CN108946809A - The method that template method prepares witch culture porous silica vanadium powder body and film is sacrificed using cotton - Google Patents
The method that template method prepares witch culture porous silica vanadium powder body and film is sacrificed using cotton Download PDFInfo
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- C01G31/00—Compounds of vanadium
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
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- C03C2217/24—Doped oxides
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
Abstract
The method that template method prepares witch culture porous silica vanadium powder body and film is sacrificed using cotton the present invention relates to a kind of, this method is with vanadic anhydride, ammonium tungstate, oxalic acid etc. for raw material, template is sacrificed in conjunction with hydro-thermal reaction and cotton, witch culture porous silica vanadium powder body has been made first, the powder is then configured to the spin-coated method of suspension, the tungsten-doped vanadium dioxide film haveing excellent performance has been made.Since witch culture porous silica vanadium powder body obtained has smaller, more meso-hole structure and biggish porosity, the visible light transmittance and sunlight modulation efficiency of film can be effectively improved, the phase transition temperature of film can also be effectively reduced in the incorporation of tungsten.
Description
Technical field
The present invention relates to inorganic nano material and thermochromic material technical fields, and in particular to a kind of to be sacrificed using cotton
The method that template prepares witch culture porous silica vanadium powder body and film.
Background technique
Vanadium dioxide (VO2) it is considered as a kind of very promising thermochromic material, because it is attached at 68 DEG C
The reversible transition from high-temperature metal phase (R phase) to cryogenic semiconductor phase (M phase) can closely be occurred, crystal structure is from cubic rutile
Structure is changed into monocline, and along with the transformation of crystal structure, the electrical and optical properties of vanadium dioxide can mutate.Its
In by M phase transition at R phase after, it is seen that the transmitance of light is almost constant, and the transmitance of near infrared light decreases, to sunlight
There is certain regulating power, this can be applied to vanadium dioxide film on window to play effect cool in summer and warm in winter.But it is pure
Vanadium dioxide film have to face following three main problem: 1. phase transition temperature is excessively high (68 DEG C)；2. to visible when low temperature
The transmitance of light is lower (< 40%)；(< 10%) 3. limited to sunlight modulation capability.
Researcher takes many methods in order to solve the above problem, including element doping (CN106966432A,
CN106517325A, CN101760735A, CN104445990A, CN105271408A), using multi-layer film structure
(CN107188426A, CN102757184A), using different film forming substrates (CN101760735A), to vanadium dioxide structure into
Row modification etc., wherein element doping is considered as the most effective method for reducing phase transition temperature of vanadium dioxide.Doped chemical packet
Tungsten, molybdenum, fluorine, zirconium, nitrogen etc. are included, it is again most mature with the research of witch culture among these.Witch culture technology is reducing phase alternating temperature at this stage
While spending, but also vanadium dioxide film visible light transmittance and sunlight modulation efficiency are all reduced to relatively low level.
In addition, although some research achievements having disclosed at present can use distinct methods while improve vanadium dioxide film visible light
Transmitance and sunlight modulation efficiency, but the phase transition temperature of film still maintains 68 DEG C or so there is no reducing.
In conclusion there is presently no one kind can be achieved at the same time " vanadium dioxide film phase transition temperature is effectively reduced ", " protects
The vanadium dioxide of the card higher visible light transmittance of film " and " guaranteeing the higher sunlight modulation efficiency of film " triple purposes
Thin-film material and preparation method thereof.
Summary of the invention
It is an object of the invention to overcome deficiencies of the prior art, a kind of utilization cotton sacrifice template is provided
The method for preparing witch culture porous silica vanadium powder body and film.This method firstly generates witch culture using cotton as template
Porous silica vanadium powder body, the vanadium dioxide film material haveing excellent performance then has been made using it.Porous silica vanadium powder
Visible light transmittance and the sun light modulation of thin-film material can be improved in the higher porosity of body and the characteristic that can reduce reunion
Efficiency, witch culture can reduce the phase transition temperature of film, thus solve above-mentioned three major issues simultaneously, so that vanadium dioxide film
Thermochromic properties it is more balanced, excellent.To achieve the above object, the technical solution adopted in the present invention is as follows:
The method that template method prepares witch culture porous silica vanadium powder body and film, including following step are sacrificed using cotton
It is rapid:
(a) vanadic anhydride, tungsten source, oxalic acid source is soluble in water, it adds ethylene glycol and then adjusts before pH value of solution obtains
Liquid solution is driven, cotton is added into precursor solution, heating carries out hydro-thermal reaction.Ethylene glycol is added first is that in order to increase solution
Adhesiveness, allows solution is more preferable, attachment more evenly on the cotton, and finally generates more vanadium oxide crystals on the cotton；Its
The water and ethylene glycol of secondary addition do not participate in reaction, and main function acts as solvent and volatilizees at high temperature so that generating in reaction kettle
Certain pressure, to meet the pressure condition of vanadium dioxide crystallization.
(b) cotton is taken out after the reaction was completed, and washed, dry, calcination obtains powder, after powder is mixed with ammonium hydrogen carbonate
It is made annealing treatment, obtains the witch culture porous silica vanadium powder body of M phase.
(c) witch culture porous silica vanadium powder body obtained is dispersed in alcoholic solvent and obtains suspension, suspension is revolved
It applies on substrate, is tungsten-doped vanadium dioxide film after dry.
According to above scheme, the molar ratio in vanadic anhydride and tungsten source, oxalic acid source is 1:0.03-0.1:3-3.5, the tungsten
Source is selected from one of wolframic acid or soluble tungstate salt (such as ammonium tungstate), and the oxalic acid source refers to can generate oxalic acid in aqueous solution
The compound of radical ion, including oxalic acid and its hydrate, Soluble oxalate salt and its hydrate.
According to above scheme, the preparation method of precursor solution is as follows in step (a): by vanadic anhydride, tungsten source, oxalic acid
Source, which is dissolved in 80-90 DEG C of water, stirs 15-25min, and ethylene glycol is added after its cooled to room temperature, is then adjusted with ammonium hydroxide
The pH to 7-8 of solution.
According to above scheme, the total volume of precursor solution is no more than the 80% of reactor volume, water in precursor solution
Volume ratio with ethylene glycol is 1:1, and the cotton of addition and the mass ratio of vanadic anhydride are 0.75-1.5:1.
According to above scheme, hydrothermal temperature is 160-180 DEG C, reaction time 20-24h.
According to above scheme, repeatedly, then cotton deionized water and alcoholic solvent in step (b) after hydro-thermal reaction are washed
Dry 12-36h under 60-90 DEG C of environment is placed it in, 400-450 DEG C of calcination is then heated to the heating rate of 5-10 DEG C/min
1-2h, last cooled to room temperature.
According to above scheme, powder is uniformly mixed with ammonium hydrogen carbonate according to the mass ratio of 1.5-2:1 in step (b), true
Reciprocal of duty cycle is to be heated to 400-480 DEG C of heat preservation 30-60min in the environment of 40-50Pa with the heating rate of 5-10 DEG C/min, has been annealed
At rear cooled to room temperature.
According to above scheme, PVP (polyvinylpyrrolidone) is also added into step (c) suspension, PVP is mixed with tungsten
The mass ratio of miscellaneous porous silica vanadium powder body is 1:2, suspension solid content 8%-10%.
According to above scheme, the revolving speed of substrate is 500-1000r/min, spin-coating time 10-40s when suspension spin coating,
5-10min is dried after the completion of spin coating at 70-80 DEG C.
According to above scheme, M phase witch culture porous silica vanadium diameter of particle that step (b) obtains 50-200nm it
Between, the tungsten-doped vanadium dioxide film thickness that step (c) obtains is between 500nm-1500nm.
Compared with prior art, the invention has the following advantages:
(1) raw material is simple, and the preparation process of powder and film is simple, low for equipment requirements, thus production cost is low.With five
V 2 O, ammonium tungstate, two oxalic acid hydrates and cotton are raw material, will mix the attachment of tungsten powder body on the cotton with hydro-thermal method, and pass through two
Secondary annealing removes template for the first time and obtains porous powder, and second of ammonia using ammonium bicarbonate breaks down generation restores to obtain
Spin-coating method plated film can be used in obtained powder and PVP and dehydrated alcohol by hypovanadic oxide powder after mixing.
(2) the mesoporous powder aperture being prepared is smaller and quantity is more, and the porosity of powder greatly increases, and can significantly mention
High vanadium dioxide film visible light transmittance；The partial size of powder is smaller, it is not easy to and reunite, is uniformly dispersed in the medium, Neng Goubao
Demonstrate,prove film visible light transmittance, while film can plate it is thicker, thus the modulation efficiency of sunlight be able to achieve it is as big as possible.
(3) phase transition temperature of vanadium dioxide can be effectively reduced in the incorporation of tungsten, and doping is more uniform, effect is preferable, realizes
Three main performances of vanadium dioxide film are all very excellent and more balanced.
Detailed description of the invention
Fig. 1 is the XRD spectrum of witch culture porous silica vanadium powder body prepared by the embodiment of the present invention 1；
Fig. 2 is the full spectrogram of XPS of witch culture porous silica vanadium powder body prepared by the embodiment of the present invention 1；
Fig. 3 is the XPS tungsten atom energy spectrum diagram of witch culture porous silica vanadium powder body prepared by the embodiment of the present invention 1；
Fig. 4 is the TEM figure of witch culture porous silica vanadium powder body prepared by the embodiment of the present invention 1；
Fig. 5 is nitrogen adsorption-desorption curve and the hole of witch culture porous silica vanadium powder body prepared by the embodiment of the present invention 1
Diameter distribution map；
Fig. 6 is the DSC map of witch culture porous silica vanadium powder body prepared by the embodiment of the present invention 1；
Fig. 7 is visible-infrared transmission of the tungsten-doped vanadium dioxide film of the preparation of the embodiment of the present invention 1 at different temperatures
Rate spectrogram；
Fig. 8 is the XRD spectrum of witch culture porous silica vanadium powder body prepared by the embodiment of the present invention 2；
Fig. 9 is nitrogen adsorption-desorption curve and the hole of witch culture porous silica vanadium powder body prepared by the embodiment of the present invention 2
Diameter distribution map；
Figure 10 is the DSC map of witch culture porous silica vanadium powder body prepared by the embodiment of the present invention 2；
Figure 11 is tungsten-doped vanadium dioxide film at different temperatures visible-infrared prepared by the embodiment of the present invention 2
Cross rate spectrogram.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.
Embodiment 1
1) 0.4g (0.0022mol) vanadic anhydride, 0.0046g (7.326*10 are weighed-7Mol) ammonium tungstate and 0.832g
(0.0066mol) two oxalic acid hydrate adds 30mL deionized water in 100mL beaker, places the beaker in 80 DEG C of water-baths
Stirring 20min obtains blue precursor solution；
2) it takes out beaker to keep stirring, 30mL ethylene glycol is added after it is cooled to room temperature, continue stirring 10min and obtain
One solution；
3) ammonium hydroxide is slowly added dropwise into above-mentioned uniform solution, adjusts the pH to 7 of solution；
4) mixed solution and 0.4g absorbent cotton are added to together in 100mL reaction kettle, reaction kettle is put into baking oven
180 DEG C of hydro-thermal reactions for 24 hours, are taken out after its cooled to room temperature；
5) absorbent cotton in reaction kettle is taken out, is first washed with deionized twice, then primary with ethanol washing, then puts
Enter in 80 DEG C of baking ovens and dries for 24 hours；
6) dried absorbent cotton is put into Muffle furnace, is warming up to 450 DEG C with the rate of 5 DEG C/min, keep the temperature 1h, heat preservation
After cool to room temperature with the furnace, obtain the porous vanadic anhydride powder of yellow witch culture；
7) powder and 0.1g ammonium hydrogen carbonate for taking 0.2g step 6) to obtain are uniformly mixed and are placed in vacuum drying oven (vacuum
Spend 40Pa), 480 DEG C are warming up to the rate of 10 DEG C/min, 30min is kept the temperature, cools to room temperature with the furnace after heat preservation, mixed
Tungsten M-phase vanadium dioxide powder；
8) powder, 0.25g PVP and the 8mL ethanol solution for taking 0.5g step 7) to obtain, mixed grinding is uniform, then with
The revolving speed of 8000r/min is centrifuged 5min, and suspension is taken to be dried to obtain powder；
9) the drying powder for taking 0.1g step 8) to obtain adds it to ultrasonic disperse in 0.9g dehydrated alcohol and is suspended
Liquid.Suspension is coated on the common soda-lime-silica glass substrate that cleans up using spin-coating method, first with 500r/min when spin coating
Spin coating 10s, then with 1000r/min spin coating 20s, on hot plate in 80 DEG C of dry 5min, as witch culture porous five after film forming
V 2 O film.
For the performance for fully understanding the porous vanadic anhydride powder of witch culture made from the present embodiment and film, phase has been carried out
The test answered.
1.X x ray diffraction analysis x
German Brooker AXS company DB Advance type X-ray diffraction analysis instrument, copper target Cu-K α as radiation source (λ=
0.154178nm), rated output power 3KW, 20-80 ° of scanning range, 4 ° of scanning speed is per minute.
2.X X-ray photoelectron spectroscopy X
Thermo Fisher Scientific Inc. of U.S. ESCALAB 250Xi/ESCALAB 250Xi type x-ray photoelectron energy
Spectrometer tests the XPS line scanning of powder.
3. multichannel specific surface area and pore analysis
II 3020/TriStar of U.S. Mike company's T riStar, II 3020 type multichannel specific surface area and Porosimetry,
Nitrogen adsorption-the desorption curve and the pore-size distribution in powder for testing powder.
4. UV, visible light near infrared spectrometer
Japanese Shimadzu Corporation UV-3600 type UV, visible light near infrared spectrometer, respectively when testing film 20 and 90 DEG C
Transmitance within the scope of wavelength 300-2500nm calculates the parameters such as light transmittance according to following integral formula.
Fig. 1-6 is respectively the X-ray diffraction of witch culture M phase porous silica vanadium powder body made from 1 step 7 of embodiment
(XRD) figure, x-ray photoelectron spectroscopy (XPS) full spectrogram, tungsten atom xps energy spectrum figure, transmission electron microscope picture (TEM), nitrogen adsorption-
Desorption curve and graph of pore diameter distribution, differential scan calorimetric (DSC) figure.As can be seen from Figure 1 product is M phase hypovanadic oxide crystal
Structure illustrates that the derivative of not tungsten generates, and tungsten has been likely to enter vanadium dioxide lattice.In conjunction with the x-ray photoelectron of powder
Energy spectrum diagram (Fig. 2-3) is it is found that tungsten atom has been entered in the lattice of hypovanadic oxide powder really instead of part vanadium atom.From figure
4 can intuitively see diameter of particle between 50~200nm, and with the presence of a large amount of hole in powder.From the N of Fig. 52Absorption is de-
The adsorption desorption curve that attached curve and graph of pore diameter distribution can be seen that powder belongs to the IV type adsorption isotherm with H3 type hysteresis loop
Line, is a kind of mesoporous material, and aperture size is mainly between 2-14nm.The DSC curve of Fig. 6 illustrates: the tungsten of 0.4% atomic ratio
Doping is so that powder phase transition temperature falls below 43 DEG C.High/low temperature shown in Fig. 7 is visible-infrared light transmittance the result shows that, this is thin
The visible light transmittance of film is higher, and it is 61.61% that visible light transmittance, which is calculated, by integral formula, sunlight modulation efficiency
Still it is up to 11.37%.
In summary result is it is found that the thermochromic properties of the film are more balanced and all very excellent.
Embodiment 2
1) 0.4g (0.0022mol) vanadic anhydride, 0.0023g (7.326*10 are weighed-7Mol) ammonium tungstate and 0.832g
(0.0066mol) two oxalic acid hydrate adds 30mL deionized water in 100mL beaker, places the beaker in 80 DEG C of water-baths
25min is stirred, blue precursor solution is obtained；
2) it takes out beaker to keep stirring, 30mL ethylene glycol is added after it is cooled to room temperature, continue stirring 10min and obtain
One solution；
3) ammonium hydroxide is slowly added dropwise into above-mentioned uniform solution, adjusts the pH to 8 of solution；
4) mixed solution and 0.35g absorbent cotton are added to together in 100mL reaction kettle, reaction kettle is put into baking oven
In, in 180 DEG C of hydro-thermal reaction 20h, taken out after its cooled to room temperature；
5) absorbent cotton in reaction kettle is taken out, is first washed with deionized twice, then primary with ethanol washing, then puts
Enter in 80 DEG C of baking ovens and dries for 24 hours；
6) dried absorbent cotton is put into Muffle furnace, is warming up to 450 DEG C with the rate of 10 DEG C/min, keeps the temperature 1h, protects
Cool to room temperature after temperature with the furnace；
7) powder and 0.1g ammonium hydrogen carbonate for taking 0.2g step 6) to obtain, are placed in vacuum drying oven (vacuum degree for mixture
50Pa), 480 DEG C are warming up to the rate of 10 DEG C/min, keep the temperature 30min, wait keep the temperature after cool to room temperature with the furnace, mixed
Tungsten M-phase vanadium dioxide powder；
8) powder for taking 0.5g step 7) to obtain is mixed with 0.25g PVP and 8mL ethanol solution, and grinding is uniform, with
The revolving speed of 8000r/min is centrifuged 5min, and suspension is taken to be dried to obtain powder；
9) the drying powder for taking 0.1g step 8) to obtain adds it to ultrasonic disperse in 0.9g dehydrated alcohol and is suspended
Liquid.Suspension is coated on the common soda-lime-silica glass substrate cleaned up using spin-coating method.First with 500r/min when spin coating
Spin coating 10s, then with 1000r/min spin coating 20s, on hot plate in 80 DEG C of dry 5min, as witch culture porous five after film forming
V 2 O film.
Fig. 8 shows that the porous vanadic anhydride powder of witch culture made from embodiment 2 is also M phase structure, is able to achieve reversible gold
Category-semiconductor transition.BET test result (Fig. 9) also illustrates that the powder has meso-hole structure.It can be with from the DSC curve of Figure 10
Find out, the witch culture of 0.2% atomic ratio makes the phase transition temperature of film be reduced to 56.9 DEG C, according to optical transmission spectra figure (figure
11) the thin film low temperature visible light transmittance being calculated is 59.69%, solar energy modulation efficiency is 12.46%.
The above experimental data also demonstrates that the optical property of the porous vanadium pentoxide films of the witch culture of this component is more excellent
It is different.
Claims (10)
1. sacrificing the method that template method prepares witch culture porous silica vanadium powder body and film using cotton, which is characterized in that packet
Include following steps:
(a) vanadic anhydride, tungsten source, oxalic acid source is soluble in water, adding ethylene glycol, then adjusting pH value of solution obtains presoma
Solution, cotton is added into precursor solution, and heating carries out hydro-thermal reaction；
(b) cotton is taken out after the reaction was completed, and washed, dry, calcination obtains powder, carries out after powder is mixed with ammonium hydrogen carbonate
Annealing, obtains the witch culture porous silica vanadium powder body of M phase；
(c) witch culture porous silica vanadium powder body obtained is dispersed in alcoholic solvent and obtains suspension, suspension is spin-coated on
It is tungsten-doped vanadium dioxide film after dry on substrate.
2. the method as described in claim 1, it is characterised in that: mole of vanadic anhydride and tungsten source, oxalic acid source in step (a)
Than for 1:0.03-0.1:3-3.5, the tungsten source is selected from one of wolframic acid or soluble tungstate salt, the oxalic acid source is selected from grass
One of acid or its hydrate, Soluble oxalate salt or its hydrate.
3. the method as described in claim 1, which is characterized in that the preparation method of precursor solution is as follows in step (a): by five
V 2 O, tungsten source, oxalic acid source, which are dissolved in 80-90 DEG C of water, stirs 15-25min, and second is added after its cooled to room temperature
Then glycol adjusts the pH to 7-8 of solution with ammonium hydroxide.
4. the method as described in claim 1, it is characterised in that: the total volume of precursor solution is no more than reactor volume
80%, the volume ratio of water and ethylene glycol is 1:1 in precursor solution, and the cotton of addition and the mass ratio of vanadic anhydride are
0.75-1.5:1。
5. the method as described in claim 1, it is characterised in that: hydrothermal temperature is 160-180 DEG C, reaction time 20-
24h。
6. the method as described in claim 1, it is characterised in that: cotton deionized water in step (b) after hydro-thermal reaction and
Alcoholic solvent washing repeatedly, then places it in dry 12-36h under 60-90 DEG C of environment, then with the heating rate of 5-10 DEG C/min
It is heated to 400-450 DEG C of calcination 1-2h, last cooled to room temperature.
7. the method as described in claim 1, it is characterised in that: in step (b) powder and ammonium hydrogen carbonate according to 1.5-2:1 matter
Amount is heated to 400-480 DEG C of guarantor in the environment that vacuum degree is 40-50Pa than being uniformly mixed with the heating rate of 5-10 DEG C/min
Warm 30-60min, cooled to room temperature after the completion of annealing.
8. the method as described in claim 1, it is characterised in that: be also added into PVP, PVP and tungsten in step (c) suspension
The mass ratio for adulterating porous silica vanadium powder body is 1:2, suspension solid content 8%-10%.
9. the method as described in claim 1, it is characterised in that: the revolving speed of substrate is 500-1000r/min when suspension spin coating,
Spin-coating time is 10-40s, dries 5-10min after the completion of spin coating at 70-80 DEG C.
10. such as the described in any item methods of claim 1-9, it is characterised in that: the M phase witch culture porous two that step (b) obtains
For vanadium oxide diameter of particle between 50-200nm, the tungsten-doped vanadium dioxide film thickness that step (c) obtains is 500nm-
Between 1500nm.
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| CN201810819979.3A CN108946809A (en) | 2018-07-24 | 2018-07-24 | The method that template method prepares witch culture porous silica vanadium powder body and film is sacrificed using cotton |
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| CN109678208A (en) * | 2017-10-19 | 2019-04-26 | 深圳市寒暑科技新能源有限公司 | A kind of hollow vanadic anhydride material and preparation method thereof for Zinc ion battery |
| CN111484256A (en) * | 2019-01-25 | 2020-08-04 | 武汉理工大学 | VO (volatile organic compound)2Preparation method of-ZnO composite particle film |
| WO2021242109A1 (en) * | 2020-05-29 | 2021-12-02 | Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno | Thermochromic materials and preparation method |
| CN113773707A (en) * | 2021-10-29 | 2021-12-10 | 湖北大学 | Waterproof vanadium dioxide intelligent temperature control coating and preparation method thereof |
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Cited By (4)
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| CN109678208A (en) * | 2017-10-19 | 2019-04-26 | 深圳市寒暑科技新能源有限公司 | A kind of hollow vanadic anhydride material and preparation method thereof for Zinc ion battery |
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| CN113773707A (en) * | 2021-10-29 | 2021-12-10 | 湖北大学 | Waterproof vanadium dioxide intelligent temperature control coating and preparation method thereof |
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