CN114920296A - Vanadium oxide composite powder and preparation method and application thereof - Google Patents
Vanadium oxide composite powder and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000000843 powder Substances 0.000 title claims abstract description 62
- 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 title claims abstract description 36
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011858 nanopowder Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 108010053481 Antifreeze Proteins Proteins 0.000 abstract description 14
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 abstract 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 31
- 239000012855 volatile organic compound Substances 0.000 description 23
- 230000007704 transition Effects 0.000 description 16
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 12
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000000411 transmission spectrum Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses vanadium oxide composite powder and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) adding water into vanadium pentoxide and oxalic acid dihydrate, stirring, and adjusting the pH value by using a dilute acid solution to obtain vanadyl oxalate solution; (2) dropwise adding a proper amount of alkali liquor into the vanadyl oxalate solution obtained in the step (1) to prepare slurry, and drying in vacuum to obtain a reaction precursor; (3) and (3) placing the precursor obtained in the step (2) in a tube furnace, vacuumizing, introducing protective gas, starting a set temperature rise program, and starting a solid-phase reaction to obtain the vanadium oxide composite powder. The invention realizes the effective regulation and control of the widths of the thermal hysteresis loop of the vanadium oxide powder and the energy-saving film through the controllable regulation and control of the components of the composite powder, and is beneficial to the application of an intelligent window.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic thermochromic oxide materials, and particularly relates to a preparation method of vanadium oxide composite powder.
Background
Thermochromic vanadium dioxide (VO) 2 ) Has unique metal-insulator phase transition characteristics and is a hot point for researching materials and condensed physical directions. VO (volatile organic compound) 2 The intrinsic phase transition temperature of (1) is 68 ℃, and the common transformation of structure and electrons occurs during the phase transition, namely VO is lower than the phase transition temperature 2 A monoclinic phase (M1 phase) in the semiconductor or insulating state; above the phase transition temperature, VO 2 Is a rutile phase (rutile, R phase) in a metallic state. Before and after phase transition, VO 2 Of (2) a lightThe chemical property (near infrared transmission state) and the electrical property (resistivity, etc.) can be obviously changed, and the characteristic makes VO 2 The method has good application prospect in the fields of photoelectric switches, infrared detection, intelligent windows, optical storage devices and the like.
VO 2 The phase transition characteristics of (1) are phase transition temperature, phase transition hysteresis line, changes of optical properties and electrical properties before and after phase transition, and the like, VO 2 The smart window applications of (a) require materials that meet basic performance requirements: the phase transition temperature is close to room temperature, the slow line width is narrow, and the optical performance comprises higher visible light transmittance and larger near infrared transmittance change value before and after phase transition. At present, researchers have proposed a number of methods to achieve phase transition temperature and optical property adjustment, such as element doping, stress and defect engineering, recombination technology, film system design, and the like. However, the study of the thermal hysteresis width adjustment is yet to be further explored. Therefore, the adjustable hysteresis line width is realized by preparing the vanadium oxide composite powder.
Disclosure of Invention
Aiming at the existing problems, the invention provides a preparation method of vanadium oxide composite powder, which realizes adjustable hysteresis line width by adjusting the components of the composite powder. The method mainly comprises the following steps:
step 1, adding vanadium pentoxide and oxalic acid dihydrate into deionized water according to the mass ratio (1-2):1, fully stirring (stirring for 5-6 h), dropwise adding a dilute acid solution, adjusting the pH value to 1.5-2.5, continuously stirring for 1-5h in a water bath at 60-80 ℃, reacting for 5-8h at the temperature of 100-200 ℃, and performing suction filtration to obtain a blue clear solution;
step 2, placing a proper amount of clear blue solution in a beaker, dropwise adding alkali liquor, adjusting the pH value to 7-10, stirring for 20-60min, centrifuging the obtained suspension, adding deionized water into the obtained slurry, sequentially performing ultrasonic treatment, stirring and centrifugation, and drying the obtained slurry to obtain a reaction precursor;
step 3, taking a proper amount of precursor, placing the precursor into a quartz boat, placing the quartz boat in a tube furnace, vacuumizing, introducing protective gas, keeping the temperature at the constant temperature of 300-800 ℃ for 30min-10h, and naturally cooling to room temperature to obtain VO 2 -V 6 O 13 And (3) composite powder.
In the invention, in the step 1, the mass ratio of the vanadium pentoxide to the oxalic acid dihydrate is 1:1, 1.5:1, 2:1 and the like according to the formula (1-2: 1).
The acid solution used in the step 1 is sulfuric acid or hydrochloric acid, and the concentration is 0.5 mol/L-2 mol/L.
The alkali liquor used in the step 2 is ammonia water, sodium hydroxide or potassium hydroxide solution, and the concentration is 0.5-2 mol/L.
The drying mode in the step 2 is vacuum drying, the temperature is 50-120 ℃, and the time is 8-48 h.
Centrifugation as indicated in step 2 means centrifugation at 8000 rpm.
The ultrasonic treatment in the step 2 is carried out at 600W.
The stirring in step 1 and step 2 is carried out at 800 rpm.
In the step 3, the absolute vacuum degree of the vacuumizing is less than or equal to 10Pa, the protective gas is any one of nitrogen, argon and helium, and the flow rate is 10-50 sccm.
During the solid phase reaction in the step 3, the temperature is raised to 300-800 ℃ at a speed of 10-20 ℃/min.
The invention develops a method for preparing composite powder to realize adjustable thermal hysteresis width. Regulating VO in the composite powder by regulating the temperature and time of the solid phase reaction 2 And V 6 O 13 Thereby realizing the adjustment of the thermal hysteresis width. The vanadium oxide composite powder maintains the phase change characteristic of vanadium dioxide powder, can be used as a key material for preparing energy-saving coatings and paints, organic-inorganic nano composite films and the like, improves the temperature control response of the energy-saving films, and is applied to the field of building energy conservation.
Drawings
FIG. 1 is an X-ray diffraction chart of the vanadium oxide composite powder obtained in example 1;
FIG. 2 is an X-ray diffraction chart of the vanadium oxide composite powder obtained in example 2;
FIG. 3 is an X-ray diffraction chart of the vanadium oxide composite powder obtained in example 3;
FIG. 4 is an X-ray diffraction chart of the vanadium dioxide powder prepared in the comparative example;
FIG. 5 is a scanning electron microscope image of the vanadium oxide composite powder prepared in example 1;
FIG. 6 is a DSC curve of the vanadium oxide composite powder obtained in example 1;
FIG. 7 is a DSC curve of the vanadium dioxide powder prepared in the comparative example;
FIG. 8 is a transmission spectrum of a film of the vanadium oxide composite powder obtained in example 1;
FIG. 9 is a thermal hysteresis curve of the vanadium oxide composite film obtained in example 1;
FIG. 10 is a transmission spectrum of a vanadium dioxide composite film produced by a comparative example;
FIG. 11 is a thermal hysteresis loop of a vanadium dioxide composite film prepared by a comparative example.
Detailed Description
In order to explain the present invention in more detail, the following detailed description is given with reference to specific examples.
Example 1
A preparation method of vanadium oxide composite powder comprises the following steps:
step 1, adding 1g of vanadium pentoxide and 1g of oxalic acid dihydrate into 80mL of deionized water, stirring at the rotating speed of 800rpm for 6h, dropwise adding 1mol/L of dilute sulfuric acid solution, adjusting the pH value to 2, continuously stirring in a water bath at 60 ℃ (the rotating speed is 800 rpm) for 1h, reacting at the temperature of 150 ℃ for 6h, and performing suction filtration to obtain a blue clear solution;
step 2, taking 40mL of clear blue solution, placing the clear blue solution in a beaker, slowly adding 1mol/L ammonia water solution dropwise, adjusting the pH value to 8, stirring at the rotation speed of 800rpm for 20min, centrifuging the obtained suspension (the rotation speed is 8000rpm and 3 min), adding 40mL of deionized water into the obtained slurry, sequentially performing ultrasonic treatment (the ultrasonic power is 600W and 10min), stirring (the rotation speed is 800rpm and 10min) and centrifuging (the rotation speed is 8000rpm and 3 min), and drying the obtained slurry at 80 ℃ for 12h to obtain a reaction precursor;
step 3, taking 0.1g of precursor, putting the precursor into a quartz boat, putting the quartz boat into a tube furnace, vacuumizing until the absolute vacuum degree is less than or equal to 10Pa, introducing 30sccm of nitrogen, heating to 550 ℃ at the speed of 20 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain 0.07gVO 2 -V 6 O 13 And (3) composite powder.
Preparing a composite nano powder film: adding 20mg of vanadium oxide composite powder and polyvinylpyrrolidone (K-30) into 1mL of ethanol according to the mass ratio of 1:2.5, stirring at the rotating speed of 600rpm for 5 hours, and performing ultrasonic treatment (the ultrasonic power is 600W) for 24 hours to obtain slurry. 60 mu L of slurry is taken and evenly coated on 15mm multiplied by 15mm quartz glass, the quartz glass is rotated for 3s at the low speed of 400rpm, then the quartz glass is spin-coated for 30s at the speed of 3000rpm and dried for 20min in an oven at the temperature of 80 ℃, and a composite nano powder film with the thickness of 1 mu m is obtained.
FIG. 1 is an XRD pattern of the composite powder obtained in example 1, VO 2 And V 6 O 13 Mixed phase of (3), estimating VO from the map 2 Is 71.4 wt.%. FIG. 5 is a scanning electron microscope picture of the vanadium oxide composite powder prepared in example 1, wherein the composite powder has a nanosheet shape. FIG. 6 is a DSC curve of the vanadium oxide composite powder obtained in example 1, and it was found that the phase transition temperatures in the heating zone and the cooling zone were 67.5 ℃ and 60.4 ℃, respectively, and the thermal hysteresis width of the powder was 7.1 ℃. Fig. 8 is a transmission spectrum of the vanadium oxide composite powder film prepared in example 1, which shows that the composite powder has thermochromic properties (the temperature-changing transmittance is significantly changed), that is, the infrared transmittance is higher than the phase-changing temperature, and the energy-saving film transmits infrared light, and when the temperature is lower than the phase-changing temperature, the infrared transmittance is low, and the energy-saving film can block the infrared light from passing through. Fig. 9 is a thermal hysteresis curve (transmittance change curve with temperature) of the vanadium oxide composite film prepared in example 1, which is measured at a wavelength of 1500nm, and when the vanadium oxide composite film is heated and cooled, the transmittance change curve is not coincident, a certain hysteresis exists, the vanadium oxide composite film shows a phase change characteristic of vanadium dioxide, and the thermal hysteresis width of the composite film is 12.6 ℃.
Example 2
A preparation method of vanadium oxide composite powder specifically comprises the following steps:
step 1, adding 1g of vanadium pentoxide and 1g of oxalic acid dihydrate into 80mL of deionized water, stirring at the rotating speed of 800rpm for 6h, dropwise adding 1mol/L of dilute sulfuric acid solution, adjusting the pH value to 2, continuously stirring in a water bath at 60 ℃ (the rotating speed is 800 rpm) for 1h, reacting at the temperature of 150 ℃ for 6h, and performing suction filtration to obtain a blue clear solution;
step 2, placing 40mL of clear blue solution in a beaker, slowly dropwise adding 1mol/L ammonia water solution, adjusting the pH value to 8, stirring at the rotating speed of 800rpm for 20min, centrifuging the obtained suspension (the rotating speed is 8000rpm and 3 min), adding 40mL of deionized water into the obtained slurry, sequentially performing ultrasonic treatment (the ultrasonic power is 600W and 10min), stirring (the rotating speed is 800rpm and 10min) and centrifuging (the rotating speed is 8000rpm and 3 min), and drying the obtained slurry at 80 ℃ for 12h to obtain a reaction precursor;
step 3, taking 0.1g of precursor, putting the precursor into a quartz boat, putting the quartz boat into a tube furnace, vacuumizing until the absolute vacuum degree is less than or equal to 10Pa, introducing 30sccm nitrogen, heating to 550 ℃ at a speed of 20 ℃/min, preserving heat for 3h, and naturally cooling to room temperature to obtain 0.08gVO 2 -V 6 O 13 And (3) composite powder.
Preparing a composite nano powder film: adding 20mg of vanadium oxide composite powder and polyvinylpyrrolidone (K-30) into 1mL of ethanol according to the mass ratio of 1:2.5, stirring at the rotating speed of 600rpm for 5h, and performing ultrasonic treatment (the ultrasonic power is 600W) for 24h to obtain slurry. 60 mu L of slurry is taken and evenly coated on 15mm multiplied by 15mm quartz glass, the quartz glass is rotated for 3s at the low speed of 400rpm, then the quartz glass is spin-coated for 30s at the speed of 3000rpm and dried for 20min in an oven at the temperature of 80 ℃, and a composite nano powder film with the thickness of 1 mu m is obtained.
FIG. 2 is an XRD pattern of the composite powder obtained in example 2, which is VO 2 And V 6 O 13 Mixed phase of (3), estimating VO from the map 2 Is 48.8 wt.%. DSC tests the phase change of the composite powder, and finds that the phase change temperatures of the heating section and the cooling section are 67.3 ℃ and 61.1 ℃ respectively, and the thermal hysteresis width of the powder is 6.2 ℃.
Example 3
A preparation method of vanadium oxide composite powder comprises the following steps:
step 1, adding 1g of vanadium pentoxide and 1g of oxalic acid dihydrate into 80mL of deionized water, stirring at the rotating speed of 800rpm for 6h, dropwise adding 1mol/L of dilute sulfuric acid solution, adjusting the pH value to 2, continuously stirring in a water bath at 60 ℃ (the rotating speed is 800 rpm) for 1h, reacting at the temperature of 150 ℃ for 6h, and performing suction filtration to obtain a blue clear solution;
step 2, placing 40mL of clear blue solution in a beaker, slowly dropwise adding 1mol/L ammonia water solution, adjusting the pH value to 8, stirring at the rotating speed of 800rpm for 20min, centrifuging the obtained suspension (the rotating speed is 8000rpm and 3 min), adding 40mL of deionized water into the obtained slurry, sequentially performing ultrasonic treatment (the ultrasonic power is 600W and 10min), stirring (the rotating speed is 800rpm and 10min) and centrifuging (the rotating speed is 8000rpm and 3 min), and drying the obtained slurry at 80 ℃ for 12h to obtain a reaction precursor;
step 3, taking 0.1g of precursor, putting the precursor into a quartz boat, putting the quartz boat into a tube furnace, vacuumizing until the absolute vacuum degree is less than or equal to 10Pa, introducing 30sccm of nitrogen, heating to 700 ℃ at the speed of 20 ℃/min, preserving heat for 3h, and naturally cooling to room temperature to obtain 0.08gVO 2 -V 6 O 13 And (3) composite powder.
Preparing a composite nano powder film: adding 20mg of vanadium oxide composite powder and polyvinylpyrrolidone (K-30) into 1mL of ethanol according to the mass ratio of 1:2.5, stirring at the rotating speed of 600rpm for 5 hours, and performing ultrasonic treatment (the ultrasonic power is 600W) for 24 hours to obtain slurry. 60 mu L of slurry is taken and evenly coated on 15mm multiplied by 15mm quartz glass, the quartz glass is rotated for 3s at the low speed of 400rpm, then the quartz glass is spin-coated for 30s at the speed of 3000rpm and dried for 20min in an oven at the temperature of 80 ℃, and a composite nano powder film with the thickness of 1 mu m is obtained.
FIG. 3 is an XRD pattern of the composite powder obtained in example 3, VO 2 And V 6 O 13 Mixed phase of (2), estimating VO from the map 2 Is 23.4 wt.%. DSC tests the phase change of the composite powder, and finds that the phase change temperatures of the heating section and the cooling section are 67.4 ℃ and 62.4 ℃ respectively, and the thermal hysteresis width of the powder is 5.0 ℃.
Comparative example
The preparation method of the vanadium dioxide powder specifically comprises the following steps:
step 1, adding 1g of vanadium pentoxide and 1g of oxalic acid dihydrate into 80mL of deionized water, stirring at the rotating speed of 800rpm for 6h, dropwise adding 1mol/L of dilute sulfuric acid solution, adjusting the pH value to 2, continuously stirring in a water bath at 60 ℃ (the rotating speed is 800 rpm) for 1h, reacting at the temperature of 150 ℃ for 8h, and performing suction filtration to obtain a blue clear solution;
step 2, taking 40mL of clear blue solution, placing the clear blue solution in a beaker, slowly adding 1mol/L ammonia water solution dropwise, adjusting the pH value to 8, stirring at the rotation speed of 800rpm for 20min, centrifuging the obtained suspension (the rotation speed is 8000rpm and 3 min), adding 40mL of deionized water into the obtained slurry, and sequentially performing ultrasonic treatment (the ultrasonic power is 600W and 10min) and stirring (the rotation speed is 800rpm and 10min) to obtain a reaction precursor solution;
and 3, transferring the reaction precursor solution into a 50mL hydrothermal kettle, heating to 260 ℃ at the speed of 5 ℃/min, and carrying out hydrothermal reaction for 24 hours. After the reaction is finished, taking the precipitate, washing, centrifuging (the rotating speed is 8000rpm, 3 min), repeating for 3 times, pouring out the supernatant, baking the obtained precipitate at the temperature of 60 ℃ for 12h to obtain VO 2 And (3) powder.
And step 4, taking 20mg of vanadium dioxide powder, adding the vanadium dioxide powder and polyvinylpyrrolidone (K-30) into 1mL of ethanol according to the mass ratio of 1:2.5, stirring for 5 hours at the rotating speed of 600rpm, and performing ultrasonic treatment (the ultrasonic power is 600W) for 24 hours to obtain slurry. 60 mu L of slurry is uniformly coated on 15mm multiplied by 15mm quartz glass, the quartz glass is rotated at the low speed of 400rpm for 3s, then the quartz glass is spin-coated at the speed of 3000rpm for 30s, and the composite nano powder film with the thickness of 1 mu m is obtained after drying in an oven for 20 min.
FIG. 4 shows VO in comparative example 2 XRD pattern of the powder is pure phase VO 2 . FIG. 7 shows VO 2 DSC curve of powder. The phase transition temperatures of the heating section and the cooling section are 67.5 ℃ and 41.3 ℃ respectively, and the thermal hysteresis width of the powder is 26.2 ℃. FIG. 10 shows the transmission spectrum of the vanadium oxide composite powder film prepared in the comparative example, VO obtained by hydrothermal reaction 2 The powder has a characteristic variable temperature spectrum, namely, the powder is higher than the phase change temperature, the infrared transmittance is higher, and the energy-saving film transmits infrared light; when the temperature is lower than the phase transition temperature, the infrared transmittance is low, and the material is based on VO 2 The energy-saving film can block the infrared light from passing through. Fig. 11 is a thermal hysteresis curve (a change curve of transmittance along with temperature) of the vanadium oxide composite film prepared by the comparative example, which is measured at a wavelength of 1500nm, when the vanadium dioxide energy-saving film is heated and cooled, the change curve of the transmittance of the vanadium dioxide energy-saving film is not coincident, a certain hysteresis exists, and the thermal hysteresis width is 25.7 ℃.
Claims (9)
1. The preparation method of the vanadium oxide composite powder is characterized by comprising the following steps:
(1) adding vanadium pentoxide and oxalic acid dihydrate into deionized water according to the mass ratio of (1-2):1, fully stirring, dropwise adding a dilute acid solution, adjusting the pH value to 1.5-2.5, continuously stirring for 1-5h in a water bath at 60-80 ℃, then reacting for 5-8h at the temperature of 100-200 ℃, and performing suction filtration to obtain a solution;
(2) putting the solution obtained in the step (1) into a beaker, dropwise adding alkali liquor, adjusting the pH value to 7-10, stirring for 20-60min, centrifuging the obtained suspension, adding deionized water into the obtained slurry, sequentially performing ultrasonic treatment, stirring and centrifugation, and drying the obtained slurry to obtain a reaction precursor;
(3) putting the precursor obtained in the step (2) into a quartz boat, putting the quartz boat into a tube furnace, vacuumizing, introducing protective gas, keeping the temperature at the constant temperature of 800 ℃ for 30min-10h, and naturally cooling to room temperature to obtain VO 2 -V 6 O 13 And (3) composite powder.
2. The method according to claim 1, wherein the acid solution in step (1) is sulfuric acid or hydrochloric acid with a concentration of 0.5 mol/L to 2 mol/L.
3. The preparation method according to claim 1, wherein the alkali solution in the step (2) is an ammonia solution, a sodium hydroxide solution or a potassium hydroxide solution, and the concentration is 0.5 mol/L-2 mol/L.
4. The preparation method according to claim 1, wherein the drying manner in the step (2) is vacuum drying at 50-120 ℃ for 8-48 h.
5. The method according to claim 1, wherein the degree of vacuum in step (3) is less than or equal to 10Pa, the protective gas is any one of nitrogen, argon and helium, and the flow rate is 10-50 sccm.
6. The preparation method as claimed in claim 1, wherein the temperature of step (3) is raised to 300-800 ℃ at 10-20 ℃/min.
7. The vanadium oxide composite powder prepared by the preparation method according to any one of claims 1 to 6.
8. The use of the vanadium oxide composite powder according to claim 7 in the field of thermochromism.
9. A composite nano powder film prepared from the vanadium oxide composite powder according to claim 7, which is obtained by: adding vanadium oxide composite powder and polyvinylpyrrolidone K-30 into ethanol according to the mass ratio of 1 (1-4), stirring and mixing uniformly, performing ultrasonic treatment for 20-30 h to obtain slurry, taking the slurry, uniformly coating the slurry on quartz glass, and drying to obtain a composite nano powder film, wherein the loading capacity of the vanadium oxide composite powder on the quartz glass is 0.005 mg/mm 2 ~0.1mg/mm 2 。
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