CN114368784B - Vanadium dioxide/carbon microsphere thermochromic composite material and preparation method and application thereof - Google Patents
Vanadium dioxide/carbon microsphere thermochromic composite material and preparation method and application thereof Download PDFInfo
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- CN114368784B CN114368784B CN202111586041.XA CN202111586041A CN114368784B CN 114368784 B CN114368784 B CN 114368784B CN 202111586041 A CN202111586041 A CN 202111586041A CN 114368784 B CN114368784 B CN 114368784B
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 87
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 239000004005 microsphere Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 239000003973 paint Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 40
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 38
- 239000002244 precipitate Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 229960005070 ascorbic acid Drugs 0.000 claims description 19
- 235000010323 ascorbic acid Nutrition 0.000 claims description 19
- 239000011668 ascorbic acid Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 14
- 239000011246 composite particle Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000027311 M phase Effects 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009450 smart packaging Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- -1 ventilating Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005303 weighing 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the field of functional composite materials, and particularly relates to a vanadium dioxide/carbon microsphere thermochromic composite material, and a preparation method and application thereof. The composite material is a composite structure formed by blending vanadium dioxide powder with carbon microspheres, and is formed by mixing vanadium dioxide and carbon, wherein the size of the vanadium dioxide powder is 0.1-1 mu m, and the diameter of the carbon microspheres is 3-5 mu m; the carbon microspheres account for 30-50% of the composite material by mass, the preparation adopts a hydrothermal treatment method, a reducing agent and a carbon source are combined into a whole, and vanadium dioxide precursors are reduced and carbonized. The vanadium dioxide/carbon microsphere thermochromic composite material obtained by the invention has excellent thermochromic performance, simple preparation process and low cost, and is suitable for mass production. The composite material of the invention can be widely applied to the fields of intelligent temperature control coatings and paints.
Description
Technical Field
The invention relates to a vanadium dioxide/carbon microsphere thermochromic composite material, and a preparation method and application thereof, and belongs to the field of composite materials.
Background
The 21 st century is the key moment for the rapid development of socioeconomic performance, and energy is the most challenging problem facing mankind in this century. The saving of the prior non-renewable energy sources is the core of most attention in reasonable energy utilization, and the energy saving level is one of important marks for measuring the advanced degree of national science and technology and industrial level. Since the mid 20 th century, many compounds with metal-semiconductor phase transition properties have been discovered successively. The crystal structure of the compound is transformed along with the change of the temperature within a certain range, and mutation from a metal phase (M) to a semiconductor phase (S) or an insulator phase (I), abbreviated as MST transformation or M1 transformation, can occur at the same time of the transformation of the crystal structure. And it was found that the compounds having such phase transition properties are low-valence compounds of transition elements such as titanium, vanadium, chromium, iron, nickel and niobium.
Among a plurality of metal oxides having metal-semiconductor (MST) transition characteristics to provide a metal oxide with a high-k metal-semiconductor transition characteristic to VO 2 Most studied because its phase transition temperature is 68 ℃, closest to room temperature, and the electrical and optical properties vary greatly before and after phase transition. During phase change, the resistivity can change by up to 2-5 orders of magnitude; the change in transmittance in the infrared band (for example, at 2.5 μm) can be more than 60%. VO (VO) 2 The infrared regulation function of the (C) is obvious, and the phase transition temperature of the (C) can be reduced by chemical or physical means, such as doping, particle size control and the like. If VO is utilized 2 The phase change property of the polymer can be made into an intelligent coating, and the polymer can be applied to the field of intelligent surfaces or intelligent packaging. When the indoor temperature is low, the infrared light transmittance is high, so that more infrared light enters the indoor, and the indoor temperature is improved; when the room temperature is higher, the infrared light transmittance is reduced, the infrared light is prevented from entering the room, and the heat-resistant effect is achieved, so that the intelligent control of the indoor temperature is realized. This makes VO 2 Has great application prospect in the fields of intelligence and energy conservation.
Disclosure of Invention
The technical problems solved by the invention are as follows: the vanadium dioxide material is easy to oxidize, has poor particle dispersibility and oversized particles, so that the optical performance of the vanadium dioxide material is deteriorated, and the thermochromic function is lost.
Therefore, the invention provides a vanadium dioxide/carbon microsphere thermochromic composite material with simple process and low cost and a preparation method thereof, and is characterized in that: in V form 2 O 5 The vanadium dioxide/carbon microsphere thermochromic composite material is prepared by adopting a hydrothermal treatment method and can be widely applied to the fields of intelligence and energy conservation.
Specifically, the invention provides the following technical scheme:
the vanadium dioxide/carbon microsphere thermochromic composite material is characterized by being a composite structure formed by blending vanadium dioxide powder and carbon microspheres.
Optionally, the size of the vanadium dioxide powder is 0.1-1 mu m; the diameter of the carbon microsphere is 3-5 mu m.
Optionally, the size of the vanadium dioxide powder is 0.2-1 mu m; the diameter of the carbon microsphere is 3-4.3 mu m.
Optionally, the carbon microspheres comprise 30-50% by mass, preferably 36-50% by mass of the composite material.
Alternatively, the carbon microspheres are formed by a blending reaction during the hydrothermal treatment to produce vanadium dioxide.
The method for preparing the vanadium dioxide/carbon microsphere thermochromic composite material is characterized by comprising the following steps of:
(1) Preparing a vanadium dioxide precursor: will V 2 O 5 Mixing with 18-36% HCl aqueous solution, adding ascorbic acid, ventilating, and alkali washing to obtain precipitate;
(2) Hydrothermal reaction: transferring the precipitate obtained in the step (1) into a reaction kettle, adding water, performing hydrothermal reaction at 200-250 ℃ for 24-60h, and cooling to obtain a product;
(3) And (3) heat treatment: and (3) drying the product obtained in the step (2), and then raising the temperature to 300-800 ℃ under the protection of inert gas, and preserving the heat to obtain the vanadium dioxide/carbon microsphere composite material.
Optionally, step (1) the V 2 O 5 The mixing mass ratio of the aqueous solution of HCl and the aqueous solution of HCl is 1:2-8, preferably 1:3-7.5.
Optionally, stirring the mixed solution in the step (1) in a water bath, wherein the temperature of the water bath is 50-70 ℃.
Optionally, the ascorbic acid in step (1) is added in an amount of 3-5g, preferably 3-4.5g; ascorbic acid and V 2 O 5 The mass ratio of (2) is 1-2:1, preferably 1.25-2:1.
Optionally, the ascorbic acid in step (1) acts as a reducing agent and as a carbon source.
Optionally, the alkaline washing in the step (1) adopts 30-50 mass% NaOH solution until the pH value of the reaction system is 6.5-8.
Optionally, the ventilation body in the step (1) plays a role of removing air, and is composed of one or more than two of nitrogen, argon and helium.
Optionally, in the hydrothermal reaction in the step (2), the material of the inner container of the reaction kettle is para-polyphenol PPL, and the filling degree is 30-70 vol%.
Optionally, the water added in the hydrothermal reaction in the step (2) is 60-140ml deionized water.
Optionally, the inert gas in the heat treatment in the step (3) is at least one of nitrogen, argon and helium.
Optionally, the heating rate of the heat treatment in the step (3) is 5-10 ℃/min, and the heat preservation time is 1-4h.
The vanadium dioxide/carbon microsphere thermochromic composite material prepared by the preparation method.
The vanadium dioxide/carbon microsphere thermochromic composite material or the vanadium dioxide/carbon microsphere thermochromic composite material prepared by the preparation method disclosed by the invention is applied to the fields of intelligent temperature control coatings and paints.
The beneficial effects obtained by the invention are as follows:
the invention provides a vanadium dioxide/carbon microsphere thermochromic composite material and a preparation method thereof, wherein the vanadium dioxide powder has smaller size and good dispersibility, ensures good optical performance and realizes thermochromic temperature control effect; moreover, the preparation method adopts a hydrothermal treatment technology, has simple process and can achieve accurate shape control and controllability of the material, in addition, the ascorbic acid is used as a reducing agent and a carbon source, so that the raw material cost is obviously reduced, and the product is easier to realize large-scale industrial application.
Drawings
FIG. 1 is a scanning electron micrograph (magnification: 1000 times) of the vanadium dioxide/carbon microsphere composite particles prepared in example 1.
FIG. 2 is a scanning electron micrograph (magnification: 5000 times) of the vanadium dioxide/carbon microsphere composite particles prepared in example 2.
FIG. 3 is a scanning electron micrograph (magnification: 5000 times) of the vanadium dioxide/carbon microsphere composite particles prepared in example 3.
FIG. 4 is a scanning electron micrograph (magnification: 5000 times) of the vanadium dioxide/carbon microsphere composite particles prepared in example 4.
FIG. 5 is a scanning electron micrograph (magnification: 5000 times) of the vanadium dioxide/carbon microsphere composite particles prepared in example 5.
FIG. 6 is a scanning electron micrograph (magnification: 5000 times) of the vanadium dioxide/carbon microsphere composite particles prepared in comparative example 2.
FIG. 7 is an optical transmission curve of the vanadium dioxide/carbon microsphere composite particles of example 4 applied to a medium surface.
Detailed Description
As described above, the invention provides a vanadium dioxide/carbon microsphere thermochromic composite material, which is a microsphere structure formed by compounding vanadium dioxide with carbon microspheres, wherein the size diameter of the vanadium dioxide powder is in the range of 0.1-1 mu m; the diameter of the carbon microsphere is 3-5 mu m, and the carbon microsphere accounts for 30-50% of the mass of the composite material.
The vanadium dioxide can realize automatic photo-thermal adjustment according to the change of the ambient temperature, the appearance is sheet-shaped or granular, the three-dimensional size is 0.1-1 mu m, and the optical performance of the composite material is hardly affected because the content of the carbon microsphere is relatively low.
In a preferred embodiment of the invention, a method for preparing a vanadium dioxide/carbon microsphere thermochromic composite material is provided, which is implemented according to the following steps:
step 1, preparing vanadium dioxide precursor
Will V 2 O 5 Mixing with 18-36 mass% HCl aqueous solution, stirring in water bath at 50-70deg.C for 30-120min at a stirring rate of 250-400 r/min, and dissolving in water bath at a mass ratio of 1:25-50; then adding ascorbic acid into the mixed solution, stirring in a water bath to promote dissolution, wherein the water bath temperature is 50-70 ℃, the stirring speed is 250-400 r/min, and the stirring time is 60-120min to obtain mixed liquid. Introducing nitrogen gas to remove air and prevent oxidation of reactant, adding 30-50% NaOH solution until the reaction system is weakly alkaline (pH 6.5-8)Precipitating; the precipitate was filtered off and collected.
Step 2, hydrothermal reaction
Transferring the vanadium dioxide precursor obtained in the step 1 into a reaction kettle, adding deionized water, placing the reaction kettle into a drying box for hydrothermal reaction, cooling to room temperature along with a furnace after the reaction is finished, collecting precipitate, washing with water, and filtering to obtain a reaction product; wherein the temperature of the hydrothermal reaction is 200-250 ℃ and the reaction time is 24-60 h.
Step 3, annealing treatment
Drying the black product at 50-70 ℃ for 8-12 h, then placing the dried product into a tube furnace, heating from room temperature to 300-800 ℃ at a heating rate of 5-10 ℃/min, and then carrying out heat treatment on the composite material precursor under the protection of inert gas for 1-4 h; thus obtaining the vanadium dioxide/carbon microsphere composite material.
Uniformly dispersing the vanadium dioxide/carbon microsphere composite particles in a commercially available high-transparency double-sided adhesive tape to obtain a thermochromic film sample; the sample was stuck on a common glass sheet of a proper size (length. Times. Width: 25X25mm, thickness: 1 mm) to obtain a thermochromic intelligent glass. The spectral transmittance spectrum of the glass was measured at low temperature (25 ℃) and high temperature (90 ℃) by a spectrophotometer equipped with a heating accessory, and the optical properties of the thermochromic glass were evaluated using a glass sheet with a blank double-sided tape as a standard.
The present invention is described in detail below by way of specific examples, wherein table 1 shows the raw materials and equipment parameter information used, and table 2 shows the dimensions, component proportions, amounts of raw materials for reaction and proportion parameters of the composite materials.
Table 1 raw materials and apparatus used in the embodiment
TABLE 2 essential parameters and material ratios of vanadium dioxide/carbon microsphere composite materials
Example 1
Will be 1.5gV 2 O 5 Mixing with 10ml of 18 mass% HCl in 90ml of deionized water, stirring in water bath to promote dissolution, wherein the water bath temperature is 50 ℃, and the stirring speed is 250r/min; 3g of ascorbic acid is weighed and added into the mixed solution, the mixed solution is obtained by stirring and dissolving in a water bath, the temperature of the water bath is 50 ℃, the stirring speed is 250r/min, and the stirring time is 1h. Nitrogen is introduced into the mixed liquid, and then 30 mass percent NaOH solution is slowly added until the pH value of the reaction system is 6.5, precipitate is generated, and the precipitate is collected after washing and filtering. Transferring the precipitate into a 200ml PPL reactor liner (the filling degree is 30 vol%) and adding 60ml deionized water, placing the reactor into a drying oven for hydrothermal reaction, cooling to room temperature along with the furnace after the reaction, collecting the precipitate, washing with water and filtering to obtain a reaction product; wherein the temperature of the hydrothermal reaction is 200 ℃ and the reaction time is 24 hours. Drying the reaction product at 50 ℃ for 8 hours, then placing the dried product into a GSL-1400X tube furnace, heating from room temperature to 300 ℃ at a heating rate of 5 ℃/min, and then carrying out heat treatment on the precursor of the composite material under the protection of nitrogen for 1 hour; the vanadium dioxide/carbon microsphere composite material is obtained, fig. 1 shows a scanning electron microscope image of the vanadium dioxide/carbon microsphere composite particle prepared in the embodiment, wherein the average diameter of the carbon microsphere is about 3 μm, the mass fraction of the carbon microsphere is about 50% and the average diameter of the vanadium dioxide powder is 1 μm, and the composite material can be stably stored for more than 42 days.
Example 2
Will be 2gV 2 O 5 Mixing 10ml 27% HCl in 100ml deionized water, stirring in water bath at 60deg.C at 300r/min; weighing 3.5g of ascorbic acid, adding into the mixed solution, stirring in water bath to promote dissolution to obtain mixed liquid, and water bathThe temperature was 60℃and the stirring rate was 300r/min, and the stirring time was 1h. Nitrogen is introduced into the mixed liquid, and then 40 mass percent NaOH solution is slowly added until the pH value of the reaction system is 7.1, precipitate is generated, and the precipitate is collected after washing and filtering. Transferring the precipitate into a 200ml PPL reactor liner (the filling degree is 40 vol%) and adding 80ml deionized water, placing the reactor into a drying oven for hydrothermal reaction, cooling to room temperature along with the furnace after the reaction, collecting the precipitate, washing with water and filtering to obtain a reaction product; wherein the temperature of the hydrothermal reaction is 210 ℃ and the reaction time is 48 hours. Drying the reaction product at 50 ℃ for 8 hours, then placing the dried product into a GSL-1400X tube furnace, heating from room temperature to 500 ℃ at a heating rate of 10 ℃/min, and then carrying out heat treatment on the precursor of the composite material under the protection of argon for 2 hours; the vanadium dioxide/carbon microsphere composite material is obtained, and a scanning electron microscope image of the vanadium dioxide/carbon microsphere composite particle prepared in the embodiment is shown in fig. 2, wherein the average diameter of the carbon microsphere is 3.7 μm, the mass fraction is 47%, the average diameter of the vanadium dioxide powder is 0.7 μm, and the composite material can be stably stored for more than 42 days.
Example 3
Will be 2.67gV 2 O 5 Mixing with 10ml 36 mass% HCl in 90ml deionized water, stirring in water bath to promote dissolution, wherein the water bath temperature is 60 ℃ and the stirring speed is 300r/min; 4g of ascorbic acid is weighed and added into the mixed solution, the mixed solution is obtained by stirring and dissolving in a water bath, the water bath temperature is 60 ℃, the stirring speed is 300r/min, and the stirring time is 1h. Nitrogen is introduced into the mixed liquid, 50 mass percent NaOH solution is slowly added until the pH value of the reaction system is 7.5, precipitate is generated, and the precipitate is collected after washing and filtering. Transferring the precipitate into a 200ml PPL reactor liner (the filling degree is 50 vol%) and adding 100ml deionized water, placing the reactor into a drying oven for hydrothermal reaction, cooling to room temperature along with the furnace after the reaction, collecting the precipitate, washing with water and filtering to obtain a reaction product; wherein the temperature of the hydrothermal reaction is 220 ℃, and the reaction time is 60 hours. Drying the reaction product at 60deg.C for 12 hr, placing the dried product into GSL-1400X tube furnace, heating to 800 deg.C at 5 deg.C/min, and helium-treatingUnder the protection effect, carrying out heat treatment on the composite material precursor, wherein the heat treatment time is 2 hours; the vanadium dioxide/carbon microsphere composite material is obtained, and a scanning electron microscope image of the vanadium dioxide/carbon microsphere composite particle prepared in the embodiment is shown in fig. 3, wherein the average diameter of the carbon microsphere is 4.1 μm, the mass fraction is 47%, the average diameter of the vanadium dioxide powder is 0.4 μm, and the composite material can be stably stored for more than 35 days.
Example 4
Will be 3.6gV 2 O 5 Mixing with 10ml 36 mass% HCl in 90ml deionized water, stirring in water bath to promote dissolution, wherein the water bath temperature is 70 ℃, and the stirring speed is 400r/min; 4.5g of ascorbic acid is weighed and added into the mixed solution, the mixed solution is obtained by stirring and dissolving in a water bath, the water bath temperature is 70 ℃, the stirring speed is 400r/min, and the stirring time is 1h. Nitrogen is introduced into the mixed liquid, and then 40 mass percent NaOH solution is slowly added until the pH value of the reaction system is 8, so that precipitate is generated, and the precipitate is collected after washing and filtering. Transferring the precipitate into a 200ml PPL reactor liner (the filling degree is 60 vol%) and adding 120ml deionized water, placing the reactor into a drying oven for hydrothermal reaction, cooling to room temperature along with the furnace after the reaction, collecting the precipitate, washing with water and filtering to obtain a reaction product; wherein the temperature of the hydrothermal reaction is 250 ℃, and the reaction time is 60 hours. Drying the reaction product at 60 ℃ for 12 hours, then heating the dried product GSL-1400X tube furnace from room temperature to 800 ℃ at a heating rate of 5 ℃/min, and then carrying out heat treatment on the composite material precursor under the protection of helium for 4 hours; the vanadium dioxide/carbon microsphere composite material is obtained, fig. 4 shows a scanning electron microscope image of the vanadium dioxide/carbon microsphere composite particle prepared in the embodiment, wherein the average diameter of the carbon microsphere is 4.3 μm, the mass fraction is 36%, the average diameter of the vanadium dioxide powder is 0.2 μm, and the composite material can be stably stored for more than 28 days. In addition, as can be seen from fig. 7, the light transmittance of the glass prepared in this example at low temperature (25 ℃ C., upper curve) is significantly higher than that at high temperature (90 ℃ C., lower curve), so that the good solar light regulating effect of the present invention at different temperature environments is also exhibited.
Example 5
Will be 5gV 2 O 5 Mixing with 10ml 36 mass% HCl in 90ml deionized water, stirring in water bath to promote dissolution, wherein the water bath temperature is 70 ℃, and the stirring speed is 400r/min; 5g of ascorbic acid is weighed and added into the mixed solution, the mixed solution is obtained by stirring and dissolving in a water bath, the temperature of the water bath is 70 ℃, the stirring speed is 400r/min, and the stirring time is 2h. Nitrogen is introduced into the mixed liquid, and then 40 mass percent NaOH solution is slowly added until the pH value of the reaction system is 8, so that precipitate is generated, and the precipitate is collected after washing and filtering. Transferring the precipitate into a 200ml PPL reactor liner (the filling degree is 70 vol%) and adding 140ml deionized water, placing the reactor into a drying oven for hydrothermal reaction, cooling to room temperature along with the furnace after the reaction, collecting the precipitate, washing with water and filtering to obtain a reaction product; wherein the temperature of the hydrothermal reaction is 250 ℃, and the reaction time is 60 hours. Drying the reaction product at 60 ℃ for 12 hours, then placing the dried product into a GSL-1400X tube furnace, heating from room temperature to 800 ℃ at a heating rate of 5 ℃/min, and then carrying out heat treatment on the composite material precursor under the protection of helium for 4 hours; the vanadium dioxide/carbon microsphere composite material is obtained, as shown in figure 5, wherein the average diameter of the carbon microsphere is 5 mu m, the mass fraction is 30%, the average diameter of the vanadium dioxide powder is 0.1 mu m, and the composite material can be stably stored for more than 21 days.
Comparative example 1
Will be 5gV 2 O 5 Mixing 10ml 27% HCl in 100ml deionized water, stirring in water bath at 60deg.C at 300r/min; then 2.5mL N was added dropwise to the above mixed solution 2 H 4 ·H 2 O solution, stirring and dissolving in water bath to obtain mixed liquid, wherein the water bath temperature is 60 ℃, the stirring speed is 300r/min, and the stirring time is 1h. Nitrogen is introduced into the mixed liquid, and then 40 mass percent NaOH solution is slowly added until the pH value of the reaction system is 6.5, precipitate is generated, and the precipitate is collected after washing and filtering. Transferring the precipitate into a 200ml PPL reactor liner (with the filling degree of 70 vol%) and adding 140ml deionized water, placing the reactor into a drying oven for hydrothermal reaction, cooling to room temperature with the furnace after the reaction, and collecting the precipitateWashing and filtering the mixture to obtain a reaction product; wherein the temperature of the hydrothermal reaction is 210 ℃ and the reaction time is 48 hours. Drying the reaction product at 50 ℃ for 8 hours, then placing the dried product into a GSL-1400X tube furnace, heating from room temperature to 500 ℃ at a heating rate of 10 ℃/min, and then carrying out heat treatment on the precursor of the composite material under the protection of argon for 2 hours; thus obtaining the vanadium dioxide material with single component.
For the vanadium dioxide/carbon microsphere composite material obtained in any one of examples 1 to 5 and the pure vanadium dioxide material obtained in comparative example 1, 5g each was weighed, put into a beaker having a volume of 25ml (capped with a plastic film to prevent contamination or scattering of external dust), put into an outdoor direct sunlight environment in summer, taken out every 7 days to observe the color change, and analyzed for phase change by XRD, and the results are shown in table 1. The vanadium dioxide/carbon microsphere composite materials obtained in any of examples 1-5 were slow in color change during the test time, and the internal phases were all M-phase vanadium dioxide/carbon during 28 days; the pure vanadium dioxide particles obtained in comparative example 1 were partially oxidized to vanadium pentoxide 21 days later, demonstrating that the vanadium dioxide/carbon microsphere composites obtained in examples 1-5 had better environmental stability than pure vanadium dioxide particles.
TABLE 1 environmental stability test of materials of examples 1-5 and comparative example 1
Comparative example 2
Will be 5gV 2 O 5 Mixing with 10ml 27% HCl in 100ml deionized water, stirring in water bath at 60deg.C at a stirring rate of 300r/min; 5g of ascorbic acid is weighed and added into the mixed solution, the mixed solution is obtained by stirring and dissolving in a water bath, the water bath temperature is 60 ℃, the stirring speed is 300r/min, and the stirring time is 1h. Introducing nitrogen into the mixed liquid, and slowly addingAnd (3) 40% NaOH solution until the pH of the reaction system is 7.1, generating precipitate, washing and filtering, and collecting the precipitate. Transferring the precipitate into a 200ml PPL reactor liner (with the filling degree of 70%), adding 140ml deionized water, placing the reactor into a drying oven for hydrothermal reaction, cooling to room temperature along with a furnace after the reaction is finished, collecting the precipitate, washing with water, and filtering to obtain a reaction product; wherein the temperature of the hydrothermal reaction is 210 ℃ and the reaction time is 48 hours. Drying the reaction product at 50 ℃ for 8 hours, and then putting the dried product into a 500 ℃ tube furnace (GSL-1400X) under the protection of argon, and carrying out heat treatment on the precursor of the composite material for 2 hours; thus obtaining the vanadium dioxide/carbon microsphere composite material. The carbon microspheres in the obtained composite material are broken, and the appearance of vanadium dioxide is irregular. As can be seen from FIG. 6, compared with examples 1-5, the carbon microspheres have more cracks and incomplete morphology, which indicates that the stress in the structure transformation process is slowly released in the formation process of the vanadium dioxide/carbon microsphere composite material by the heat treatment process of gradually increasing the temperature through program temperature control, thereby being beneficial to maintaining the regularity of the morphology of the vanadium dioxide powder and the carbon microspheres.
In conclusion, the preparation process is simple, low in cost and convenient for mass production; the obtained vanadium dioxide/carbon microsphere thermochromic composite material has high transmittance, excellent stability and dispersibility, can be widely used for preparing intelligent temperature control coatings and films, and plays a role in energy conservation and environmental protection.
Claims (22)
1. The vanadium dioxide/carbon microsphere thermochromic composite material is characterized by being a composite structure formed by blending vanadium dioxide powder and carbon microspheres, wherein the size of the vanadium dioxide powder is 0.1-1 mu m; the diameter of the carbon microsphere is 3-5 mu m;
the vanadium dioxide/carbon microsphere thermochromic composite material is prepared by the following steps:
(1) Preparing a vanadium dioxide precursor: will V 2 O 5 Mixing with 18-36% HCl aqueous solution, adding ascorbic acid, introducing inert gas, and alkaline washing to obtain precipitate;
(2) Hydrothermal reaction: transferring the precipitate obtained in the step (1) into a reaction kettle, adding water, performing hydrothermal reaction at 200-250 ℃ for 24-60h, and cooling to obtain a product;
(3) And (3) heat treatment: and (3) drying the product obtained in the step (2), and then raising the temperature to 300-800 ℃ under the protection of inert gas, and preserving the heat to obtain the vanadium dioxide/carbon microsphere composite material.
2. The vanadium dioxide/carbon microsphere thermochromic composite material according to claim 1, wherein the vanadium dioxide powder has a size of 0.2-1 μm; the diameter of the carbon microsphere is 3-4.3 mu m.
3. The vanadium dioxide/carbon microsphere thermochromic composite material according to claim 1, wherein the carbon microsphere comprises 30-50% of the composite material by mass fraction.
4. The vanadium dioxide/carbon microsphere thermochromic composite material according to claim 1, wherein the carbon microspheres comprise 36-50% of the composite material by mass.
5. The vanadium dioxide/carbon microsphere thermochromic composite material according to any one of claims 1-4, wherein the carbon microspheres are formed by a blending reaction during the hydrothermal treatment to prepare vanadium dioxide.
6. The method for preparing the vanadium dioxide/carbon microsphere thermochromic composite material according to any one of claims 1 to 5, comprising the following steps:
(1) Preparing a vanadium dioxide precursor: will V 2 O 5 Mixing with 18-36% HCl aqueous solution, adding ascorbic acid, introducing inert gas, and alkaline washing to obtain precipitate;
(2) Hydrothermal reaction: transferring the precipitate obtained in the step (1) into a reaction kettle, adding water, performing hydrothermal reaction at 200-250 ℃ for 24-60h, and cooling to obtain a product;
(3) And (3) heat treatment: and (3) drying the product obtained in the step (2), and then raising the temperature to 300-800 ℃ under the protection of inert gas, and preserving the heat to obtain the vanadium dioxide/carbon microsphere composite material.
7. The process of claim 6, wherein V in step (1) 2 O 5 The mixing mass ratio of the aqueous solution of HCl and the aqueous solution of HCl is 1:2-8.
8. The process of claim 7, wherein V in step (1) 2 O 5 The mixing mass ratio of the aqueous solution of HCl and the aqueous solution of HCl is 1:3-7.5.
9. The method of claim 6, wherein the mixing solution in step (1) is stirred in a water bath at a temperature of 50-70 ℃.
10. The method of claim 7, wherein the mixing of the solution in step (1) is performed by stirring in a water bath at a temperature of 50-70 ℃.
11. The method of claim 6, wherein the ascorbic acid and V in step (1) 2 O 5 The adding mass ratio of (2) is 1-2:1.
12. The method of claim 11, wherein the ascorbic acid and V in step (1) 2 O 5 The adding mass ratio of (2) is 1.25-2:1.
13. The method of claim 7, wherein the ascorbic acid and V in step (1) 2 O 5 The adding mass ratio of (2) is 1-2:1.
14. The method of claim 9, wherein the ascorbic acid and V in step (1) 2 O 5 The adding mass ratio of (2) is 1-2:1.
15. The method of any one of claims 6-14, wherein the ascorbic acid of step (1) acts as a reducing agent and as a carbon source.
16. The process according to any one of claims 6 to 14, wherein the alkaline washing in step (1) is performed with 30 to 50 mass% NaOH solution to a pH of 6.5 to 8 in the reaction system.
17. The method according to any one of claims 6 to 14, wherein the inert gas introduced in step (1) serves to exclude air and is composed of one or more of nitrogen, argon and helium.
18. The method of any one of claims 6 to 14, wherein in the hydrothermal reaction of step (2), the reactor liner material is para-polyphenol PPL and the degree of filling is 30 to 70% by volume.
19. The process according to any one of claims 6 to 14, wherein 60 to 140ml of deionized water is added in the hydrothermal reaction of step (2).
20. The method according to any one of claims 6 to 14, wherein the inert gas in the heat treatment in step (3) is at least one of nitrogen, argon and helium.
21. The method according to any one of claims 6 to 14, wherein the heating rate of the heat treatment in step (3) is 5 to 10 ℃/min and the holding time is 1 to 4 hours.
22. The vanadium dioxide/carbon microsphere thermochromic composite material according to any one of claims 1 to 5 or the vanadium dioxide/carbon microsphere thermochromic composite material prepared by the preparation method according to claims 6 to 21 is applied to the fields of intelligent temperature control coatings and paints.
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