is high in pressure, long in period, low in yield, large in energy consumption and difficult in industrial preparation. Bin, etc. adding vanadyl sulfate and ammonia water into proper amount of water, stirring to obtain brown precipitate, washing and dispersing the precipitate to prepare suspension, adding hydrogen peroxide and stirring to obtain vanadium dioxide gel, drying for 6 hr and heating at 550 deg.c for 1.5 hr to obtain vanadium dioxide nanopowder (A)J. Colloid Interf. Sci. 2016, 462, 42–47). Although the sol-gel method can obtain nanoparticles with smaller size, the method has the disadvantages of complex operation process, long time consumption and the like. Zhang Ximing, etc. uses vanadium pentoxide, hydrochloric acid, hydrazine hydrochloride and ammonium hydrogen carbonate as raw material, and makes them produce mutual reaction to form precipitate, then the obtained precipitate is cleaned, and is heated for a period of time at 550 deg.C under the condition of filling nitrogen gas so as to obtain the pure monoclinic phase nano vanadium dioxide (A), (B), (C), (J. Solid State Chem. 2001, 156, 274 -280). Although the pyrolysis method is easy to obtain a single precursor and obtain vanadium dioxide particles with smaller size, the selected vanadium pentoxide and hydrazine hydrochloride belong to highly toxic substances, and are not beneficial to environmental protection and industrial production. In a word, the current preparation of doped nano vanadium dioxide has technical bottlenecks of long period, low yield, high energy consumption, high raw material toxicity, large wastewater amount and the like, and a new synthesis method with high yield, rapidness, high efficiency, simple process, environmental friendliness and the like is urgently needed to be found.
Disclosure of Invention
The invention aims to overcome the defects of the prior synthesis technology and provides a novel method for preparing monoclinic phase doped vanadium dioxide nano powder.
The invention is realized by the following technical scheme.
The preparation method of the doped vanadium dioxide nano powder comprises the following steps.
(1) According to product V1-xMxO2The preparation amount and the molar ratio of the doping elements to vanadium in the chemical composition formula are determined, the doping element source reactant and ammonium metavanadate with corresponding mass are weighed, the solid organic acid and the ammonium salt thereof are weighed according to 0.5-6 times of the molar number of the metal elements in the product, and the solid organic acid and the ammonium salt thereof are added into a ball milling tank of a ball mill for ball milling for 0.5-5 hours.
(2) And (2) drying the ball-milled product obtained in the step (1) in air at 60-120 ℃ for 0.5-8 hours.
(3) And (3) taking out the solid product obtained in the step (2), calcining for 0.5-6 hours at 200-800 ℃ in a flowing atmosphere of specific gas, and cooling to room temperature to obtain a final product.
M in the step (1) is one or two of doping elements W or Mo, and x is more than or equal to 0 and less than or equal to 0.25.
The doping element source reactant in the step (1) is one or more of ammonium paratungstate, ammonium metatungstate, tungstic acid, ammonium molybdate or molybdic acid, and the solid organic acid and the ammonium salt thereof are one or more of citric acid, tartaric acid, oxalic acid, ammonium citrate, ammonium tartrate or ammonium oxalate.
And (3) the specific gas in the step (3) is nitrogen, argon or a mixed gas of nitrogen, argon and air or oxygen.
The invention is mainly characterized in that: (1) the monoclinic phase vanadium dioxide powder tungsten-doped vanadium dioxide nano powder is obtained by controlling a precursor prepared by thermal decomposition mechanochemical reaction in one step, and the product has uniform size and pure phase; (2) the method has the characteristics of simple equipment, easily obtained raw materials, high yield, short time, low cost, easiness in mass preparation and environmental friendliness, and has a good industrial application prospect.
Drawings
FIG. 1 is the X-ray diffraction pattern of the sample of example 1 and VO of JCDPS No. 43-10512The two phases are in monoclinic phase.
FIG. 2 is a scanning electron micrograph of the sample in example 1, and the product is a highly dispersed spherical particle of 50-70 nm as shown in the figure.
FIG. 3 is the X-ray diffraction pattern of the sample of example 2 and VO of JCDPS No. 43-10512The two phases are in monoclinic phase.
FIG. 4 is a scanning electron micrograph of the sample of example 2, and the product is a dispersed spherical particle of 60-70 nm as shown in the figure.
Detailed Description
The invention will be further illustrated by the following examples.
Example 1.
Respectively weighing 5.849g of ammonium metavanadate and 8.303 g of oxalic acid dihydrate, adding the weighed materials into a ball milling tank of a planetary ball mill, carrying out ball milling for 1 hour, taking out the materials, putting the materials into an oven, drying the materials for 2 hours at 100 ℃ in the air, then putting the materials into a tubular furnace with flowing nitrogen atmosphere, calcining the materials for 2 hours at 650 ℃, and cooling the materials to room temperature to obtain the vanadium dioxide nano powder.
Example 2.
Respectively weighing 5.849g, ammonium metavanadate, 0.2309g of ammonium paratungstate and 18.909g of oxalic acid dihydrate, adding the weighed materials into a ball milling tank of a planetary ball mill, ball-milling for 2 hours, taking out, drying the materials in an oven at 120 ℃ in the air for 2 hours, then calcining the materials in a tube furnace with flowing nitrogen atmosphere at 600 ℃ for 2 hours, and cooling the materials to room temperature to obtain W0.02V0.98O2And (4) nano powder.
Claims (1)
1. A preparation method of doped vanadium dioxide nano powder is characterized by comprising the following steps: respectively weighing 5.849g of ammonium metavanadate, 0.2309g of ammonium paratungstate and 18.909g of oxalic acid dihydrate, adding the materials into a ball milling tank of a planetary ball mill, ball-milling for 2 hours, taking out, drying the materials in an oven at 120 ℃ in air for 2 hours, then calcining the materials in a tube furnace with flowing nitrogen atmosphere at 600 ℃ for 2 hours, and cooling the materials to room temperature to obtain W0.02V0.98O2And (4) nano powder.
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| CN110923814A (en) * | 2019-11-25 | 2020-03-27 | 北京理工大学重庆创新中心 | Preparation method of nano vanadium dioxide film |
| CN111186860A (en) * | 2020-01-06 | 2020-05-22 | 济南大学 | Preparation method for preparing monoclinic-phase vanadium dioxide nano powder from precursor obtained by thermal decomposition and ball milling |
| CN112456555B (en) * | 2020-12-22 | 2022-12-13 | 济南大学 | Solid phase preparation method of doped vanadium dioxide nano powder |
| CN114684854A (en) * | 2022-03-30 | 2022-07-01 | 东风汽车集团股份有限公司 | Preparation method of nano vanadium trioxide |
| 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 |
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| CN100384747C (en) * | 2005-12-16 | 2008-04-30 | 大连理工大学 | Method for preparing high purity vanadium dioxide particles |
| CN101481142B (en) * | 2009-02-18 | 2012-05-23 | 大连理工大学 | Method for preparing hypovanadic oxide doped powder material |
| CN103466706B (en) * | 2013-09-26 | 2018-01-02 | 新疆大学 | A kind of method that solid state reaction prepares stratiform vanadium pentoxide nanometer material |
| RU2602896C1 (en) * | 2015-07-28 | 2016-11-20 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | Method of producing vanadium dioxide nanoparticles |
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Non-Patent Citations (2)
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| Synthesis of Thermochromic W-Doped VO2(M/R) Nanopowders by a Simple Solution-Based Process;Lihua Chen等;《Journal of Nanomaterials》;20121231;第1-8页 * |
| 锂离子电池正极材料V2O5的固相化学合成及改性研究;荣亚凌;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180115;第11-27页 * |
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