CN111747657A - Preparation method of molybdenum-doped tungsten oxide nanostructure electrochromic film - Google Patents
Preparation method of molybdenum-doped tungsten oxide nanostructure electrochromic film Download PDFInfo
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 57
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011521 glass Substances 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 14
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 14
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 7
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims abstract description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940116411 terpineol Drugs 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 238000007650 screen-printing Methods 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 2
- 238000002390 rotary evaporation Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 10
- 239000010409 thin film Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Images
Classifications
-
- 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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1524—Transition metal compounds
-
- 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
- C03C2217/219—CrOx, MoOx, WOx
-
- 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
- C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
-
- 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
- C03C2218/119—Deposition methods from solutions or suspensions by printing
Abstract
The invention discloses a preparation method of a molybdenum-doped tungsten oxide nanostructure electrochromic film, which adopts the technical scheme that the method comprises the following steps: dissolving tungstic acid in hydrogen peroxide, heating and stirring in an oil bath until a clear solution is obtained, adding molybdenum oxide, ethylene glycol and deionized water into the clear solution, heating an oil bath, condensing and refluxing to obtain molybdenum-doped tungsten oxide nano sol, centrifuging and washing for later use; dissolving ethyl cellulose in ethanol at room temperature, stirring to obtain clear and transparent sol, adding terpineol and the molybdenum-doped tungsten oxide nano sol prepared in the previous step into the sol, and performing rotary evaporation on an organic solvent to obtain molybdenum-doped tungsten oxide nano slurry; uniformly attaching the molybdenum-doped tungsten oxide nano slurry to an ITO (indium tin oxide) or FTO (fluorine-doped tin oxide) conductive glass substrate by adopting a screen printing or blade coating method, calcining by using a muffle furnace, and naturally cooling to obtain the molybdenum-doped tungsten oxide nano structural electrochromic film.
Description
The application is a divisional application, and the original application name is: a method for preparing a screen printing molybdenum doped tungsten oxide nanostructure electrochromic film is disclosed, and the application number is as follows: 2017102708795, filing date: 20170424.
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of electrochromism, and particularly relates to a preparation method of a molybdenum-doped tungsten oxide nanostructure electrochromism film.
[ background of the invention ]
A phenomenon that a material exhibits a reversible color change when a voltage is applied to the material is called electrochromism, and electrochromic materials include organic materials and inorganic materials, which are receiving attention due to their good cycle stability, and tungsten oxide is a representative substance among inorganic materials.
At present, magnetron sputtering is mostly adopted for preparing large-area tungsten oxide electrochromic films, but a plurality of problems exist: the cost is expensive and the energy consumption is large. One continuous magnetron sputtering instrument is tens of millions in movement and has large power consumption. And secondly, the tungsten oxide film prepared by magnetron sputtering is too compact, is not beneficial to the insertion and the extraction of lithium ions in the color changing process, and has the problems of overlong response time, poor energy utilization rate and the like. How to prepare the electrochromic film with large area and loose and porous microstructure by a simple and cheap process is a problem to be solved urgently in the engineering process.
[ summary of the invention ]
The invention provides a preparation method of a molybdenum-doped tungsten oxide nanostructure electrochromic film, and the prepared film has a loose and porous structure, is beneficial to embedding and removing electrolyte ions in an electrochromic process, has the advantages of short response time, high color change speed and the like, and is hopeful to be applied and popularized in the electrochromic industrialization process.
The invention is realized by the following technical scheme:
a preparation method of a molybdenum-doped tungsten oxide nanostructure electrochromic film comprises the following steps:
a. dissolving tungstic acid in hydrogen peroxide, heating and stirring in an oil bath until a clear solution is obtained, adding molybdenum oxide, ethylene glycol and deionized water into the clear solution, heating an oil bath, condensing and refluxing to obtain molybdenum-doped tungsten oxide nano sol, centrifuging and washing for later use;
b. at room temperature, dissolving ethyl cellulose in ethanol, stirring to obtain clear and transparent sol, adding terpineol and the molybdenum-doped tungsten oxide nano sol prepared in the step a into the sol, and rotationally evaporating an organic solvent to obtain molybdenum-doped tungsten oxide nano slurry;
c. uniformly attaching the molybdenum-doped tungsten oxide nano slurry to an ITO (indium tin oxide) or FTO (fluorine-doped tin oxide) conductive glass substrate by adopting a screen printing or blade coating method, calcining by using a muffle furnace, and naturally cooling to obtain the molybdenum-doped tungsten oxide nano structural electrochromic film.
Preferably, the initial heating temperature of the oil bath in the step a is 85-95 ℃, the temperature of an oil bath pot after adding molybdenum oxide, ethylene glycol and deionized water is 100-130 ℃, the centrifugation speed is 8000-12000 rpm, the centrifugation time is 15-25 min, and deionized water and ethanol are adopted for washing.
Preferably, in the ethylcellulose sol in the step b, the mass ratio of the ethylcellulose to the ethanol is 1: 8-1: 12. the ethyl cellulose is generally insoluble in water, and the proportion of the ethyl cellulose and the ethanol is selected to be proper, so that the dissolving and volatilization of organic matters can be facilitated, and the porosity of the film is improved.
Preferably, the mass ratio of the molybdenum-doped tungsten oxide, the ethyl cellulose sol and the terpineol in the step b is 1: 4: 5-1: 6: 3. the tungsten oxide nano particles have small size, and after redundant organic matters are volatilized, a main body structure of the porous film is formed.
Preferably, the ITO or FTO conductive glass in the step c is subjected to ultrasonic cleaning treatment and surface activity treatment, wherein the ultrasonic cleaning treatment is to perform ultrasonic treatment on the ITO or FTO conductive glass for 10-15 minutes by using a detergent, deionized water, acetone and ethanol respectively, and dry the ITO or FTO conductive glass in an oven at the temperature of 60-80 ℃. The glass is ultrasonically cleaned by using a mixed solution of a detergent, deionized water, acetone and ethanol, so that foreign matters on the surface are effectively removed, and the glass can be removed by ultrasonic oscillation even though insoluble chemical substances are adsorbed.
Preferably, the surface active treatment is to carry out surface active treatment on the ITO or FTO conductive glass by using a plasma instrument, the working power is 150-250 w, the time is 5-10 min, and the pressure change sequence of oxygen is controlled to be 120Pa, 40Pa, 90Pa and 68Pa during working. The surface of the conductive glass is subjected to surface active treatment, particularly the pressure of oxygen is controlled, the nanoscale material adhesion rate is favorably controlled, and the service life of the electrochromic layer is prolonged.
Preferably, the heat treatment temperature of the muffle furnace in the step c is 350-480 ℃, and the heat preservation time is 1-3 h. The muffle furnace has stable high-temperature condition, is beneficial to the full volatilization of organic matters, and is suitable for the mass production of large-area porous structure films.
Compared with the prior art, the invention has the following advantages:
(1) according to the preparation method of the electrochromic film with the molybdenum-doped tungsten oxide nano structure, the molybdenum-doped tungsten oxide film is adopted for screen printing, the thickness of the film layer can be controlled to be 50-400 nm, the size of tungsten oxide nano particles is small, electron transmission is facilitated, the transmission efficiency is improved, and therefore the color changing efficiency is improved;
(2) according to the preparation method of the electrochromic film with the molybdenum-doped tungsten oxide nanostructure, the molybdenum-doped tungsten oxide nano sol prepared based on a condensation reflux method is a simple and convenient method for preparing a large-area electrochromic layer, after the molybdenum-doped tungsten oxide film is subjected to heat treatment, a loose and porous microstructure is generated due to volatilization of organic matters, so that the ion embedding and ion separation in the color changing process are facilitated, the molybdenum-doped tungsten oxide film is prepared by screen printing, and the key problem encountered in the industrialization of an electrochromic intelligent window is solved;
(2) the preparation method of the electrochromic film with the molybdenum-doped tungsten oxide nanostructure, disclosed by the invention, has the advantages of low process energy consumption and low cost, is beneficial to greatly reducing the production cost of enterprises, and is expected to be popularized in the engineering of electrochromic intelligent windows.
[ description of the drawings ]
FIG. 1 is an electron micrograph of a cross section of a screen printed molybdenum doped tungsten oxide film of example 1;
FIG. 2 is a digital photograph of the assembled device of example 1 before discoloration;
FIG. 3 is a digital photograph of the assembled device of example 1 after discoloration;
FIG. 4 is a graph of the transmittance of the assembled device of example 1;
FIG. 5 is a current-potential diagram of the assembled device in example 2;
fig. 6 is a cyclic voltammogram of the assembled device of example 2.
[ detailed description ] embodiments
The preparation method of the electrochromic film with the molybdenum-doped tungsten oxide nano structure is described by combining specific embodiments
Example 1:
a. dissolving 5g of tungstic acid in 60mL of 30% hydrogen peroxide, heating the solution in an oil bath to 95 ℃, stirring the solution to obtain a clear solution, adding 1.44g of molybdenum oxide, 70mL of ethylene glycol and 70mL of deionized water into the clear solution, heating an oil bath pot to 120 ℃, condensing and refluxing the solution for 10 hours to obtain nano tungsten oxide sol, centrifuging the solution at 10000rpm for 20 minutes, pouring out supernatant, and washing precipitates by using ionized water and ethanol respectively;
b. dissolving ethyl cellulose in ethanol at room temperature, wherein the mass ratio of the ethyl cellulose to the ethanol is 1: stirring to obtain clear and transparent sol, taking 15g of the sol, adding 12g of terpineol and 3g of molybdenum-doped tungsten oxide nano sol, and rotationally evaporating the organic solvent at 90 ℃ to prepare molybdenum-doped tungsten oxide nano slurry;
c. respectively carrying out ultrasonic treatment on ITO or FTO conductive glass for 15 minutes by using a detergent, deionized water, acetone and ethanol, drying the ITO or FTO conductive glass in an oven at the temperature of 70 ℃, carrying out surface active treatment on the ITO or FTO conductive glass by using a plasma instrument at the working power of 200w for 5 minutes, controlling the pressure change sequence of oxygen to be 120Pa, 40Pa, 90Pa and 68Pa during working, taking 1g of the prepared molybdenum-doped tungsten oxide nano slurry, uniformly attaching the molybdenum-doped tungsten oxide nano slurry to the ITO or FTO conductive glass by using a blade coating method, carrying out heat treatment on the ITO or FTO conductive glass by using a muffle furnace, setting the temperature of the muffle furnace to be 450 ℃, keeping the temperature for 2 hours, and naturally cooling to obtain the molybdenum-doped tungsten oxide nano-structure electrochromic film with the thickness of 50 nm.
FIG. 1 is an electron micrograph of a cross section of a screen-printed molybdenum-doped tungsten oxide thin film of example 1;
to further understand the electrochromic properties of the molybdenum-doped tungsten oxide thin film prepared in example 1, the prepared thin film was assembled into a device, and the change in light transmittance of the device was measured using a two-electrode system in combination with an electrochemical workstation and an ultraviolet spectrophotometer, and the results showed that the device turned blue when negative pressure (-3V) was applied to the device; a positive pressure (2V) was applied thereto, and the device was discolored.
Fig. 2 and 3 are front and rear digital photographs of the assembled device in example 1, fig. 2 is a transparent state, fig. 3 is a colored state, fig. 4 is a transmittance diagram of the assembled device in example 1, and the light modulation range is 35%, illustrating that the electrochromic device has good cycle stability.
Example 2:
a. 5g of tungstic acid was dissolved in 60mL of 30% hydrogen peroxide, heated to 95 ℃ in an oil bath and stirred to obtain a clear solution. Adding 1.44g of molybdenum oxide, 70mL of ethylene glycol and 70mL of deionized water into the obtained clear solution, heating the oil bath to 110 ℃, and carrying out condensation reflux for 12 hours to obtain the tungsten oxide nano sol. Then, centrifuging at 10000rpm/min for 20min, and pouring out supernatant; finally, washing the precipitate by respectively adopting ionized water and ethanol;
b. dissolving ethyl cellulose in ethanol at room temperature, wherein the mass ratio of the ethyl cellulose to the ethanol is 1: and 5, stirring to obtain clear and transparent sol. Then, 9g of terpineol and 3g of molybdenum-doped tungsten oxide nano sol are added into 18g of clear ethyl cellulose sol, and the organic solvent is evaporated in a rotating manner at 90 ℃ to prepare molybdenum-doped tungsten oxide nano slurry;
c. respectively carrying out ultrasonic treatment on ITO or FTO conductive glass for 15 minutes by using a detergent, deionized water, acetone and ethanol, and drying by using an oven at the temperature of 70 ℃; performing surface active treatment on ITO or FTO conductive glass by using a plasma instrument, wherein the working power is 200w, the time is 8min, the pressure change sequence of oxygen in working is controlled to be 120Pa, 40Pa, 90Pa and 68Pa, and uniformly attaching 1g of molybdenum-doped tungsten oxide nano slurry prepared in the previous step to the ITO or FTO conductive glass by using a blade coating method. And then carrying out heat treatment on the film by using a muffle furnace, setting the temperature of the muffle furnace at 400 ℃, keeping the temperature for 1h, and naturally cooling to obtain the electrochromic film with the molybdenum-doped tungsten oxide nano structure, wherein the thickness of the obtained film layer is 400 nm.
To further understand the electrochromic properties of the molybdenum-doped tungsten oxide thin film prepared in example 2, the prepared thin film was assembled into a device, and the change in light transmittance of the device was measured using a two-electrode system in combination with an electrochemical workstation and an ultraviolet spectrophotometer, and the results showed that the device turned blue when negative pressure (-3V) was applied to the device; a positive pressure (2V) was applied thereto, and the device was discolored.
FIG. 5 is a current-potential diagram of the assembled device of example 2, with a light modulation range of 35%; fig. 6 is a cyclic voltammogram of the assembled device of example 2, illustrating that the electrochromic device has better capacitance.
The invention relates to a preparation method of a molybdenum-doped tungsten oxide nanostructure electrochromic film, which is a simple and convenient method for preparing a large-area electrochromic layer based on molybdenum-doped tungsten oxide nano sol prepared by a condensation reflux method, wherein after the molybdenum-doped tungsten oxide film is subjected to heat treatment, a loose and porous microstructure is generated due to volatilization of organic matters, so that ions can be embedded and removed in the process of color change, the molybdenum-doped tungsten oxide film is prepared by screen printing, the thickness of the film layer can be controlled to be 50-400 nm, the size of tungsten oxide nano particles is small, the electronic transmission is facilitated, the transmission efficiency is improved, and the color change efficiency is improved.
Claims (1)
1. A preparation method of a molybdenum-doped tungsten oxide nanostructure electrochromic film is characterized by comprising the following steps:
a. dissolving 5g of tungstic acid in 60mL of 30% hydrogen peroxide, heating the solution in an oil bath to 95 ℃, stirring the solution to obtain a clear solution, adding 1.44g of molybdenum oxide, 70mL of ethylene glycol and 70mL of deionized water into the clear solution, heating an oil bath pot to 120 ℃, condensing and refluxing the solution for 10 hours to obtain nano tungsten oxide sol, centrifuging the solution at 10000rpm for 20 minutes, pouring out supernatant, and washing precipitates by using ionized water and ethanol respectively;
b. dissolving ethyl cellulose in ethanol at room temperature, wherein the mass ratio of the ethyl cellulose to the ethanol is 1: stirring to obtain clear and transparent sol, taking 15g of the sol, adding 12g of terpineol and 3g of molybdenum-doped tungsten oxide nano sol, and rotationally evaporating the organic solvent at 90 ℃ to prepare molybdenum-doped tungsten oxide nano slurry;
c. respectively carrying out ultrasonic treatment on ITO or FTO conductive glass for 15 minutes by using a detergent, deionized water, acetone and ethanol, drying the ITO or FTO conductive glass in an oven at the temperature of 70 ℃, carrying out surface activity treatment on the ITO or FTO conductive glass by using a plasma instrument at the working power of 200w for 5 minutes, controlling the pressure change sequence of oxygen to be 120Pa, 40Pa, 90Pa and 68Pa during working, uniformly attaching 1g of prepared molybdenum-doped tungsten oxide nano slurry to the ITO or FTO conductive glass by adopting a blade coating method, carrying out heat treatment on the ITO or FTO conductive glass by using a muffle furnace, setting the temperature of the muffle furnace to be 450 ℃, keeping the temperature for 2 hours, and naturally cooling to obtain the molybdenum-doped tungsten oxide nano structure electrochromic film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010444685.4A CN111747657A (en) | 2017-04-24 | 2017-04-24 | Preparation method of molybdenum-doped tungsten oxide nanostructure electrochromic film |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010444685.4A CN111747657A (en) | 2017-04-24 | 2017-04-24 | Preparation method of molybdenum-doped tungsten oxide nanostructure electrochromic film |
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| CN108574019A (en) * | 2018-02-28 | 2018-09-25 | 广东工业大学 | A kind of tungstic acid semiconductive thin film and its preparation method and application |
| CN108424004A (en) * | 2018-04-17 | 2018-08-21 | 上海艾谡新材料有限公司 | A kind of preparation method of nanoscale molybdenum oxide electrochomeric films |
| CN110376816B (en) * | 2019-07-16 | 2021-01-15 | 西安交通大学 | Self-powered tungsten oxide-based electrochromic device based on aluminum ion hydrogel and preparation method thereof |
| CN110467357B (en) * | 2019-08-01 | 2021-10-22 | 西安理工大学 | Tungsten oxide film with horn-shaped pore structure and preparation method thereof |
| CN110488549B (en) * | 2019-09-10 | 2021-10-26 | 南京邮电大学 | Large-area patterned solid electrochromic film and preparation method and application thereof |
| CN110627372B (en) * | 2019-09-30 | 2022-03-04 | 东北大学秦皇岛分校 | Method for preparing lithium titanate electrochromic film |
| US20210271145A1 (en) * | 2020-02-25 | 2021-09-02 | Sage Electrochromics, Inc. | Approaches to modifying a color of an electrochromic stack in a tinted state |
| CN113754307A (en) * | 2021-09-29 | 2021-12-07 | 中山市中佳新材料有限公司 | Thermochromic film and preparation method thereof |
| CN115432939B (en) * | 2022-03-22 | 2024-04-09 | 苏州科技大学 | High-performance tungsten trioxide/bismuth tungstate film and preparation method thereof |
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| CN107098596B (en) | 2020-06-23 |
| CN107098596A (en) | 2017-08-29 |
| CN111646706A (en) | 2020-09-11 |
| CN111646705A (en) | 2020-09-11 |
| CN111704365A (en) | 2020-09-25 |
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