CN114890472B - Ellipsoidal hierarchical structure M-phase vanadium dioxide powder and preparation method thereof - Google Patents
Ellipsoidal hierarchical structure M-phase vanadium dioxide powder and preparation method thereof Download PDFInfo
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 102
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000843 powder Substances 0.000 title claims abstract description 78
- 230000027311 M phase Effects 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 8
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical group [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 241000533950 Leucojum Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 238000000151 deposition Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention discloses an M-phase vanadium dioxide powder with an ellipsoidal hierarchical structure and a preparation method thereof. The three-dimensional size of the ellipsoidal M-phase vanadium dioxide is distributed at 0.5-2 mu M, the two-dimensional size of the M-phase vanadium dioxide nanosheets is distributed at 20-250 nm, the ellipsoidal structure consists of a shell and a core, wherein the shell is formed by arranging the M-phase vanadium dioxide nanosheets in a direction parallel to the long axis of the ellipsoid, and the core nanosheets are vertically arranged with the shell nanosheets. The two ends of the shell are open. The hydrothermal reaction raw material is simple, the operation is simple and convenient, and the production safety is high. The subsequent annealing treatment temperature is low. Therefore, the production cost is low, and the method is suitable for industrialized mass production; the powder has higher crystallinity and specific morphology, and can be widely applied to the fields of intelligent energy-saving films, infrared detectors, photoelectric switch materials and the like.
Description
Technical Field
The invention relates to an ellipsoidal hierarchical structure M-phase vanadium dioxide powder and a preparation method thereof.
Background
Vanadium dioxide (VO) 2 ) It is considered as a very promising thermochromic material because it undergoes a reversible phase change from a high temperature metallic phase (R phase) to a low temperature semiconductor phase (M phase) at around 68 ℃ and its crystal structure changes from a tetragonal rutile structure to a monoclinic structure, with the change in crystal structure, the electrical and optical properties of vanadium dioxide are mutated. The special properties of the phase change material enable the M-phase vanadium dioxide to show considerable application prospect in the fields of intelligent energy-saving films, thermistor switches, infrared detectors, photoelectric switch materials and the like. But in its commercial application processIn the preparation process, the oxidation-reduction environment is strictly controlled to prevent the valence change of the vanadium element. Furthermore, even with vanadium ions of +4 valence, there are a large number of allotrope structures, as is known at present A, B, C, D, M (M 1 、M 2 、M 3 ) Structures such as R, T, and the formation energy difference between allotropes is small.
In order to obtain M, R phase vanadium dioxide, a variety of methods have been adopted by the scientific technicians, including sol-gel method, magnetron sputtering method, thermal decomposition method, chemical vapor deposition method, pulse laser deposition method, hydrothermal method, etc. Aiming at the application of vanadium dioxide in the aspect of intelligent energy-saving films, a composite film based on vanadium dioxide powder is considered to be the most effective method for improving the thermochromic performance of the vanadium dioxide intelligent energy-saving film. The prior method for preparing vanadium dioxide powder is mainly a hydrothermal method, chinese patent No. 101391814A discloses a method for preparing rutile phase vanadium dioxide powder by a one-step hydrothermal method, which adopts a doping method to control the morphology of powder, and synthesizes particles, nano rods and snowflake powder, but the hydrothermal reaction condition is harsh, the reaction is required to be carried out for 1-7 days at the high temperature of 240 ℃, the high pressure generated by the high-temperature hydrothermal reaction increases the reaction risk, and in addition, the quantity of the doping agent is required to be strictly controlled to control the morphology of the powder, so that the process is complex. Most of the prior reports are that the B-phase vanadium dioxide powder is synthesized first and then the M-phase vanadium dioxide powder is obtained through high-temperature treatment at 400-800 ℃, but the original structure of the powder is damaged by the subsequent high temperature. Thereafter, chinese patent No. 104045345A discloses a D-phase vanadium dioxide nano star powder and a preparation method thereof, wherein the D-phase vanadium dioxide powder is subjected to subsequent low-temperature annealing treatment to obtain M-phase vanadium dioxide powder, the morphology of the powder can be effectively maintained unchanged by the low-temperature annealing treatment, but the preparation of a hydrothermal reaction solution needs to strictly control pH, and the reaction time needs to be 3 days at 180 ℃, so that the synthesis process is complicated.
Disclosure of Invention
Based on the defects in the prior art, the technical problem solved by the invention is to provide the M-phase vanadium dioxide powder with an ellipsoidal hierarchical structure and the preparation method thereof, wherein the powder is uniform in shape and assembled into the ellipsoidal structure by the nano-sheets. Also provides a method for preparing the powder.
In order to solve the technical problems, the invention provides a preparation method of M-phase vanadium dioxide powder with an ellipsoidal hierarchical structure, which comprises the following steps:
1) Adding vanadium pentoxide and oxalic acid dihydrate into deionized water to perform oxidation-reduction reaction to obtain vanadyl oxalate aqueous solution, adding polyvinylpyrrolidone (PVP) into the vanadyl oxalate aqueous solution, fully stirring, and performing ultrasonic treatment until the solution is uniform;
2) Carrying out hydrothermal reaction on the solution obtained in the step 1), and carrying out centrifugal separation, full washing and drying on the reacted solution to obtain D-phase vanadium dioxide powder with an ellipsoidal hierarchical structure;
3) And annealing the D-phase vanadium dioxide powder to obtain the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure.
As the optimization of the technical scheme, the preparation method of the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure further comprises the following technical characteristics:
as an improvement of the technical scheme, the three-dimensional size of the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure is distributed at 0.5-2 mu M, the two-dimensional size of the M-phase vanadium dioxide nano-sheet is distributed at 20-250 nm, the ellipsoidal structure consists of a shell and a core, wherein the shell is formed by arranging the M-phase vanadium dioxide nano-sheet in parallel with the direction of the long axis of the ellipsoid, and the core nano-sheet is vertically arranged with the shell nano-sheet; the two ends of the shell are open.
As an improvement of the above technical solution, in the step 1), the ratio of the vanadium pentoxide to the oxalic acid dihydrate is 1:1 to 3, the concentration of the vanadyl oxalate aqueous solution is 0.05 to 0.1mol/L.
As an improvement of the above technical scheme, in the step 1), the mass of the PVP is 2-16% of the mass of the vanadyl oxalate aqueous solution.
As an improvement of the technical scheme, in the step 2), the hydrothermal reaction temperature is 160-200 ℃ and the reaction time is 10-24 h.
As an improvement of the technical scheme, in the step 2), the centrifugal separation rotating speed is 6000-11000 r/min, and the time is 5-15 min; the solvent is ethanol, water, acetone or a combination thereof during washing, and the washing times are 5-15 times until PVP is sufficiently washed; the drying temperature is 50-80 ℃ and the drying time is 12-48 h.
As an improvement of the technical scheme, in the step 3), the annealing temperature is 250-400 ℃, the time is 30-120 min, and the vacuum degree in a hearth is 50-1000 Pa during annealing.
The invention also provides an ellipsoidal hierarchical structure M-phase vanadium dioxide powder, wherein the ellipsoidal hierarchical structure M-phase vanadium dioxide powder is an ellipsoidal M-phase vanadium dioxide structure assembled by M-phase vanadium dioxide nano-sheets according to a specific orientation, the three-dimensional size of the ellipsoidal M-phase vanadium dioxide nano-sheets is distributed at 0.5-2 mu M, the two-dimensional size of the M-phase vanadium dioxide nano-sheets is distributed at 20-250 nm, the ellipsoidal structure consists of a shell and an inner core, the shell is formed by arranging the M-phase vanadium dioxide nano-sheets in a direction parallel to the long axis of the ellipsoid, the inner core nano-sheets are vertically arranged with the shell nano-sheets, and two ends of the shell are opened.
As the optimization of the technical scheme, the ellipsoidal hierarchical structure M-phase vanadium dioxide powder provided by the invention further comprises part or all of the following technical characteristics:
as an improvement of the technical scheme, the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure is prepared by any one of the methods.
As an improvement of the technical scheme, the ellipsoidal hierarchical structure D-phase vanadium dioxide powder also has crystal lattice oxygen vacancies in the crystal structure, and M-phase vanadium dioxide powder with different concentrations of crystal lattice oxygen vacancies can be obtained by annealing under different vacuum degrees.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention synthesizes ellipsoidal D-phase vanadium dioxide powder with a hierarchical structure by adopting a hydrothermal method, wherein the ellipsoidal microstructure is assembled by D-phase vanadium dioxide nanosheets, and then ellipsoidal M-phase vanadium dioxide powder with a hierarchical structure is prepared by lower-temperature heat treatment.
PVP is used as a surfactant, ellipsoidal powder assembled by the D-phase vanadium dioxide nano-sheets is synthesized under a milder hydrothermal condition, the subsequent low-temperature heat treatment ensures that the morphology is not changed, and the obtained M-phase vanadium dioxide nano-sheets have good crystallinity.
The preparation method is simple, the condition is mild, and the raw materials are simple. The method takes vanadium pentoxide, oxalic acid dihydrate (reducer) and PVP (surfactant) as raw materials, and synthesizes the D-phase vanadium dioxide powder with an ellipsoidal hierarchical structure by a hydrothermal method at a lower temperature, and the synthesis condition of the D-phase powder is mild compared with the prior art.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and appreciated, as well as the other objects, features and advantages of the present invention, as described in detail below in connection with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is an XRD pattern of M-phase vanadium dioxide prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of M-phase vanadium dioxide prepared in example 2 of the present invention;
FIG. 3 is an XRD pattern of M-phase vanadium dioxide prepared in example 3 of the present invention;
FIG. 4 is an SEM image of M-phase vanadium dioxide prepared in example 3 of the invention;
FIG. 5 is a DSC of M-phase vanadium dioxide prepared in example 3 of the present invention.
Detailed Description
The following detailed description of the invention, which is a part of this specification, illustrates the principles of the invention by way of example, and other aspects, features, and advantages of the invention will become apparent from the detailed description.
Example 1
1) Weighing 0.455g of vanadium pentoxide and 0.9455g of oxalic acid dihydrate, adding into 80ml of deionized water to obtain a mixed solution, reacting the mixed solution at 80 ℃ for 30min to obtain an vanadyl oxalate aqueous solution, adding 4.224g of PVP into the vanadyl oxalate aqueous solution, fully stirring for 1h, and carrying out ultrasonic treatment for 1h until PVP is completely dissolved and the solution is uniform;
2) The solution is placed in a 100ml reaction kettle, the reaction kettle is placed in an oven for reaction for 10 hours at 180 ℃, and the solution after the reaction is centrifugally separated by 10000r/min for 10 min. And then centrifugally washing the powder 10000r/min for 5min, washing with water for 3 times and washing with ethanol for 4 times. And drying the washed powder in a drying oven at 80 ℃ for 12 hours to obtain the D-phase vanadium dioxide powder with the ellipsoidal hierarchical structure.
3) Placing the D-phase vanadium dioxide powder into a tube furnace for annealing, vacuumizing the tube furnace to 500Pa, and annealing at 250 ℃ for 1h to obtain M-phase vanadium dioxide powder with an ellipsoidal hierarchical structure;
example 2
1) Weighing 0.455g of vanadium pentoxide and 0.9455g of oxalic acid dihydrate, adding into 80ml of deionized water to obtain a mixed solution, reacting the mixed solution at 80 ℃ for 30min to obtain an vanadyl oxalate aqueous solution, adding 4.8g of PVP into the vanadyl oxalate aqueous solution, fully stirring for 1h, and carrying out ultrasonic treatment for 1h until PVP is completely dissolved and the solution is uniform;
2) The solution is placed in a 100ml reaction kettle, the reaction kettle is placed in an oven for reaction at 180 ℃ for 13h, and the solution after the reaction is centrifugally separated by 10000r/min for 10 min. And then centrifugally washing the powder 10000r/min for 5min, washing with water for 3 times and washing with ethanol for 4 times. And drying the washed powder in a drying oven at 80 ℃ for 12 hours to obtain the D-phase vanadium dioxide powder with the ellipsoidal hierarchical structure.
3) Placing the D-phase vanadium dioxide powder into a tube furnace for annealing, vacuumizing the tube furnace to 500Pa, and annealing at 350 ℃ for 1h to obtain M-phase vanadium dioxide powder with an ellipsoidal hierarchical structure;
example 3
1) Weighing 0.455g of vanadium pentoxide and 0.9455g of oxalic acid dihydrate, adding into 80ml of deionized water to obtain a mixed solution, reacting the mixed solution at 80 ℃ for 30min to obtain an vanadyl oxalate aqueous solution, adding 4.8g of PVP into the vanadyl oxalate aqueous solution, fully stirring for 1h, and carrying out ultrasonic treatment for 1h until PVP is completely dissolved and the solution is uniform;
2) The solution is placed in a 100ml reaction kettle, the reaction kettle is placed in an oven for reaction at 180 ℃ for 24 hours, and the solution after the reaction is centrifugally separated by 10000r/min for 10 min. And then centrifugally washing the powder 10000r/min for 5min, washing with water for 3 times and washing with ethanol for 4 times. And drying the washed powder in a drying oven at 80 ℃ for 12 hours to obtain the D-phase vanadium dioxide powder with the ellipsoidal hierarchical structure.
3) Placing the D-phase vanadium dioxide powder into a tube furnace for annealing, vacuumizing the tube furnace to 500Pa, and annealing at 400 ℃ for 1h to obtain M-phase vanadium dioxide powder with an ellipsoidal hierarchical structure;
to fully understand the structural composition and performance of the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure prepared in the examples.
Performance test of the powder obtained in the examples
X-ray diffraction analysis
An Empyrean type X-ray diffraction analyzer of the Panac company of Netherlands, a copper target Cu-K alpha is used as a radiation source (lambda= 0.154178 nm), rated output power is 4KW, the scanning range is 10-80 degrees, and the scanning speed is 5 degrees per minute.
2. Field emission scanning electron microscope
The surface morphology of the films was tested by Zeiss Ultra Plus field emission scanning electron microscopy, zeiss, germany.
3. Differential scanning calorimetric analysis
A TA-DSC2500 type differential scanning calorimeter of the American TA company is used for testing the phase transition temperature of the M-phase vanadium dioxide powder under the nitrogen atmosphere.
FIG. 1 is an XRD pattern of the M-phase vanadium dioxide obtained in example 1, and the diffraction peak corresponds to a standard M-phase vanadium dioxide card, which shows that the D-phase vanadium dioxide obtained in the application can be completely converted into M-phase vanadium dioxide powder by annealing at a lower temperature (250 ℃); FIG. 2 is an XRD pattern of the M-phase vanadium dioxide obtained in example 2, which also shows that the XRD diffraction peak intensity of the obtained M-phase vanadium dioxide powder increases when the annealing temperature of the D-phase vanadium dioxide powder increases, compared with example 1, indicating that the powder crystallinity also increases; FIG. 3 is an XRD pattern of the M-phase vanadium dioxide obtained in example 3, wherein the crystallinity of the M-phase vanadium dioxide powder is further improved compared with that of examples 1 and 2, and the M-phase vanadium dioxide powder is subjected to mild temperature annealing at 400 ℃ to obtain M-phase vanadium dioxide with very good crystallinity; fig. 4 is an SEM morphology graph of the M-phase vanadium dioxide obtained in example 3, and it can be seen from the graph that the obtained M-phase vanadium dioxide powder has a uniform particle distribution and a very obvious hierarchical structure, i.e. the M-phase vanadium dioxide nanosheets are assembled into ellipsoidal M-phase vanadium dioxide particles according to a specific direction; FIG. 5 is a DSC graph of M-phase vanadium dioxide obtained in example 3, showing that the average phase transition temperature of vanadium dioxide is 56.7℃and is reduced by 11.3℃compared with the phase transition temperature of 68℃of bulk vanadium dioxide. Moreover, the measured phase transition enthalpy is still as high as 46.7J/g and is very close to that of massive vanadium dioxide, which shows that the defect content in the obtained M-phase vanadium dioxide is very low and the crystallinity is good.
The present invention can be realized by the respective raw materials listed in the present invention, and the upper and lower limits and interval values of the respective raw materials, and the upper and lower limits and interval values of the process parameters (such as temperature, time, etc.), and examples are not listed here.
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (8)
1. The preparation method of the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure is characterized by comprising the following steps of:
1) Adding vanadium pentoxide and oxalic acid dihydrate into deionized water to perform oxidation-reduction reaction to obtain vanadyl oxalate aqueous solution, adding polyvinylpyrrolidone (PVP) into the vanadyl oxalate aqueous solution, fully stirring, and performing ultrasonic treatment until the solution is uniform;
2) Carrying out hydrothermal reaction on the solution obtained in the step 1), and carrying out centrifugal separation, full washing and drying on the reacted solution to obtain D-phase vanadium dioxide powder with an ellipsoidal hierarchical structure;
3) Annealing the D-phase vanadium dioxide powder to obtain M-phase vanadium dioxide powder with an ellipsoidal hierarchical structure; the ellipsoidal hierarchical structure M-phase vanadium dioxide powder is an ellipsoidal M-phase vanadium dioxide structure assembled by M-phase vanadium dioxide nano-sheets according to a specific orientation, the three-dimensional size of the ellipsoidal M-phase vanadium dioxide nano-sheets is distributed at 0.5-2 mu M, the two-dimensional size of the M-phase vanadium dioxide nano-sheets is distributed at 20-250 nm, the ellipsoidal structure consists of a shell and a core, wherein the shell is formed by arranging the M-phase vanadium dioxide nano-sheets in parallel to the direction of the long axis of the ellipsoid, the core nano-sheets are vertically arranged with the shell nano-sheets, and two ends of the shell are opened.
2. The method for preparing the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure according to claim 1, which is characterized by comprising the following steps: in the step 1), the ratio of the vanadium pentoxide to the oxalic acid dihydrate is 1: 1-3, wherein the concentration of the vanadyl oxalate aqueous solution is 0.05-0.1 mol/L.
3. The method for preparing the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure according to claim 1, which is characterized by comprising the following steps: in the step 1), the mass of PVP is 2-16% of the mass of vanadyl oxalate aqueous solution.
4. The method for preparing the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure according to claim 1, which is characterized by comprising the following steps: in the step 2), the hydrothermal reaction temperature is 160-200 ℃ and the reaction time is 10-24 h.
5. The method for preparing the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure according to claim 1, which is characterized by comprising the following steps: in the step 2), the centrifugal separation rotating speed is 6000-11000 r/min, and the time is 5-15 min; the solvent is ethanol, water, acetone or a combination thereof during washing, and the washing times are 5-15 times until PVP is sufficiently washed; the drying temperature is 50-80 ℃ and the drying time is 12-48 h.
6. The method for preparing the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure according to claim 1, which is characterized by comprising the following steps: in the step 3), the annealing temperature is 250-400 ℃, the time is 30-120 min, and the vacuum degree in a hearth is 50-1000 Pa during annealing.
7. An ellipsoidal hierarchical structure M-phase vanadium dioxide powder is characterized in that: the M-phase vanadium dioxide powder with the ellipsoidal hierarchical structure is prepared by the method of any one of claims 1-6.
8. The ellipsoidal hierarchical M-phase vanadium dioxide powder according to claim 7, wherein: the ellipsoidal hierarchical structure D-phase vanadium dioxide powder has crystal structure with crystal lattice oxygen vacancies, and M-phase vanadium dioxide powder with different concentration of crystal lattice oxygen vacancies can be obtained by annealing under different vacuum degrees.
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| CN113522320A (en) * | 2021-07-26 | 2021-10-22 | 广东工业大学 | Ellipsoidal bismuth oxyhalide photocatalyst and preparation method and application thereof |
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| Shuo Wang et al..Facile synthesis of VO2 (D) and its transformation to VO2(M) with enhanced thermochromic properties for smart windows.Ceramics International.2020,第第46卷卷(第第10期期),第2.1和4章节. * |
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