Photoelectric dual-regulation wide-spectrum response color-changing device and preparation method thereof
By adopting the structure of fluorine-doped tin oxide glass transparent conductive layer, nano-tungsten oxide composite layer and polyaniline counter electrode layer, the existing photo-electric dual-regulated color change devices have high cost and sensitivity to light in the fixed wavelength range, and a low-cost, simple-prepared wide spectrum response color change device is achieved to meet the efficient application needs under variable light sources.
Patent Information
- Application Number
- CN202510517925.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-24
- Publication Date
- 2025-06-06
AI Technical Summary
The existing photo-electric dual-control color-changing devices are costly, complex in manufacturing process, and are sensitive to light in a fixed wavelength range, which limits their application in natural light and variable light sources.
The structures including fluorine-doped tin oxide glass transparent conductive layer, nano-tungsten oxide composite (NH4)6[P2Mo18O62]·14.2H2O color change layer, LiClO4 composite poly(ethylene glycol) methacrylate ion storage layer and polyaniline counter electrode layer are adopted to achieve photo-electric dual-regulated wide spectrum response by optimizing the preparation process and selecting low-cost raw materials.
It realizes the response of the device to ultraviolet and visible light in a wide range of low-cost and simple preparation processes, and the absorbance increases by 0.4102 within 2 hours, and the transmittance increases by 24.48% at a voltage of 0V to -1.9V, meeting the application needs of variable light sources.
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Figure CN120103649A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of color-changing devices, and in particular to a photoelectric dual-regulation wide-spectrum-response color-changing device and a preparation method thereof. Background Art
[0002] At a time when materials science is booming, the single functions of traditional materials and devices cannot meet the growing diversified needs. Smart materials and devices have become the focus of research, with wide applications and huge potential. With the continuous breakthroughs in technology, the combination of electrochromic and photochromic materials provides a new solution that not only realizes the controllable color change of materials under different environmental stimuli, showing excellent photochromic-electrochromic versatility, but also meets the needs of various scenarios such as smart windows that automatically adjust transmittance according to light and temperature. The currently reported optical-electrical dual-control color-changing devices are relatively expensive and have a complex manufacturing process. However, by optimizing the preparation process and selecting low-cost raw materials, the cost of this type of multifunctional material is gradually decreasing, and it is expected to achieve large-scale production and application while ensuring high performance, opening up new paths for the development of smart devices.
[0003] In addition, existing photochromic-electrochromic materials are sensitive to light within a fixed wavelength range, which limits their application under natural light and variable light sources. Developing a wide spectrum response with dual photo-electric control can absorb sunlight more widely and improve the utilization rate of sunlight, which is of great significance to real life. Summary of the invention
[0004] In view of this, the present invention provides a photoelectric dual-control wide spectrum response color-changing device and a preparation method thereof. The preparation method is simple, the materials are readily available, the cost is low, and it responds to a wide range of ultraviolet and visible light. Under the intensity of one sun, the absorbance increases by 0.4102 within 2 hours. At a voltage of 0V to -1.9V, as the voltage decreases, the transmittance of the device increases by 24.48%. This solves the problem that the current photoelectric dual-control color-changing device has a high cost, a complex manufacturing process, and is limited to light sensitivity within a fixed wavelength range.
[0005] In order to achieve the above-mentioned purpose, the present invention adopts the following technical scheme: a photoelectric dual-control wide spectrum response color-changing device, comprising: a glass transparent conductive layer with a fluorine-doped tin oxide surface, a nano-tungsten oxide composite (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O color change layer, LiClO 4The composite poly(ethylene glycol) methacrylate (PEGMA) ion storage layer, polyaniline counter electrode layer and transparent conductive layer are stacked from top to bottom. The preparation method of the above-mentioned optical-electrical dual-control wide spectrum response color-changing device is as follows;
[0006] 1)WO 3 Nanoparticles were prepared as follows: 0.6-2.5 mg mL -1 Tungstic acid solution 15mL, 0.0031mg·mL -1 0.1093g sodium acetate solution, 0.1093g HCI solution, fluorine-doped tin oxide glass; heated at 180℃ for 6h; after cooling, annealed at 500℃ for 2h to obtain nano WO 3 . Its thickness is greater than 20nm.
[0007] 2) The surface prepared in 1) is nano-WO 3 The fluorine-doped tin oxide glass was repeatedly immersed in polyethyleneimine solution and (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O solution, each time for 2 to 5 minutes, rinse and blow dry. After 21 to 40 times, a color-changing layer is obtained, and its thickness is greater than 100nm.
[0008] 3) Polyaniline is deposited on another piece of glass with a surface of fluorine-doped tin oxide by electrodeposition, with a voltage window of -0.2V to +0.8V, and the deposition is repeated 15 to 25 times to obtain a counter electrode layer.
[0009] 4) Poly(ethylene glycol) methyl ether methacrylate (PEGMA), LiClO 4 Add 8500 UV light-curing adhesive into a mortar in a mass ratio of 5:1:0.1 and grind thoroughly to obtain electrolyte glue.
[0010] 5) On the counter electrode layer prepared in 3), the electrolyte gel prepared in 4) is dripped, and evenly spin-coated on the counter electrode layer at a rotation speed of 2000, from top to bottom, staggered and stacked on the color-changing layer prepared in 2), and cured twice under ultraviolet light, with curing times of 90s to 120s and 180s to 300s respectively.
[0011] Compared with the prior art, the present invention has the following advantages:
[0012] The preparation method of this product is simple, and the device assembly only needs to be carried out at room temperature, which is low in cost. The device of this product can be reused, has good stability, and responds to a wide range of ultraviolet and visible light. Under the light signal, the color change is obvious under ultraviolet / visible light irradiation. Under the intensity of one sun, the absorbance increases by 0.4102 within 2 hours. Under the electrical signal, it fades quickly and has high transmittance. At a voltage of 0V to -1.9V, as the voltage decreases, the transmittance of the device increases by 24.48%. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1 This is a structural diagram of Embodiment 1 of the present invention.
[0014] Figure 2 This is the absorbance curve of Example 10 of the present invention under UV / visible light irradiation
[0015] Figure 3 Spectrum diagram of Example 10 of the present invention at different voltages DETAILED DESCRIPTION
[0016] The following non-limiting embodiments may enable a person skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.
[0017] The experimental methods described in the following examples are conventional methods unless otherwise specified. The reagents and materials are commercially available unless otherwise specified.
[0018] Combination Figure 1 The color-changing device is stacked from top to bottom: the transparent conductive layer 1 is glass with fluorine-doped tin oxide on the surface, and the color-changing layer 2 is nano WO 3 The compound (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O, the ion storage layer 3 is lithium perchlorate composite poly (ethylene glycol) methyl ether methacrylate, and the counter electrode layer 4 is polyaniline.
[0019] In the present invention, the nano WO in the color-changing layer 3 Prepare according to the following method: add 15 mL of tungstic acid solution to a 25 mL reactor, 0.0031 mg·mL -1 0.1093g sodium acetate solution, 0.1093g HCI solution, fluorine-doped tin oxide glass; heated at 180℃ for 6h; after cooling, annealed at 500℃ for 2h to obtain WO 3 Nano, thickness greater than 20nm. The preferred mass concentration of tungstic acid solution is 0.6~2.5mg·mL -1 .
[0020] In the present invention, the color-changing layer (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O and WO 3 The nanocomposite membrane was prepared by the following method: the generated nano-WO 3 glass, respectively, at 0.125 mg·mL -1 The polyethyleneimine solution and (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O solution, and the reaction was repeated 21 to 40 times to obtain nano-WO 3 Compound (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O color-changing layer. The preferred (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 The mass concentration of O is 0.015-0.030 mg·mL -1 The preferred nano-WO 3 Composite (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 The time of each O is 2 to 5 minutes. The thickness of the preferred color-changing layer is greater than 100 nm.
[0021] In the present invention, the counter electrode layer is prepared according to the following method: 2.16 g H 2 SO 4 and deionized water, stirred vigorously until dissolved, and put in activated fluorine-doped tin oxide glass. Using the electrodeposition method, the voltage window is -0.2V to +0.8V, and 15 to 25 layers are deposited to obtain the counter electrode layer. The preferred voltage window for the electrodeposition of polyaniline in the counter electrode layer is -0.2V to +0.8V, and 15 to 25 layers are deposited.
[0022] In the present invention, the device is prepared according to the following method: the electrolyte glue in the above is evenly spin-coated on the counter electrode layer at a rotation speed of 2000, and then cured and semi-cured under ultraviolet light, and stacked on the color-changing layer from top to bottom, and encapsulated to obtain the device. Preferably, the device is cured twice under ultraviolet light, and the curing time is 90 to 120 seconds and 180 to 300 seconds respectively.
[0023] Example 1
[0024] Preparation of raw materials:
[0025] Nano WO 3 Layer synthesis: add 15 mL of 2.2 mg mL -1 Tungstic acid solution, 0.0031 mg·mL -1 0.1093g sodium acetate solution, 0.1093g HCI solution, fluorine-doped tin oxide glass; the reactor was heated at 180℃ for 6h. After cooling, annealing was performed at 500℃ for 2h to obtain nano WO 3 layer.
[0026] Preparation of color-changing layer: The generated WO 3 Nanolayer glass, immersed in 0.125 mg mL -1 2min, immersed in 0.025mg·mL -1 NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O solution for 2 minutes. Repeat the above steps 40 times to obtain a color-changing layer.
[0027] Preparation of ion storage layer: 2.5110 g of poly(ethylene glycol) methacrylate (PEGMA) and 0.5160 g of LiClO 4 Put it into a mortar, add UV ultraviolet curing glue, and grind it thoroughly until a clear and transparent viscous liquid appears to obtain an ion storage layer.
[0028] Preparation of the counter electrode layer: Take 2.56 mL of aniline and add 2.16 g of H 2 SO 4 and 80 mL of deionized water, stirred vigorously until dissolved, and put in the glass with fluorine-doped tin oxide on the surface. Using the electrodeposition method, the voltage window is -0.2V to +0.8V, and 15 layers are deposited to obtain the counter electrode.
[0029] The device was prepared by evenly spin-coating the electrolyte gel on the counter electrode layer at a rotation speed of 2000, semi-curing it under ultraviolet light for 90 seconds, and then staggeredly stacking it on the color-changing layer from top to bottom, fully curing it under ultraviolet light for 120 seconds, and encapsulating it to obtain the device.
[0030] Based on the above materials provided by the present invention, the applicant tested different amounts of tungstate solution and (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 The different numbers of O composite layers were studied, and the light reaction steps were as follows: different amounts of tungstate were used to generate WO 3 The nanolayer was illuminated for 2 hours at room temperature with a light intensity of one sun, and the absorbance before and after illumination was measured to obtain the absorbance difference.
[0031] Examples 2-6 in Table 1 show the effect of different amounts of composite materials on their transmittance under visible light.
[0032] Table 1 Application effects of different amounts of composite materials
[0033]
[0034] In Table 1, the mass concentration of tungstic acid in Example 2-6 is 0.64 mg·mL -1 , 1.60mg·mL -1 , 2.24mg·mL -1 Hydrothermal generation of WO 3 Nanolayer; Example 2 is tungstate mass concentration of 0.64mg·mL -1 Generate WO 3 Nanolayer, compound 40 times (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O; Example 3 is a tungstate mass concentration of 1.60 mg mL -1 Generate WO 3 Nanolayer, compound 40 times (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O. Examples 4, 5, and 6 are tungstic acid with a mass concentration of 2.24 mg·mL -1 Hydrothermal generation of WO 3When the nano layer is used, the composite is 25, 30, 40 times (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O.
[0035] Specifically, from the experimental data of Examples 2, 3, and 6, it can be seen that the hydrothermal WO generated by different mass concentrations of tungstate solutions 3 Nanolayer, compounded with the same number of (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O, under visible light, as the amount of tungstate solution increases, the color changes greatly, the absorbance difference becomes larger, and the transmittance decreases.
[0036] In Examples 4, 5, and 6, under the same experimental conditions, the hydrothermal WO generated by the same mass concentration of tungstate solution 3 Nanolayer, compounded with different times (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O, 25, 30 and 40 times respectively. Under visible light, the color changes significantly, the absorbance difference becomes larger, and the transmittance decreases.
[0037] In addition, electrochemical tests were carried out on the composite material to examine the electrical response of the material. The experiment selected a single wavelength of 690nm and examined the transmittance of the composite film at a voltage of -0.7V.
[0038] Examples 7-9 in Table 2 reflect the effects of a single wavelength of 690 nm and a voltage of -0.7 V on the composite material under the same experimental conditions.
[0039] Table 2 Effect of voltage on composite materials
[0040]
[0041] In Table 2, Examples 7-9 are at a single wavelength of 690nm and a voltage of -0.7V, (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O compound 25, 30, 40 times.
[0042] Specifically, it can be seen from the data of Examples 7-9 that at a single wavelength of 690 nm, the mass concentration of tungstic acid is 2.24 mg·mL -1 , (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O is compounded 25, 30, and 40 times. From the experimental data, it can be seen that at a voltage of -0.7 V, the color changes significantly, the difference in absorbance before and after illumination becomes larger, and the transmittance decreases.
[0043] Example 10
[0044] Based on the above materials provided by the present invention, the applicant selected a transparent conductive layer of fluorine-doped tin oxide glass on the surface, and a tungstic acid mass concentration of 2.24 mg·mL -1 , WO 3 Nanolayer composite 40 times (NH 4 ) 6 [P 2 Mo 18 O 62 ]·14.2H 2 O, the counter electrode layer is -0.2V~+0.8V, and 15 layers of polyaniline are electrodeposited. The process is completed in two steps of curing and semi-curing at room temperature. The curing times are 90s and 180s respectively. The device is assembled and subjected to visible light illumination experiments and different voltage experiments.
[0045] Visible light experimental conditions: room temperature, light intensity 102.32mV·cm -2 , lighting time 2h.
[0046] Different voltage experimental conditions: room temperature, voltage 0V~-1.9V.
[0047] The response of the device to visible light was investigated by monitoring the curve of the absorbance of the device under illumination over time. Figure 2 At room temperature, the light intensity is 102.32 mV·cm -2 , the device achieved an absorbance increase of 0.4102 within 2 hours under visible light. It was observed that its absorbance showed a significant dynamic response with the change of illumination time. Specifically, when the device was exposed to visible light, its absorbance rose rapidly under illumination, and this process was accompanied by a uniform change in the color of the device, from a transparent state to a dark state, thereby achieving efficient absorption and regulation of sunlight.
[0048] The effect of voltage on absorbance was investigated by monitoring the visible spectrum of the device at different voltages. The visible spectrum of the device at different voltages in the lithium-ion solid electrolyte was measured in the voltage range of 0V to -1.9V. Figure 3 , Figure 3 The visible spectrum of the device under different voltages. It can be seen from the figure that as the voltage decreases, the transmittance of the device increases by 24.48%. The device has no color change under open circuit voltage. When the negative voltage is gradually increased, the color of the device gradually deepens to blue. This shows that the device can dynamically control the color by controlling the applied voltage, showing a transition from colorless to dark blue.
[0049] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the scheme disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.
[0050] The embodiments of the present invention are described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions and variations of these embodiments are made without departing from the principles and spirit of the present invention, and still fall within the protection scope of the present invention.
Claims
1. A photoelectric dual-control wide spectrum response color-changing device and its preparation method. Characterized by: include: Transparent conductive layer, nano-WO3 composite (NH4)6[P2Mo 18 O 62 ]·14.2H2O color-changing layer, LiClO4 composite poly(ethylene glycol) methacrylate (PEGMA) ion storage layer, polyaniline counter electrode layer, and transparent conductive layer are stacked from top to bottom.
2. The color-changing device according to claim 1, characterized in that: Its transparent conductive layer is tin oxide glass with fluorine doped surface.
3. The color-changing device according to claim 1, characterized in that: The thickness of nano WO3 in the color-changing layer is greater than 20nm, and the mass concentration of prepared tungstic acid is 0.6~2.5mg·mL -1 .
4. The color-changing device according to claim 1, characterized in that: Its color-changing layer is phosphomolybdate (NH4)6[P2Mo 18 O 62 ]·14.2The mass concentration of H2O is 0.015~0.030mg·mL -1 .
5. The color-changing device according to claim 1, characterized in that: The color-changing layer contains nano-WO3 layers and (NH4)6[P2Mo 18 O 62 ]·The recombination time of 14.2H2O is 2 to 5 minutes, and its thickness is greater than 100nm.
6. The color-changing device according to claim 1, characterized in that: The color-changing layer contains nano-WO3 layers and (NH4)6[P2Mo 18 O 62 ]·14.2H2O recombination times are 21 to 40 times, and its thickness is greater than 100nm.
7. The color-changing device according to claim 1, characterized in that: The ion storage layer is poly(ethylene glycol) methacrylate (PEGMA) dissolved with LiClO4. The device is cured under ultraviolet light in two steps, with the curing time being 90 to 120 seconds and 180 to 300 seconds respectively.
8. A photoelectric dual-control wide spectrum response color-changing device and its preparation method, characterized in that: The method is prepared according to any one of claims 1 to 7.