CN107935405B - Preparation method of antimony-doped tin oxide electrochromic film - Google Patents
Preparation method of antimony-doped tin oxide electrochromic film Download PDFInfo
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- CN107935405B CN107935405B CN201711181059.5A CN201711181059A CN107935405B CN 107935405 B CN107935405 B CN 107935405B CN 201711181059 A CN201711181059 A CN 201711181059A CN 107935405 B CN107935405 B CN 107935405B
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000005507 spraying Methods 0.000 claims abstract description 75
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 45
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011521 glass Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000005361 soda-lime glass Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000007921 spray Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 12
- 239000012159 carrier gas Substances 0.000 claims abstract description 12
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 12
- 230000005540 biological transmission Effects 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 25
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 15
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 description 21
- 238000005562 fading Methods 0.000 description 21
- 238000003760 magnetic stirring Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 5
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 238000003764 ultrasonic spray pyrolysis Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- 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
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
- C03C17/253—Coating containing SnO2
-
- 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
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
- C03C2217/244—Doped oxides with Sb
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention discloses a preparation method of an antimony-doped tin oxide electrochromic film, which comprises the following specific steps: step 1, preparing a spraying liquid: firstly, adding antimony trichloride into acetylacetone, then adding stannic chloride pentahydrate, after the mixed solution is cooled to room temperature, adding acetic anhydride into the mixed solution, stirring the mixed solution at room temperature for 30min, finally adding absolute ethyl alcohol, and stirring the mixed solution at room temperature for 20min to obtain an ATO spraying liquid; step 2, preparing an ATO film: firstly, placing a soda-lime glass substrate into a heating furnace, heating to 350-450 ℃, driving the soda-lime glass substrate to move to a spraying chamber by a transmission device, spraying the ATO spraying liquid prepared in the step 1 on the surface of the soda-lime glass substrate by using an ultrasonic spraying spray gun by taking nitrogen as carrier gas, cooling by strong wind after spraying is finished, unloading coated glass, and finally obtaining the antimony-doped tin oxide electrochromic film. The preparation method has simple process and does not need special vacuum environment and reaction chamber.
Description
Technical Field
The invention belongs to the technical field of photoelectrons, and particularly relates to a preparation method of an antimony-doped tin oxide electrochromic film.
Background
The Antimony doped Tin Oxide (ATO) film has very strong corrosion resistance, good conductivity, high visible light transmittance, ultraviolet interception and high middle and far infrared reflection capability, has very large application and development prospects in the field of building energy-saving glass, and can be plated on the surface of common transparent glass to prepare Low-radiation glass (Low-e glass) with heat insulation performance. The traditional Low-e glass has the characteristics of high transmittance in a visible spectrum section and high reflectivity in a middle and far infrared wave band, and can ensure indoor lighting and isolate middle and far infrared radiant heat. However, the solar heat radiation is mainly concentrated in the near infrared band, and as people seek higher and higher living comfort, the glass window is urgently expected to adjust the solar heat radiation according to the needs, so that the Low-e coated glass is required to have adjustability for near infrared transmission light. The ATO film with the nanoscale crystal grain size has the characteristic of local surface plasma vibration absorption, the characteristic can be adjusted through electrochemical doping, the absorption rate of the ATO film in a certain near-infrared band is changed, the electrochromic performance in a near-infrared region is obtained, and the indoor solar radiation heat intake is adjusted. Application No. 201280036901.5 discloses a preparation method of TCO material similar to ATO, which obtains a composite film with near-infrared modulation capability, but the preparation method of TCO material provided by the above invention utilizes colloid technology with very complicated process, centrifugation and solution washing are the key steps of the technology, just because these steps result in high loss rate of TCO nanoparticles, and the material preparation time is long, which is not suitable for industrial mass production. Therefore, the technical problem of industrial production of the ATO nanocrystalline electrochromic film is solved, and the technology is in the forefront.
Disclosure of Invention
The invention aims to provide a preparation method of an antimony doped tin oxide electrochromic film, which solves the technical problem of industrial production of an ATO nanocrystalline electrochromic film.
The technical scheme adopted by the invention is that the preparation method of the antimony doped tin oxide electrochromic film comprises the following specific steps:
step 1, preparing a spraying liquid: firstly, adding antimony trichloride into acetylacetone, stirring for 30min at 50-60 ℃, then adding stannic chloride pentahydrate, continuing to stir for 1 h at 50-60 ℃, adding acetic anhydride into the mixed solution after the mixed solution is cooled to room temperature, stirring for 30min at room temperature, finally adding absolute ethyl alcohol, and stirring for 20min at room temperature to obtain an ATO spraying solution;
step 2, preparing an ATO film: firstly, placing a soda-lime glass substrate into a heating furnace, heating to 350-450 ℃, driving the soda-lime glass substrate to move to a spraying chamber by a transmission device, spraying the ATO spraying liquid prepared in the step 1 on the surface of the soda-lime glass substrate by using an ultrasonic spraying spray gun by taking nitrogen as carrier gas, cooling by strong wind after spraying is finished, unloading coated glass, and finally obtaining the antimony-doped tin oxide electrochromic film.
The present invention is also characterized in that,
in the step 1, the raw material ratio for preparing the ATO spraying liquid is as follows: the molar ratio of stannic chloride, antimony chloride, absolute ethyl alcohol, acetylacetone and acetic anhydride is 1: 0.01-0.05: 45-50: 4-7.2: 1.0 to 2.0.
In the step 2, the pressure of the carrier gas is 1 bar-1.5 bar.
In the step 2, the ultrasonic frequency of the ultrasonic spray gun is 2.4MHz, and the power is 100W-300W; the distance between the ultrasonic spray gun and the soda-lime glass substrate is 3 cm-10 cm, and the spraying time is 30 s-1 min.
In the step 2, the thickness of the prepared antimony doped tin oxide electrochromic film is 150 nm-300 nm.
In the step 2, the grain size of the prepared antimony doped tin oxide electrochromic film is 5-15 nm.
In the step 2, the carrier concentration of the prepared antimony doped tin oxide electrochromic film is 5 × 1019Per cm3～8×1020Per cm3。
The preparation method has the advantages of simple process, controllable grain size, no need of special vacuum environment and reaction chamber, short coating time and high film preparation efficiency, and can be used for preparing large-area ATO nanocrystalline films in batches.
Drawings
FIG. 1 is a graph comparing the transmittance curves of the ATO films prepared in example 2 of the present invention in the faded state versus the colored state.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of an antimony-doped tin oxide electrochromic film, which comprises the following specific steps:
step 1, preparing a spraying liquid: firstly, adding antimony trichloride into acetylacetone, stirring for 30min at 50-60 ℃, then adding stannic chloride pentahydrate, continuing to stir for 1 h at 50-60 ℃, adding acetic anhydride into the mixed solution after the mixed solution is cooled to room temperature, stirring for 30min at room temperature, finally adding absolute ethyl alcohol, and stirring for 20min at room temperature to obtain an ATO spraying solution;
in the step 1, the raw material ratio for preparing the ATO spraying liquid is as follows: the molar ratio of stannic chloride, antimony chloride, absolute ethyl alcohol, acetylacetone and acetic anhydride is 1: 0.01-0.05: 45-50: 4-7.2: 1.0 to 2.0;
step 2, preparing an ATO film: firstly, placing a soda-lime glass substrate into a heating furnace, heating to 350-450 ℃, driving the soda-lime glass substrate to move to a spraying chamber by a transmission device, spraying the ATO spraying liquid prepared in the step 1 on the surface of the soda-lime glass substrate by using an ultrasonic spraying spray gun by taking nitrogen as carrier gas, cooling by strong wind after spraying is finished, unloading coated glass, and finally obtaining the antimony-doped tin oxide electrochromic film.
In the step 2, the pressure of the carrier gas is 1 bar-1.5 bar.
In the step 2, the ultrasonic frequency of the ultrasonic spray gun is 2.4MHz, and the power is 100W-300W; the distance between the ultrasonic spray gun and the soda-lime glass substrate is 3 cm-10 cm, and the spraying time is 30 s-1 min.
In the step 2, the thickness of the prepared antimony doped tin oxide electrochromic film is 150 nm-300 nm.
In the step 2, the grain size of the prepared antimony doped tin oxide electrochromic film is 5-15 nm.
In the step 2, the carrier concentration of the prepared antimony doped tin oxide electrochromic film is 5 × 1019Per cm3～8×1020Per cm3。
Example 1
A preparation method of an antimony-doped tin oxide electrochromic film comprises the following specific steps:
firstly, preparing a spraying liquid: 0.65g of antimony trichloride was added to 114.23g of acetylacetone, and magnetic stirring was carried out at 50 ℃ for 30min, then 100g of tin tetrachloride pentahydrate was added, and magnetic stirring was continued at 50 ℃ for 1 hour to obtain an orange solution. After the solution is cooled to room temperature, 29.12g of acetic anhydride is added into the solution and stirred for 30min at room temperature, and finally 591.23g of absolute ethyl alcohol is added into the solution and stirred for 20min at room temperature to obtain the ATO spraying liquid with stable performance. Wherein, the spraying liquid comprises the following components in percentage by weight: the molar ratio of stannic chloride, antimony chloride, absolute ethyl alcohol, acetylacetone and acetic anhydride is 1: 0.01: 45: 4: 1.0.
then, the film was formed by ultrasonic spray pyrolysis. Cleaning a common soda-lime glass substrate, putting the substrate into a heating furnace for heating, when the temperature of the substrate rises to 350 ℃, driving the substrate to move to a spraying chamber by a transmission device, taking nitrogen as carrier gas, opening a nitrogen valve, setting the air pressure value to be 1bar, simultaneously opening an ultrasonic magnetic vibrator switch, setting the ultrasonic frequency to be 2.4MHz and the power to be 100W, putting an ultrasonic spraying spray gun into the heating furnace, adjusting the distance between a spray gun nozzle and the glass substrate to be 3cm, setting the spraying time to be 30s, and starting spraying. And after the spraying is finished, translating the glass substrate plated with the ATO nanocrystalline film to a cooling area, cooling by strong wind, unloading the coated glass, and finishing the preparation of the ATO nanocrystalline film.
Finally, the ATO film is prepared with the thickness of 150nm, the grain size of about 5nm, and the carrier concentration of 5 × 1019Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 60%, the coloring time is 1.0s, the fading time is 1.5s, the coloring and fading cycle is 5 ten thousand times, and the coloring and fading contrast performance is only reduced by 3.0%.
Example 2
A preparation method of an antimony-doped tin oxide electrochromic film comprises the following specific steps:
firstly, preparing a spraying liquid: 2.60g of antimony trichloride was added to 171.34g of acetylacetone, and magnetic stirring was carried out at 55 ℃ for 30min, then 100g of tin tetrachloride pentahydrate was added, and magnetic stirring was continued at 55 ℃ for 1 hour to obtain an orange solution. After the solution is cooled to room temperature, 43.68g of acetic anhydride is added into the solution and stirred for 30min at room temperature, finally 617.57g of absolute ethyl alcohol is added into the solution and stirred for 20min at room temperature, and the ATO spraying solution with stable performance is obtained. Wherein, the spraying liquid comprises the following components in percentage by weight: the molar ratio of stannic chloride, antimony chloride, absolute ethyl alcohol, acetylacetone and acetic anhydride is 1: 0.04: 47: 6: 1.5.
then, the film was formed by ultrasonic spray pyrolysis. Cleaning a common soda-lime glass substrate, putting the substrate into a heating furnace for heating, when the temperature of the substrate rises to 400 ℃, driving the substrate to move to a spraying chamber by a transmission device, taking nitrogen as carrier gas, opening a nitrogen valve, setting the air pressure value to be 1.2bar, simultaneously opening an ultrasonic magnetic vibrator switch, setting the ultrasonic frequency to be 2.4MHz and the power to be 200W, putting an ultrasonic spraying spray gun into the heating furnace, adjusting the distance between the nozzle of the spray gun and the glass substrate to be 5cm, setting the spraying time to be 50s, and starting spraying. And after the spraying is finished, translating the glass substrate plated with the ATO nanocrystalline film to a cooling area, cooling by strong wind, unloading the coated glass, and finishing the preparation of the ATO nanocrystalline film.
Finally, the ATO film prepared has the thickness of 250nm, the grain size of about 10nm and the carrier concentration of 7.5 × 1020Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 70%, the coloring time is 800ms, the fading time is 900ms, the coloring and fading cycle is 5 ten thousand times, and the coloring and fading contrast performance is reduced by only 1.0%.
As can be seen from fig. 1, in the bleached state, the transmittance of the ATO film in the visible-near infrared band is maintained above 85%; in the colored state, the transmittance of the ATO film is obviously reduced in the near infrared band, and the coloring and fading effects are obvious.
Example 3
A preparation method of an antimony-doped tin oxide electrochromic film comprises the following specific steps:
first, a spray coating solution is prepared. 3.25g of antimony trichloride was added to 205.61g of acetylacetone, and magnetic stirring was carried out at 60 ℃ for 30min, then 100g of tin tetrachloride pentahydrate was added, and magnetic stirring was continued at 60 ℃ for 1 hour to obtain an orange solution. And after the solution is cooled to room temperature, adding 58.24g of acetic anhydride, stirring at room temperature for 30min, finally adding 656.99g of absolute ethyl alcohol, and stirring at room temperature for 20min to obtain the ATO spray coating liquid with stable performance. Wherein, the spraying liquid comprises the following components in percentage by weight: the molar ratio of stannic chloride, antimony chloride, absolute ethyl alcohol, acetylacetone and acetic anhydride is 1: 0.05: 50: 7.2: 2.0.
then, the film was formed by ultrasonic spray pyrolysis. Cleaning a common soda-lime glass substrate, putting the substrate into a heating furnace for heating, when the temperature of the substrate rises to 450 ℃, driving the substrate to move to a spraying chamber by a transmission device, taking nitrogen as carrier gas, opening a nitrogen valve, setting the air pressure value to be 1.5bar, simultaneously opening an ultrasonic magnetic vibrator switch, setting the ultrasonic frequency to be 2.4MHz and the power to be 300W, putting an ultrasonic spraying gun into the heating furnace, adjusting the distance between the nozzle of the spraying gun and the glass substrate to be 10cm, setting the spraying time to be 1min, and starting spraying. And after the spraying is finished, translating the glass substrate plated with the ATO nanocrystalline film to a cooling area, cooling by strong wind, unloading the coated glass, and finishing the preparation of the ATO nanocrystalline film.
Finally, the productThe thickness of the prepared ATO film is 300nm, the grain size is about 15nm, and the carrier concentration is 8.0 × 1020Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 65%, the coloring time is 1.2s, the fading time is 2.0s, the coloring and fading cycle is 5 ten thousand times, and the coloring and fading contrast performance is only reduced by 2.0%.
Example 4
A preparation method of an antimony-doped tin oxide electrochromic film comprises the following specific steps:
first, a spray coating solution is prepared. 1.30g of antimony trichloride was added to 142.78g of acetylacetone, and magnetic stirring was carried out at 60 ℃ for 30min, then 100g of tin tetrachloride pentahydrate was added, and magnetic stirring was continued at 60 ℃ for 1 hour to obtain an orange solution. And after the solution is cooled to room temperature, adding 58.24g of acetic anhydride, stirring at room temperature for 30min, finally adding 604.43g of absolute ethyl alcohol, and stirring at room temperature for 20min to obtain the ATO spray coating liquid with stable performance. Wherein, the spraying liquid comprises the following components in percentage by weight: the molar ratio of stannic chloride, antimony chloride, absolute ethyl alcohol, acetylacetone and acetic anhydride is 1: 0.02: 46: 5: 2.0.
then, the film was formed by ultrasonic spray pyrolysis. Cleaning a common soda-lime glass substrate, putting the substrate into a heating furnace for heating, when the temperature of the substrate rises to 400 ℃, driving the substrate to move to a spraying chamber by a transmission device, taking nitrogen as carrier gas, opening a nitrogen valve, setting the air pressure value to be 1.5bar, simultaneously opening an ultrasonic magnetic vibrator switch, setting the ultrasonic frequency to be 2.4MHz and the power to be 200W, putting an ultrasonic spraying spray gun into the heating furnace, adjusting the distance between the nozzle of the spray gun and the glass substrate to be 8cm, setting the spraying time to be 40s, and starting spraying. And after the spraying is finished, translating the glass substrate plated with the ATO nanocrystalline film to a cooling area, cooling by strong wind, unloading the coated glass, and finishing the preparation of the ATO nanocrystalline film.
Finally, the thickness of the prepared ATO film is 220nm, the grain size is about 8nm, and the carrier concentration is 6 × 1020Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 75%, the coloring time is 700ms, the fading time is 800ms, the coloring and fading circulation is 5 ten thousand times, and the coloring and fading contrast ratioThe performance was reduced by only 1.0%.
Example 5
A preparation method of an antimony-doped tin oxide electrochromic film comprises the following specific steps:
first, a spray coating solution is prepared. 1.95g of antimony trichloride was added to 171.34g of acetylacetone, and magnetic stirring was carried out at 60 ℃ for 30min, then 100g of tin tetrachloride pentahydrate was added, and magnetic stirring was continued at 60 ℃ for 1 hour to obtain an orange solution. And after the solution is cooled to room temperature, adding 52.41g of acetic anhydride into the solution, stirring the solution at room temperature for 30min, finally adding 630.71g of absolute ethyl alcohol, and stirring the solution at room temperature for 20min to obtain the ATO spray coating liquid with stable performance. Wherein, the spraying liquid comprises the following components in percentage by weight: the molar ratio of stannic chloride, antimony chloride, absolute ethyl alcohol, acetylacetone and acetic anhydride is 1: 0.05: 50: 7.2: 1.8.
then, the film was formed by ultrasonic spray pyrolysis. Cleaning a common soda-lime glass substrate, putting the substrate into a heating furnace for heating, when the temperature of the substrate rises to 450 ℃, driving the substrate to move to a spraying chamber by a transmission device, taking nitrogen as carrier gas, opening a nitrogen valve, setting the air pressure value to be 1.2bar, simultaneously opening an ultrasonic magnetic vibrator switch, setting the ultrasonic frequency to be 2.4MHz and the power to be 100W, putting an ultrasonic spraying spray gun into the heating furnace, adjusting the distance between the nozzle of the spray gun and the glass substrate to be 5cm, setting the spraying time to be 30s, and starting spraying. And after the spraying is finished, translating the glass substrate plated with the ATO nanocrystalline film to a cooling area, cooling by strong wind, unloading the coated glass, and finishing the preparation of the ATO nanocrystalline film.
Finally, the thickness of the prepared ATO film is 180nm, the grain size is about 6nm, and the carrier concentration is 5.5 × 1020Per cm3. The film has good near-infrared electrochromic performance, the coloring and fading contrast ratio at 2000nm is 65%, the coloring time is 1.4s, the fading time is 1.5s, the coloring and fading cycle is 5 ten thousand times, and the coloring and fading contrast performance is only reduced by 3.0%.
The preparation method has the advantages of simple process, controllable grain size, no need of special vacuum environment and reaction chamber, short coating time, high film preparation efficiency and capability of preparing large-area ATO nanocrystalline films in batches.
Claims (6)
1. A preparation method of an antimony-doped tin oxide electrochromic film is characterized by comprising the following specific steps:
step 1, preparing a spraying liquid: firstly, adding antimony trichloride into acetylacetone, stirring for 30min at 50-60 ℃, then adding stannic chloride pentahydrate, continuing to stir for 1 h at 50-60 ℃, adding acetic anhydride into the mixed solution after the mixed solution is cooled to room temperature, stirring for 30min at room temperature, finally adding absolute ethyl alcohol, and stirring for 20min at room temperature to obtain an ATO spraying solution;
step 2, preparing an ATO film: firstly, placing a soda-lime glass substrate into a heating furnace, heating to 350-450 ℃, driving the soda-lime glass substrate to move to a spraying chamber by a transmission device, spraying the ATO spraying liquid prepared in the step 1 on the surface of the soda-lime glass substrate by using an ultrasonic spraying spray gun by taking nitrogen as carrier gas, cooling by strong wind after spraying is finished, unloading coated glass, and finally obtaining the antimony-doped tin oxide electrochromic film;
in the step 1, the raw material ratio for preparing the ATO spraying liquid is as follows: the molar ratio of stannic chloride, antimony chloride, absolute ethyl alcohol, acetylacetone and acetic anhydride is 1: 0.01-0.05: 45-50: 4-7.2: 1.0 to 2.0.
2. The method for preparing the antimony doped tin oxide electrochromic film according to claim 1, wherein in the step 2, the gas pressure of the carrier gas is 1bar to 1.5 bar.
3. The preparation method of the antimony doped tin oxide electrochromic film according to claim 1, wherein in the step 2, the ultrasonic frequency of an ultrasonic spray gun is 2.4MHz, and the power is 100W-300W; the distance between the ultrasonic spray gun and the soda-lime glass substrate is 3 cm-10 cm, and the spraying time is 30 s-1 min.
4. The method for preparing the antimony doped tin oxide electrochromic film according to claim 1, wherein in the step 2, the prepared antimony doped tin oxide electrochromic film has a thickness of 150nm to 300 nm.
5. The method for preparing the antimony doped tin oxide electrochromic film according to claim 1, wherein in the step 2, the grain size of the prepared antimony doped tin oxide electrochromic film is 5 nm-15 nm.
6. The method for preparing the antimony-doped tin oxide electrochromic film according to claim 1, wherein in the step 2, the carrier concentration of the prepared antimony-doped tin oxide electrochromic film is 5 × 1019Per cm3～8×1020Per cm3。
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| CN102646759A (en) * | 2012-05-04 | 2012-08-22 | 深圳市科聚新材料有限公司 | Preparing method for transparent conductive oxide film |
| CN105036564A (en) * | 2015-06-25 | 2015-11-11 | 西安理工大学 | Nanocrystalline enhanced tungsten oxide electrochromic film and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102646759A (en) * | 2012-05-04 | 2012-08-22 | 深圳市科聚新材料有限公司 | Preparing method for transparent conductive oxide film |
| CN105036564A (en) * | 2015-06-25 | 2015-11-11 | 西安理工大学 | Nanocrystalline enhanced tungsten oxide electrochromic film and preparation method thereof |
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