CN114920296B - 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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- CN114920296B CN114920296B CN202210666702.8A CN202210666702A CN114920296B CN 114920296 B CN114920296 B CN 114920296B CN 202210666702 A CN202210666702 A CN 202210666702A CN 114920296 B CN114920296 B CN 114920296B
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- 239000000843 powder Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 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 35
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 35
- 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
- 108010053481 Antifreeze Proteins Proteins 0.000 claims abstract description 18
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 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 4
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 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
- 238000010438 heat treatment Methods 0.000 claims description 11
- 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
- 238000001816 cooling Methods 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- 239000011858 nanopowder Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 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
- 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
- 239000007789 gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 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
- 239000000243 solution Substances 0.000 claims 4
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 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
- 239000012071 phase Substances 0.000 description 28
- 230000008859 change Effects 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 12
- 230000007704 transition Effects 0.000 description 11
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 10
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000013329 compounding Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 238000000411 transmission spectrum Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 1
- 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 238000011946 reduction process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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 regulating the pH value by using a dilute acid solution to obtain a vanadyl oxalate solution; (2) Dropwise adding a proper amount of alkali liquor into the vanadyl oxalate solution in the step (1) to prepare slurry, and vacuum drying 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 heating program, and starting a solid phase reaction to obtain the vanadium oxide composite powder. According to the invention, through the controllable composite powder component regulation and control, the effective regulation and control of the thermal hysteresis loop width of the vanadium oxide powder and the energy-saving film is realized, and the intelligent window application of the vanadium oxide powder and the energy-saving film is facilitated.
Description
Technical Field
The invention belongs to the technical field of inorganic thermochromic oxide material preparation, and particularly relates to a preparation method of vanadium oxide composite powder.
Background
Thermochromic vanadium dioxide (VO) 2 ) Has unique metal-insulator phase change characteristics and is a research hot spot for physical directions of materials and condensed states. VO (VO) 2 Is 68 ℃, the common transformation of structure and electron occurs during the phase transformation, i.e. VO is below the phase transformation temperature 2 Monoclinic (M1 phase) in the semiconducting or insulating state; above the phase transition temperature, VO 2 Is a rutile phase (R phase) in a metallic state. VO before and after phase transition 2 The optical properties (near infrared transmission state) and the electrical properties (resistivity, etc.) of the material are obviously changed, and the characteristics lead to VO 2 Has good application prospect in the fields of photoelectric switches, infrared detection, intelligent windows, optical storage devices and the like.
VO 2 The phase change characteristics of (a) relate to the phase change temperature, the phase change hysteresis line, the change of the optical property and the electrical property before and after the phase change, and the like, and VO 2 The smart window applications of (a) require materials meeting basic performance requirements: the phase transition temperature is close to room temperature, the hysteresis width is narrow, the optical performance comprises high visible light transmittance and high near infrared transmittance change value before and after phase transition. At present, researchers have proposed numerous methods for achieving adjustment of phase transition temperature and optical properties, such as element doping, stress and defect engineering, compounding techniques, film system design, and the like. However, studies on thermal hysteresis width adjustment remain to be further explored. Therefore, the adjustable hysteresis width is realized mainly 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 width by adjusting the components of the composite powder. Mainly comprises the following steps:
1, adding vanadium pentoxide and oxalic acid dihydrate into deionized water according to a mass ratio (1-2), fully stirring (stirring for 5-6 h), dropwise adding a dilute acid solution, regulating the pH value to 1.5-2.5, continuously stirring in a water bath at 60-80 ℃ for 1-5h, reacting for 5-8h at 100-200 ℃, and carrying out suction filtration to obtain a blue clear solution;
step 2, taking a proper amount of clear blue solution, placing the solution into a beaker, dripping alkali solution, adjusting the pH value to 7-10, stirring for 20-60min, centrifuging the obtained suspension, adding deionized water into the obtained slurry, sequentially carrying out ultrasonic treatment, stirring and centrifuging, 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 into a tube furnace, vacuumizing, introducing protective gas, preserving 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 (5) compounding powder.
In the invention, in the step 1, the mass ratio of the vanadium pentoxide to the oxalic acid dihydrate is configured according to (1-2): 1, and can be 1:1, 1.5:1, 2:1 and the like.
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 mol/L-2 mol/L.
The drying mode in the step 2 is vacuum drying, the temperature is 50-120 ℃, and the time is 8-h h.
The centrifugation shown in step 2 refers to centrifugation at 8000 rpm.
The ultrasonic treatment in the step 2 is performed at 600W.
The stirring in step 1 and step 2 was carried out at a speed of 800 rpm.
And 3, the absolute vacuum degree of vacuumizing in the step is less than or equal to 10Pa, the shielding gas is any one of nitrogen, argon and helium, and the inflow rate is 10-50sccm.
In the solid phase reaction in the step 3, the temperature is increased to 300-800 ℃ at 10-20 ℃/min.
The invention develops a method for preparing composite powder to realize adjustable thermal hysteresis width. The VO in the composite powder is regulated by regulating the temperature and time of the solid phase reaction 2 And V 6 O 13 Thereby realizing the adjustment of the width of the thermal hysteresis. 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 adhesive 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 prepared in example 1;
FIG. 2 is an X-ray diffraction chart of the vanadium oxide composite powder prepared in example 2;
FIG. 3 is an X-ray diffraction chart of the vanadium oxide composite powder prepared 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 prepared 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 the vanadium oxide composite powder film prepared in example 1;
FIG. 9 is a thermal hysteresis curve of the vanadium oxide composite film prepared in example 1;
FIG. 10 is a transmission spectrum of the vanadium dioxide composite film produced in the comparative example;
FIG. 11 shows the thermal hysteresis loop of the vanadium dioxide composite film prepared in the comparative example.
Detailed Description
For a more detailed description of the present invention, reference will now be made in detail to specific examples.
Example 1
The preparation method of the 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 for 6 hours at a rotating speed of 800rpm, dropwise adding 1mol/L of dilute sulfuric acid solution, regulating the pH value to 2, continuously stirring in a water bath at 60 ℃ (the rotating speed is 800 rpm) for 1 hour, reacting for 6 hours at a temperature of 150 ℃, and carrying out suction filtration to obtain a blue clear solution;
step 2, placing 40mL of clear blue solution in a beaker, slowly dripping 1mol/L ammonia water solution, adjusting the pH value to 8, stirring at 800rpm for 20min, centrifuging the obtained suspension (at 8000rpm, 3 min), adding 40mL of deionized water into the obtained slurry, sequentially carrying out ultrasonic treatment (ultrasonic power is 600W,10 min), stirring (at 800rpm,10 min) and centrifuging (at 8000rpm, 3 min), and drying the obtained slurry at 80 ℃ for 12h to obtain a reaction precursor;
step 3, taking 0.1g of precursor, placing the precursor into a quartz boat, placing the quartz boat into a tube furnace, vacuumizing to the absolute vacuum degree of less than or equal to 10Pa, introducing 30sccm of nitrogen, heating to 550 ℃ at 20 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain 0.07gVO 2 -V 6 O 13 And (5) compounding powder.
Preparation of composite nano powder film: mixing 20mg of vanadium oxide composite powder with polyvinylpyrrolidone (K-30) according to a mass ratio of 1:2.5, adding into 1mL of ethanol, stirring at 600rpm for 5h, and performing ultrasonic treatment (ultrasonic power is 600W) for 24h to obtain slurry. 60 mu L of the slurry was uniformly coated on 15mm by 15mm quartz glass, spun at a low speed of 400rpm for 3s, then spun at a speed of 3000rpm for 30s, and dried in an oven at 80℃for 20min to obtain a composite nano powder film 1 mu m thick.
FIG. 1 shows XRD patterns of the composite powder obtained in example 1, VO 2 And V 6 O 13 Is used for estimating VO according to a map 2 Is 71.4. 71.4 wt wt.%. Fig. 5 is a scanning electron microscope image of the vanadium oxide composite powder prepared in example 1, wherein the composite powder has a nano-sheet morphology. FIG. 6 is a DSC curve of the vanadium oxide composite powder obtained in example 1, and the phase transition temperatures of the heating section and the cooling section were found to be 67.5℃and 60.4℃respectively, and the thermal hysteresis width of the powder was found to be 7.1 ℃. Fig. 8 is a transmittance spectrum of the vanadium oxide composite powder film prepared in example 1, which shows that the composite powder has thermochromic property (temperature change transmittance is obviously changed), that is, above the phase transition temperature, the infrared transmittance is higher, the energy-saving film transmits infrared light, and below the phase transition temperature, the infrared transmittance is low, and the energy-saving film can block the passing of infrared light. FIG. 9 is a thermal hysteresis curve (transmittance curve with temperature) of the vanadium oxide composite film prepared in example 1 at a wavelength of 1500nm, wherein the transmittance curve is not overlapped with the transmittance curve during heating and cooling, a certain hysteresis exists, the phase change characteristic of vanadium dioxide is shown, and the thermal hysteresis width of the composite film is 12.6 ℃.
Example 2
The preparation method of the 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 for 6 hours at a rotating speed of 800rpm, dropwise adding 1mol/L of dilute sulfuric acid solution, regulating the pH value to 2, continuously stirring in a water bath at 60 ℃ (the rotating speed is 800 rpm) for 1 hour, reacting for 6 hours at a temperature of 150 ℃, and carrying out suction filtration to obtain a blue clear solution;
step 2, placing 40mL of clear blue solution in a beaker, slowly dripping 1mol/L ammonia water solution, adjusting the pH value to 8, stirring at 800rpm for 20min, centrifuging the obtained suspension (at 8000rpm, 3 min), adding 40mL of deionized water into the obtained slurry, sequentially carrying out ultrasonic treatment (ultrasonic power is 600W,10 min), stirring (at 800rpm,10 min) and centrifuging (at 8000rpm, 3 min), and drying the obtained slurry at 80 ℃ for 12h to obtain a reaction precursor;
step 3, taking 0.1g of precursor, placing the precursor into a quartz boat, placing the quartz boat into a tube furnace, vacuumizing to the absolute vacuum degree of less than or equal to 10Pa, introducing 30sccm of nitrogen, heating to 550 ℃ at 20 ℃/min, preserving heat for 3 hours, and naturally cooling to room temperature to obtain 0.08gVO 2 -V 6 O 13 And (5) compounding powder.
Preparation of composite nano powder film: mixing 20mg of vanadium oxide composite powder with polyvinylpyrrolidone (K-30) according to a mass ratio of 1:2.5, adding into 1mL of ethanol, stirring at 600rpm for 5h, and performing ultrasonic treatment (ultrasonic power is 600W) for 24h to obtain slurry. 60 mu L of the slurry was uniformly coated on 15mm by 15mm quartz glass, spun at a low speed of 400rpm for 3s, then spun at a speed of 3000rpm for 30s, and dried in an oven at 80℃for 20min to obtain a composite nano powder film 1 mu m thick.
FIG. 2 shows XRD patterns of the composite powder obtained in example 2, VO 2 And V 6 O 13 Is used for estimating VO according to a map 2 Is 48.8. 48.8 wt wt.%. The DSC tests the phase change of the composite powder, and 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
The preparation method of the 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 for 6 hours at a rotating speed of 800rpm, dropwise adding 1mol/L of dilute sulfuric acid solution, regulating the pH value to 2, continuously stirring in a water bath at 60 ℃ (the rotating speed is 800 rpm) for 1 hour, reacting for 6 hours at a temperature of 150 ℃, and carrying out suction filtration to obtain a blue clear solution;
step 2, placing 40mL of clear blue solution in a beaker, slowly dripping 1mol/L ammonia water solution, adjusting the pH value to 8, stirring at 800rpm for 20min, centrifuging the obtained suspension (at 8000rpm, 3 min), adding 40mL of deionized water into the obtained slurry, sequentially carrying out ultrasonic treatment (ultrasonic power is 600W,10 min), stirring (at 800rpm,10 min) and centrifuging (at 8000rpm, 3 min), and drying the obtained slurry at 80 ℃ for 12h to obtain a reaction precursor;
step 3, taking 0.1g of precursor, placing the precursor into a quartz boat, placing the quartz boat into a tube furnace, vacuumizing to the absolute vacuum degree of less than or equal to 10Pa, introducing 30sccm of nitrogen, heating to 700 ℃ at 20 ℃/min, preserving heat for 3 hours, and naturally cooling to room temperature to obtain 0.08gVO 2 -V 6 O 13 And (5) compounding powder.
Preparation of composite nano powder film: mixing 20mg of vanadium oxide composite powder with polyvinylpyrrolidone (K-30) according to a mass ratio of 1:2.5, adding into 1mL of ethanol, stirring at 600rpm for 5h, and performing ultrasonic treatment (ultrasonic power is 600W) for 24h to obtain slurry. 60 mu L of the slurry was uniformly coated on 15mm by 15mm quartz glass, spun at a low speed of 400rpm for 3s, then spun at a speed of 3000rpm for 30s, and dried in an oven at 80℃for 20min to obtain a composite nano powder film 1 mu m thick.
FIG. 3 is an XRD pattern of the composite powder obtained in example 3, VO 2 And V 6 O 13 Is used for estimating VO according to a map 2 Is 23.4. 23.4 wt wt.%. The DSC tests the phase change of the composite powder, and 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 for 6 hours at a rotating speed of 800rpm, dropwise adding 1mol/L of dilute sulfuric acid solution, regulating the pH value to 2, continuously stirring in a water bath at 60 ℃ (the rotating speed is 800 rpm) for 1 hour, reacting for 8 hours at a temperature of 150 ℃, and carrying out suction filtration to obtain a blue clear solution;
step 2, placing 40mL of clear blue solution in a beaker, slowly dripping 1mol/L ammonia water solution, adjusting the pH value to 8, stirring at 800rpm for 20min, centrifuging the obtained suspension (at 8000rpm, 3 min), adding 40mL of deionized water into the obtained slurry, and sequentially carrying out ultrasonic treatment (ultrasonic power is 600W,10 min) and stirring (at 800rpm,10 min) to obtain a reaction precursor solution;
and step 3, transferring the reaction precursor liquid into a 50mL hydrothermal kettle, heating to 260 ℃ at a speed of 5 ℃/min, and carrying out hydrothermal reaction for 24 hours. After the reaction, taking the precipitate, washing, centrifuging (at 8000rpm for 3 min), repeating for 3 times, pouring out supernatant, and baking the obtained precipitate at 60deg.C for 12 hr to obtain VO 2 And (3) powder.
And 4, taking 20mg of vanadium dioxide powder, adding the powder and polyvinylpyrrolidone (K-30) into 1mL of ethanol according to a mass ratio of 1:2.5, stirring for 5 hours at a rotating speed of 600rpm, and performing ultrasonic treatment (the ultrasonic power is 600W) for 24 hours to obtain slurry. 60 mu L of the slurry was uniformly coated on 15mm by 15mm quartz glass, spun at a low speed of 400rpm for 3s, then spun at a speed of 3000rpm for 30s, and dried in an oven for 20min to obtain a composite nano powder film 1 mu m thick.
FIG. 4 is VO in comparative example 2 XRD pattern of powder is pure-phase VO 2 . FIG. 7 is 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 is a transmittance spectrum of the vanadium oxide composite powder film obtained in comparative example, and VO obtained by hydrothermal treatment 2 The powder has a characteristic variable-temperature spectrum, namely, is higher than the phase transition temperature, has higher infrared transmittance, and the energy-saving film transmits infrared light; below the phase transition temperature, the infrared transmittance is low, based on VO 2 The energy-saving film of the (a) can block the passing of infrared light. FIG. 11 shows the thermal hysteresis curve (transmittance curve with temperature) of the vanadium oxide composite film prepared in comparative example at 1500nm wavelength, wherein the transmittance curve of the vanadium dioxide energy-saving film is not coincident with the temperature reduction process in the heating process, and a certain hysteresis exists, and the thermal hysteresis width is 25.7 ℃.
Claims (4)
1. The preparation method of the vanadium oxide composite powder with adjustable thermal hysteresis width is characterized by comprising the following steps of:
(1) Adding vanadium pentoxide and oxalic acid dihydrate into deionized water according to a mass ratio of 1:1, fully stirring, dropwise adding a dilute acid solution, regulating the pH value to 1.5-2.5, continuously stirring in a water bath at 60-80 ℃ for 1-5h, then reacting at 100-150 ℃ for 5-8h, and carrying out suction filtration to obtain a solution;
(2) Placing the solution obtained in the step (1) into a beaker, dropwise adding an alkaline solution, adjusting the pH value to 7-10, stirring for 20-60min, centrifuging the obtained suspension, adding deionized water into the obtained slurry, sequentially carrying out ultrasonic treatment, stirring and centrifuging, and drying the obtained slurry to obtain a reaction precursor; the drying mode is vacuum drying, the temperature is 50-120 ℃ and the time is 8 h-48 h;
(3) Placing the precursor obtained in the step (2) into a quartz boat, placing into a tube furnace, vacuumizing, introducing protective gas, heating to 300-800 ℃ at 10-20 ℃/min, preserving heat at the constant temperature of 300-800 ℃ for 30min-10h, and naturally cooling to room temperature to obtain VO 2 -V 6 O 13 Composite powder; the acid solution in the step (1) is sulfuric acid or hydrochloric acid, and the concentration is 0.5 mol/L-2 mol/L; the alkali liquor in the step (2) is ammonia water, sodium hydroxide or potassium hydroxide solution, and the concentration is 0.5 mol/L-2 mol/L; and (3) the absolute vacuum degree of the vacuumizing is less than or equal to 10Pa, the shielding gas is any one of nitrogen, argon and helium, and the inflow rate is 10-50sccm.
2. The vanadium oxide composite powder with adjustable thermal hysteresis width prepared by the preparation method of claim 1.
3. The application of the vanadium oxide composite powder with adjustable thermal hysteresis width in the thermochromic field.
4. A composite nano powder film prepared by the vanadium oxide composite powder with adjustable thermal hysteresis width according to claim 3, which is characterized by being obtained by the following steps: adding vanadium oxide composite powder and polyvinylpyrrolidone K-30 into ethanol according to a mass ratio of (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 vanadium oxide composite powder is coated on the quartz glassIs 0.005 mg/mm 2 ~0.1mg/mm 2 。
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