CN112961539A - Nano tungsten oxide printing ink suitable for ink-jet printing film forming process, and preparation method and application thereof - Google Patents
Nano tungsten oxide printing ink suitable for ink-jet printing film forming process, and preparation method and application thereof 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 136
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 136
- 238000007641 inkjet printing Methods 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000007639 printing Methods 0.000 title claims abstract description 13
- 238000000227 grinding Methods 0.000 claims description 64
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 34
- 239000006185 dispersion Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 238000010790 dilution Methods 0.000 description 8
- 238000005562 fading Methods 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000011858 nanopowder Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910003091 WCl6 Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
Abstract
The invention discloses a nano tungsten oxide ink suitable for an ink-jet printing film-forming process, a preparation method and application thereof. The nano tungsten oxide ink prepared by the invention is suitable for ink-jet printing and has good printing effect. The tungsten oxide film with electrochromic property can be directly prepared by adopting the ink through ink-jet printing, and an effective solution is provided for large-area uniform preparation and low cost of the electrochromic film.
Description
Technical Field
The invention relates to nano tungsten oxide ink for ink-jet printing and a preparation method thereof, belonging to the field of ink.
Background
Tungsten oxide, also known as wolfram, of formula WO3. The light yellow orthorhombic crystal is dark in color when heated, is recovered to be light yellow after being cooled, is stable in air, has the melting point of 1473 ℃, the boiling point of over 1750 ℃ and the relative density of 7.16, is insoluble in water and inorganic acid except hydrofluoric acid, and can be dissolved in hot concentrated sodium hydroxide solution and ammonia water. The octahedral unit can incline and rotate according to different crystal forms and the surrounding environmentAnd the distortion in different modes is accompanied by the phenomenon that tungsten deviates from the center of an octahedron, and the existence of oxygen vacancies can affect unit cells, bond lengths and electronic structures to different degrees, so that the charge distribution, energy gaps, stoichiometric ratio and the like are changed. The tungsten oxide in the coloring state is dark blue, and is suitable for daily household use due to softer color and better light-blocking performance. As a novel functional material, tungsten oxide has the characteristics of low production cost, easy synthesis, low energy consumption, wide viewing angle, high coloring efficiency, strong color contrast, long service life, good stability and the like, and all of the characteristics make the tungsten oxide a research hotspot in the field of electrochromism.
The traditional methods for preparing the tungsten oxide film comprise an evaporation method, a sputtering method (CN110642526A), a sol-gel method (CN101576695A), a pulse laser deposition method, an electrodeposition method (CN105366954A), a hydrothermal method (CN108298832A) and the like, and the films prepared by the methods have the problems of low film quality and low electrochromic performance, and also have the problems of high cost, low efficiency or poor film forming uniformity and the like in the aspect of large-area preparation.
Chinese patent document CN109535843A discloses the advantages of the inkjet printing film-forming process, and the inkjet printing can be applied to low-cost, continuous, large-area large-scale industrial production, compared with other film-forming processing methods, the thickness and position control of inkjet printing is accurate, the resolution ratio of micron level is provided, full digital graphic output can be realized, the processing process can be flexibly and highly precisely controlled by a computer, and the like. Chinese patent document CN109574515A discloses an electrochromic automobile windshield and a preparation method thereof, wherein tungstic acid or WCl is used6Dissolving in organic solvent to obtain tungstic acid solution or WCl6Solutions, tungstic acid solutions or WCl6The concentration of the solution is 0.8-1.2 mol/L, and tungstic acid solution or WCl is added6Stirring the solution in water bath at 40-80 ℃ for 3h to prepare a precursor solution, and then carrying out ink-jet printing to prepare WO3And annealing the precursor film at high temperature to obtain the electrochromic layer. However, the above-mentioned ink-jet printing film-forming process is complicated and requires heatThe complex post-treatment processes such as treatment annealing and the like have the defects of high difficulty in ink-jet printing film formation, low film quality and low electrochromic performance, and cannot meet the production requirement of high-quality electrochromic materials.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art, provides the nano tungsten oxide ink suitable for the ink-jet printing film-forming process, the preparation method and the application thereof, and provides an effective solution for large-area uniform preparation and low cost of the electrochromic film. The invention discloses a preparation method of nano tungsten oxide ink for ink-jet printing, which can be used for preparing a large-area electrochromic film by ink-jet printing, and the film layer has better electrochromic performance. The preparation process is simple, the large-scale production of the electrochromic film is facilitated, the cost is low, and the prepared film has good uniformity and excellent electrochromic performance.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a nano tungsten oxide ink suitable for an ink-jet printing film forming process comprises the following components: nano tungsten oxide and a solvent; according to the mass percentage, the solid content of the tungsten oxide in the nano tungsten oxide ink is 0.1-5 wt%.
Preferably, the nano tungsten oxide is at least one of tungsten oxide and alkali metal doped tungsten oxide; preferably, the solvent is any one or a mixture of isopropanol, ethanol and ethylene glycol.
Preferably, the doping element of the alkali metal doped tungsten oxide is any one or more of Li, Na, K, Ru and Cs.
Preferably, the dispersed particle size of the nano tungsten oxide in the ink is not more than 200 nm. Further preferably, the dispersion particle size of the nano tungsten oxide in the ink is 50-100 nm.
The invention relates to a preparation method of nano tungsten oxide printing ink suitable for an ink-jet printing film-forming process, which comprises the following steps:
(1) mixing the nano tungsten oxide powder with a solvent to obtain a mixed solution;
(2) grinding the mixed solution obtained in the step (1) in a ball mill to obtain uniform and stable dispersion liquid;
(3) and (3) adding a solvent into the dispersion liquid obtained in the step (2), and adjusting parameters of the dispersion liquid to obtain a tungsten oxide ink product.
The mixing is performed for the purpose of facilitating the operation of the step (2), the specific mixture does not have obvious layering within 10min, the maximum particle size in the mixture is not more than 0.1mm, in the practical process, the mixing means is conventional dispersing means under the conditions of powder state and preparation scale, and the mixing means is standard for achieving the purpose and comprises but is not limited to grinding, ball milling, ultrasound and high-speed dispersing. The preparation method of the nano tungsten oxide ink for ink-jet printing is used for preparing a large-area electrochromic film by ink-jet printing, and the film layer has better electrochromic property.
Preferably, in the step (1), the solid content of the nano tungsten oxide powder in the mixed solution is 1-20 wt% calculated according to mass percentage. Preferably, the nano tungsten oxide powder is at least one of tungsten oxide and tungsten oxide doped with alkali metal. Further preferably, the nano tungsten oxide powder is nano tungsten oxide. Preferably, the doping element of the alkali metal doped tungsten oxide is any one or more of Li, Na, K, Ru and Cs. Further preferably the doping element is Li. Preferably, the solvent is any one or a mixture of isopropanol, ethanol and ethylene glycol. Further preferably the solvent is isopropanol. Preferably, the dispersed particle size of the nano tungsten oxide in the ink is not more than 200 nm. Further preferably, the dispersion particle size of the nano tungsten oxide in the ink is 50-100 nm. Preferably, the nano tungsten oxide ink has a haze or haze of no greater than 3%. Preferably, the solid content of the nano tungsten oxide powder of the nano tungsten oxide ink is not more than 20 wt%, preferably, the solid content of the nano tungsten oxide powder is 2-20 wt%, and more preferably, 5-20 wt%. Preferably, the solid-liquid mixing ratio of the nano tungsten oxide powder to the solvent is 100 g: (400mL-500 mL).
Preferably, in the step (2), the particle size of the grinding ball is not more than 0.5 mm. More preferably, the grain diameter of the grinding ball is 0.03-0.5 mm. Further preferably, the particle size of the grinding ball is 0.3-0.5 mm. Because of the grinding balls with different sizes, the preparation scales of different samples and the difference of the grinding efficiency of different devices, the grinding time and the grinding power required for reaching the optimal condition are different, the grinding balls in the invention account for 30-80% of the volume of the grinding cavity, the ball-milling linear speed is not lower than 10m/s, the optimized grinding time is 6-12h, the grinding rotating speed is 2000-4000rad/min, but do not represent the optimized technological parameters of all other working conditions.
Preferably, in the step (3), the solvent used for adjusting the parameters of the dispersion liquid adopts any one or a mixture of isopropanol, ethylene glycol and ethanol; the tungsten oxide solid content in the dispersion after dilution adjustment is 0.1-5 wt% calculated according to the mass percentage. Further preferably, the tungsten oxide solid content in the dispersion after dilution adjustment is 0.5 to 3 wt%. Preferably, the mixing volume ratio of the dispersion liquid and the solvent obtained in the step (2) is 10: (30-80).
The invention relates to application of nano tungsten oxide ink suitable for an ink-jet printing film-forming process, wherein the ink is used for preparing an electrochromic film by ink-jet printing, and the prepared electrochromic film is used for an electrochromic intelligent window or other electrochromic devices.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the nano tungsten oxide ink is used for ink-jet printing, the prepared film is uniform, and the film layer has good electrochromic performance and is suitable for electrochromic intelligent windows and other electrochromic devices; the modulation amplitude of the electrochromic film prepared by the nano tungsten oxide ink is more than 50 percent; meanwhile, the film has better cycle stability, the coloring time is less than 13s, and the fading time is less than 20 s;
2. the nano tungsten oxide ink for ink-jet printing uses nano powder as a raw material, has simple composition and good stability, is suitable for preparing an electrochromic film by ink-jet printing, and has uniform and controllable film layer obtained by printing; the invention provides an effective solution for large-area uniform preparation and low cost of the electrochromic film;
3. the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
Fig. 1 is an XRD chart of the nano tungsten oxide powder used in the first embodiment of the present invention.
Fig. 2 is an SEM image of the morphology of the nano tungsten oxide powder used in the first embodiment of the present invention.
FIG. 3 is a statistical chart of the particle size distribution of the nano tungsten oxide powder used in the first embodiment of the present invention.
FIG. 4 is an SEM image of the morphology of a tungsten oxide film prepared by ink-jet printing in one embodiment of the invention.
FIG. 5 is a graph showing the electrochromic characteristics of a tungsten oxide film prepared by ink-jet printing according to a first embodiment of the present invention.
FIG. 6 is a graph showing the in-situ transmittance of a tungsten oxide film prepared by inkjet printing at a fixed wavelength of 633nm according to an embodiment of the present invention. The voltages in the figure are changed to 30s at 0.8V and 30s at-0.8V.
Detailed Description
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. The invention aims to provide a nano tungsten oxide ink for ink-jet printing and a preparation method thereof, wherein the preparation method comprises the following steps: and (3) preparing the nano tungsten oxide ink.
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this embodiment, a method for preparing a nano tungsten oxide ink suitable for an inkjet printing film formation process includes the following steps:
(1) weighing 100g of nano tungsten oxide powder, mixing with 400mL of isopropanol, and uniformly grinding, WO3Has an average particle diameter of 50 nm; mixing the nano tungsten oxide powder with a solvent to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) into a grinding machine for further grinding, wherein the diameter of a grinding ball is 0.5mm, the grinding ball accounts for 50% of the volume of a grinding cavity, the linear speed of the ball grinding is 10m/s, and grinding is carried out for 6 hours to obtain uniform dispersion liquid;
(3) and (3) adding 10mL of the dispersion liquid obtained in the step (2) into 30mL of isopropanol for dilution to obtain a tungsten oxide ink product.
Experimental test analysis:
the crystallinity of the nano tungsten oxide powder selected in the above example steps is good, as shown in the XRD chart of fig. 1, and in addition, as shown in fig. 2 and 3, the particle size distribution of the powder is uniform, and the average particle size is 52.58 nm. The tungsten oxide ink prepared by the method of the embodiment uses ITO transparent conductive glass as a substrate to prepare an electrochromic film in an ink-jet printing mode. The prepared tungsten oxide electrochromic film has better uniformity as shown in figure 4. The films prepared by the methods of the above examples were subjected to an electrochromic property test, and were colored at-0.8V for 30s and bleached at +0.8V for 30s, respectively. The results are shown in fig. 5, from which it can be seen that the maximum modulation amplitude of the film at 708nm wavelength is 65%, which is superior to most literature reports. The change of the in-situ transmittance of the film is tested at a fixed wavelength of 633nm, and the voltage is changed to-0.8V for 30s and 0.8V for 30 s. As a result, as shown in FIG. 6, it was found that the film had a coloring time of 11s and a fading time of 16.5 s.
The nano tungsten oxide ink for ink-jet printing prepared by the method uses nano powder as a raw material, has simple composition and good stability, is suitable for preparing an electrochromic film by ink-jet printing, and has uniform and controllable film layer obtained by printing. The method of the embodiment provides an effective solution for large-area uniform preparation and low cost of the electrochromic film. The ink prepared by the preparation method of the nano tungsten oxide ink for ink-jet printing can be used for preparing large-area electrochromic films by ink-jet printing, and the film layer has good electrochromic performance.
Example two
In this embodiment, a method for preparing a nano tungsten oxide ink suitable for an inkjet printing film formation process includes the following steps:
(1) weighing 100g of nano tungsten oxide powder, mixing with 400mL of isopropanol, and uniformly grinding, WO3Has an average particle diameter of 50 nm; mixing the nano tungsten oxide powder with a solvent to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) into a grinding machine for further grinding, wherein the diameter of a grinding ball is 0.3mm, the grinding ball accounts for 60% of the volume of a grinding cavity, the linear speed of the ball grinding is 10m/s, and grinding is carried out for 6 hours to obtain uniform dispersion liquid;
(3) and (3) adding 10mL of the dispersion liquid obtained in the step (2) into 60mL of isopropanol for dilution to obtain a tungsten oxide ink product.
Experimental test analysis:
the nano tungsten oxide powder selected in the method steps of the above examples had good crystallinity, as shown in the XRD chart of fig. 1, and the powder had a uniform particle size distribution and an average particle size of 52.58nm as shown in fig. 2 and 3.
The tungsten oxide ink prepared by the method of the embodiment is used for preparing an electrochromic film by taking ITO transparent conductive glass as a substrate in an ink-jet printing mode. The prepared tungsten oxide electrochromic film has better uniformity. The film prepared by the method of the embodiment is subjected to an electrochromic performance test, the film is colored for 30s at-0.1V and bleached for 30s at +0.1V respectively, and the test result shows that the maximum modulation amplitude of the film at the wavelength of 678nm is 69.7%, which is superior to most literature reports. The change of in-situ transmittance of the film was tested at a fixed wavelength of 633nm, and the voltage was changed to-1V for 30s and 1V for 30 s. From the test results, the film had a coloration time of 9.2s and a fading time of 14.6 s.
The nano tungsten oxide ink for ink-jet printing prepared by the method uses nano powder as a raw material, has simple composition and good stability, is suitable for preparing an electrochromic film by ink-jet printing, and has uniform and controllable film layer obtained by printing.
EXAMPLE III
In this embodiment, a method for preparing a nano tungsten oxide ink suitable for an inkjet printing film formation process includes the following steps:
(1) weighing 100g of doped tungsten oxide powder, mixing with 400mL of isopropanol, and uniformly grinding, wherein the average particle size of the doped tungsten oxide is 50nm, and the doping element of the doped tungsten oxide powder is Li; mixing the nano tungsten oxide powder with a solvent to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) into a grinding machine for further grinding, wherein the diameter of a grinding ball is 0.5mm, the grinding ball accounts for 80% of the volume of a grinding cavity, the linear speed of the ball grinding is 10m/s, and grinding is carried out for 6 hours to obtain uniform dispersion liquid;
(3) and (3) adding 10mL of the dispersion liquid obtained in the step (2) into 80mL of isopropanol for dilution to obtain a tungsten oxide ink product.
Experimental test analysis:
the tungsten oxide ink prepared by the method of the embodiment takes ITO transparent conductive glass as a substrate to prepare an electrochromic film in an ink-jet printing mode. The prepared tungsten oxide electrochromic film has better uniformity. The film prepared by the method of the embodiment is subjected to an electrochromic performance test, the film is colored for 30s at-0.8V and bleached for 30s at +0.8V, and the test result shows that the maximum modulation amplitude of the film at the wavelength of 667nm is 56.8%. The change of in-situ transmittance of the film was tested at a fixed wavelength of 633nm, and the voltage was changed to-1V for 30s and 1V for 30 s. From the test results, the film had a coloration time of 12.3s and a fading time of 17.4 s.
The nano tungsten oxide ink for ink-jet printing prepared by the method uses nano powder as a raw material, has simple composition and good stability, is suitable for preparing an electrochromic film by ink-jet printing, and has uniform and controllable film layer obtained by printing.
Example four
In this embodiment, a method for preparing a nano tungsten oxide ink suitable for an inkjet printing film formation process includes the following steps:
(1) weighing 100g of doped tungsten oxide powder, mixing with 400mL of isopropanol, and uniformly grinding, wherein the average particle size of the doped tungsten oxide is 50nm, and the doping element of the doped tungsten oxide powder is Na; mixing the nano tungsten oxide powder with a solvent to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) into a grinding machine for further grinding, wherein the diameter of a grinding ball is 0.5mm, the grinding ball accounts for 60% of the volume of a grinding cavity, the linear speed of the ball grinding is 10m/s, and grinding is carried out for 6 hours to obtain uniform dispersion liquid;
(3) and (3) adding 10mL of the dispersion liquid obtained in the step (2) into 30mL of isopropanol for dilution to obtain a tungsten oxide ink product.
Experimental test analysis:
the tungsten oxide ink prepared by the method of the embodiment takes ITO transparent conductive glass as a substrate to prepare an electrochromic film in an ink-jet printing mode. The prepared tungsten oxide electrochromic film has better uniformity. The film prepared by the method of the embodiment is subjected to an electrochromic performance test, the film is colored for 30s at-0.8V and bleached for 30s at +0.8V, and the test result shows that the maximum modulation amplitude of the film at the wavelength of 721nm is 58.7%. The change of in-situ transmittance of the film was tested at a fixed wavelength of 633nm, and the voltage was changed to-1V for 30s and 1V for 30 s. From the test results, the film had a coloration time of 11.8s and a fading time of 17.2 s.
The nano tungsten oxide ink for ink-jet printing prepared by the method uses nano powder as a raw material, has simple composition and good stability, is suitable for preparing an electrochromic film by ink-jet printing, and has uniform and controllable film layer obtained by printing.
EXAMPLE five
In this embodiment, a method for preparing a nano tungsten oxide ink suitable for an inkjet printing film formation process includes the following steps:
(1) weighing 100g of doped tungsten oxide powder, mixing with 500mL of isopropanol, and uniformly grinding, wherein the average particle size of the doped tungsten oxide is 50nm, and the doping element of the doped tungsten oxide powder is K; mixing the nano tungsten oxide powder with a solvent to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) into a grinding machine for further grinding, wherein the diameter of a grinding ball is 0.3mm, the grinding ball accounts for 80% of the volume of a grinding cavity, the linear speed of the ball grinding is 10m/s, and grinding is carried out for 6 hours to obtain uniform dispersion liquid;
(3) and (3) adding 10mL of the dispersion liquid obtained in the step (2) into 30mL of isopropanol for dilution to obtain a tungsten oxide ink product.
Experimental test analysis:
the tungsten oxide ink prepared by the method of the embodiment takes ITO transparent conductive glass as a substrate to prepare an electrochromic film in an ink-jet printing mode. The prepared tungsten oxide electrochromic film has better uniformity. The film prepared by the method of the embodiment is subjected to an electrochromic performance test, the film is colored for 30s at-1.2V and bleached for 30s at +1.2V, and the test result shows that the maximum modulation amplitude of the film at a wavelength of 693nm is 62.5%. The change of the in-situ transmittance of the film was tested at a fixed wavelength of 633nm and the change of the voltage was-1.2V for 30s and 1.2V for 30 s. From the test results, the film had a coloration time of 11.6s and a fading time of 16.8 s.
The nano tungsten oxide ink for ink-jet printing prepared by the method uses nano powder as a raw material, has simple composition and good stability, is suitable for preparing an electrochromic film by ink-jet printing, and has uniform and controllable film layer obtained by printing.
EXAMPLE six
In this embodiment, a method for preparing a nano tungsten oxide ink suitable for an inkjet printing film formation process includes the following steps:
(1) weighing 100g of doped tungsten oxide powder, mixing with 500mL of isopropanol, and uniformly grinding, wherein the average particle size of the doped tungsten oxide is 50nm, and the doping element of the doped tungsten oxide powder is Cs; mixing the nano tungsten oxide powder with a solvent to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) into a grinding machine for further grinding, wherein the diameter of a grinding ball is 0.5mm, the grinding ball accounts for 50% of the volume of a grinding cavity, the linear speed of the ball grinding is 10m/s, and grinding is carried out for 6 hours to obtain uniform dispersion liquid;
(3) and (3) adding 10mL of the dispersion liquid obtained in the step (2) into 30mL of isopropanol for dilution to obtain a tungsten oxide ink product.
Experimental test analysis:
the tungsten oxide ink prepared by the method of the embodiment takes ITO transparent conductive glass as a substrate to prepare an electrochromic film in an ink-jet printing mode. The prepared tungsten oxide electrochromic film has better uniformity. The film prepared by the method of the embodiment is subjected to an electrochromic performance test, the film is colored for 30s at-1V and bleached for 30s at +1V, and the test result shows that the maximum modulation amplitude of the film at the wavelength of 684nm is 63.2%. The change of in-situ transmittance of the film was tested at a fixed wavelength of 633nm, and the voltage was changed to-1V for 30s and 1V for 30 s. From the test results, the film had a coloration time of 12.8s and a fading time of 17.6 s.
The nano tungsten oxide ink for ink-jet printing prepared by the method uses nano powder as a raw material, has simple composition and good stability, is suitable for preparing an electrochromic film by ink-jet printing, and has uniform and controllable film layer obtained by printing.
In summary, the nano tungsten oxide ink for inkjet printing and the preparation method thereof in the above embodiments are obtained by mixing the nano tungsten oxide powder and the solvent, dispersing and grinding the mixture uniformly by ball milling, and then adding the solvent to blend the mixture. The nano tungsten oxide ink prepared by the method of the embodiment is suitable for ink-jet printing and has a good printing effect. The tungsten oxide film with electrochromic property can be directly prepared by adopting the ink through ink-jet printing, and an effective solution is provided for large-area uniform preparation and low cost of the electrochromic film.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (10)
1. A nanometer tungsten oxide printing ink suitable for an ink-jet printing film forming process is characterized in that: the nano tungsten oxide ink comprises the following components: nano tungsten oxide and a solvent; according to the mass percentage, the solid content of the tungsten oxide in the nano tungsten oxide ink is 0.1-5 wt%.
2. The nano tungsten oxide ink suitable for an inkjet printing film forming process according to claim 1, wherein: the nano tungsten oxide is at least one of tungsten oxide and alkali metal doped tungsten oxide; the solvent is any one or a mixture of isopropanol, ethanol and glycol.
3. The nano tungsten oxide ink suitable for an inkjet printing film forming process according to claim 2, wherein: the doping element of the tungsten oxide doped with the alkali metal is any one or more of Li, Na, K, Ru and Cs.
4. The nano tungsten oxide ink suitable for an inkjet printing film forming process according to claim 1, wherein: the dispersed particle size of the nano tungsten oxide in the whole ink is not more than 200 nm.
5. The preparation method of the nano tungsten oxide ink suitable for the ink-jet printing film-forming process according to claim 1, which is characterized by comprising the following steps:
(1) mixing the nano tungsten oxide powder with a solvent to obtain a mixed solution;
(2) grinding the mixed solution obtained in the step (1) in a ball mill to obtain uniform and stable dispersion liquid;
(3) and (3) adding a solvent into the dispersion liquid obtained in the step (2), and adjusting parameters of the dispersion liquid to obtain a tungsten oxide ink product.
6. The method for preparing the nano tungsten oxide ink suitable for the inkjet printing film forming process according to claim 5, wherein the method comprises the following steps: in the step (1), the solid content of the nano tungsten oxide powder in the mixed solution is 1-20 wt% according to the mass percentage.
7. The method for preparing the nano tungsten oxide ink suitable for the inkjet printing film forming process according to claim 5, wherein the method comprises the following steps: in the step (2), the particle size of the grinding ball is not more than 0.5 mm.
8. The method for preparing the nano tungsten oxide ink suitable for the inkjet printing film forming process according to claim 5, wherein the method comprises the following steps: in the step (3), the solvent used for adjusting the parameters of the dispersion liquid adopts any one or a mixture of isopropanol, ethylene glycol and ethanol; the tungsten oxide solid content in the adjusted dispersion liquid is 0.1-5 wt% calculated according to the mass percentage.
9. The method for preparing the nano tungsten oxide ink suitable for the inkjet printing film forming process according to claim 8, wherein the method comprises the following steps: in the step (3), the tungsten oxide solid content in the adjusted dispersion liquid is 0.5 to 3 wt% in terms of mass percentage.
10. The application of the nano tungsten oxide ink suitable for the ink-jet printing film-forming process according to claim 1, wherein the ink is used for preparing an electrochromic film by ink-jet printing, and the prepared electrochromic film is used for an electrochromic intelligent window or other electrochromic devices.
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Application publication date: 20210615 |