Dynamically-controllable photoinduced-electrochromic double-response device and manufacturing method and application of dynamically-controllable photoinduced-electrochromic double-response device

Abstract

The invention discloses a photochromic-electrochromic dual-response device capable of being dynamically regulated and controlled as well as a preparation method and application thereof, and belongs to the field of color-changing materials. The device comprises a lower electrode, a photochromic and electrochromic double-response functional layer, an electrolyte layer and an upper electrode, and raw materials of the double-response functional layer are composed of molybdenum-doped tungsten oxide quantum dots and poly (3, 4-ethylenedioxythiophene)-polystyrolsulfon acid. The photochromic and electrochromic synergistic regulation and response speed of the material are remarkably improved through heteroatom doping and material nanocrystallization, and then the material is compounded with the conductive polymer to optimize ion and electron transmission ways, so that the stability and responsiveness of the material are improved; the preparation method comprises the following steps: preparing a double-response functional layer on an electrolyte layer, quickly transferring the double-response functional layer to the electrolyte layer in combination with a thermal transfer printing technology to prepare a compound, and assembling the compound with an upper electrode and a lower electrode through a multi-layer integration process, so that the obtained device realizes bidirectional reversible regulation and control on light transmittance, shows excellent heat insulation performance, and has wide application prospects in the field of intelligent windows.

Description

Technical Field

[0001] The present invention belongs to the field of color-changing materials, and particularly relates to a dynamically tunable photo-electrochromic dual-response device, a manufacturing method thereof, and an application thereof. Background Art

[0002] Photochromic and electrochromic materials exhibit unique advantages in the field of optical devices due to their ability to dynamically regulate optical properties. Photochromic materials achieve spontaneous color switching through photoinduced molecular isomerization or band transitions. Electrochromic materials rely on an electric field to drive ion insertion / extraction reactions to complete precise optical regulation. The synergistic effect of the two can effectively integrate the self-adaptive passive response of light energy and the active regulation driven by a low voltage, achieving complementary regulation in terms of response speed, energy consumption efficiency, and functional integration, and breaking through the inherent limitations of single-mode response materials in dynamic environmental adaptability. This dual-mode synergistic effect is crucial for the development of intelligent optical systems. Especially in complex environments such as alternating light and dark or dynamic thermal radiation environments, it can significantly improve the scene adaptability and energy utilization efficiency of the system. Currently, such system materials have been widely used in fields such as dynamically tunable optical smart windows, flexible wearable electronic devices, and optical sensors, becoming a frontier direction in the research of new-generation intelligent materials.

[0003] In recent years, through strategies such as active component compounding, molecular structure design, and solid-state electrolyte interface engineering, the controllable construction of photo / electrochromic dual-response functional materials has been initially realized. In particular, by combining band engineering and ion transport channel optimization technologies, the photo-electric synergistic efficiency and dynamic light regulation of materials have been significantly improved. However, due to the energy level mismatch caused by differences in the color-changing mechanism, conflicts in ion-electron conductivity / transport paths, and interfacial charge imbalance, the effective synergistic response between photochromism and electrochromism in existing systems still faces significant challenges. These key problems result in the inability of dual-response devices to achieve efficient fading after photochromism under the drive of an electric field. Although relying on thermal bleaching / chemical bleaching can accelerate the fading after photochromism, the fading time is still generally above 1 h, severely limiting its real-time dynamic optical regulation. Summary of the Invention

[0004] Object of the Invention: To solve the technical problems that it is difficult for existing photochromic and electrochromic materials to achieve controllable synergistic response and the natural fading speed after photochromism is slow, the first object of the present invention is to provide a dynamically tunable photo-electrochromic dual-response device with a fast and reversible synergistic effect of photochromism and electrochromism and capable of bidirectionally dynamically regulating optical transmittance. The second object of the present invention is to provide a manufacturing method of the above-mentioned dynamically tunable photo-electrochromic dual-response device. The third object of the present invention is to provide an application of the above-mentioned photo-electrochromic dual-response device.

[0005] Technical solution: The dynamically tunable photo - electrochromic dual - response device of the present invention includes a lower electrode, a photo - and electrochromic dual - response functional layer, an electrolyte layer, and an upper electrode. Among them, the raw materials of the photo - and electrochromic dual - response functional layer are composed of molybdenum - doped tungsten oxide quantum dots and poly(3,4 - ethylenedioxythiophene) - polystyrenesulfonic acid, with a thickness of 0.5 - 5 μm, preferably 1.61 - 3.79 μm.

[0006] Further, both the upper electrode and the lower electrode are indium tin oxide conductive glasses.

[0007] Further, the electrolyte layer is composed of acrylamide, 2 - acrylamido - 2 - methylpropane sulfonic acid, acrylic acid, and lithium chloride in a mass ratio of (4 - 6):(1 - 2):(2 - 4):(2 - 4), with a thickness of 2 - 5 mm, preferably 3 - 4 mm.

[0008] The preparation method of the photo - electrochromic dual - response device of the present invention includes the following steps:

[0009] (1) Using sodium tungstate dihydrate, ammonium molybdate tetrahydrate, a solvent, an acid solution, and ethylene glycol as raw materials, a molybdenum - doped tungsten oxide quantum dot solution is prepared by a hydrothermal method;

[0010] (2) The molybdenum - doped tungsten oxide quantum dot solution is mixed evenly with poly(3,4 - ethylenedioxythiophene) - polystyrenesulfonic acid solution, a solvent, and a surfactant to obtain a photo - and electrochromic dual - response functional layer solution, which is coated on the surface of indium tin oxide conductive glass and forms a photo - and electrochromic dual - response functional layer after annealing treatment;

[0011] (3) Using acrylamide, 2 - acrylamido - 2 - methylpropane sulfonic acid, acrylic acid, and lithium chloride as raw materials, a polyacrylamide / 2 - acrylamido - 2 - methylpropane sulfonic acid / acrylic acid / lithium chloride hydrogel electrolyte layer is prepared;

[0012] (4) The photo - and electrochromic dual - response functional layer is transferred to the surface of the polyacrylamide / 2 - acrylamido - 2 - methylpropane sulfonic acid / acrylic acid / lithium chloride hydrogel electrolyte layer by a thermal transfer technique to form a composite;

[0013] (5) The composite is sandwiched between the upper electrode and the lower electrode to form a sandwich structure, and a dynamically tunable photo - electrochromic dual - response device is prepared.

[0014] Further, in step (1), the specific preparation process of the molybdenum-doped tungsten oxide quantum dot solution is as follows: Sodium tungstate dihydrate and ammonium molybdate tetrahydrate are completely dissolved in a solvent, and an acid solution is slowly added dropwise and stirred until precipitation is complete. The supernatant is removed by centrifugation, and the precipitate is washed with the solvent until the pH is 2-3. The washed precipitate is added to an ethylene glycol solution and heated and stirred to form a clear and transparent solution, and the molybdenum-doped tungsten oxide quantum dot solution is prepared by a hydrothermal reaction; wherein, the molar ratio of sodium tungstate dihydrate to ammonium molybdate tetrahydrate in the solvent is 10-100:1, and the dosage ratio of sodium tungstate dihydrate to the solvent is 0.025-0.05 mol: 20-30 mL; the acid solution is hydrochloric acid with a mass fraction of 36-38%, and the parameters of the centrifugation are: the centrifugation speed is 8000-12000 r / min, and the centrifugation time is 5-10 min; the temperature of the heating and stirring is 90±5°C, and the parameters of the hydrothermal reaction are: the hydrothermal reaction temperature is 160-200°C, and the hydrothermal reaction time is 40-56 h.

[0015] Further, in step (2), the mass ratio of the molybdenum-doped tungsten oxide quantum dot solution, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid solution, solvent, and surfactant is (0.56-2.24):(2-4):(5.76-7.44):(0.005-0.01), preferably 1.12-2:6-10:4:0.01-0.05; the mass concentration of the polystyrene sulfonic acid solution is 1-1.3%, the solvent is deionized water, and the surfactant is Triton-X100.

[0016] Further, in step (2), when the area of the indium tin oxide conductive glass is 4-12 cm 2 ², the coating volume of the photoinduced and electrochromic dual-responsive functional layer solution used is 50-250 μL, and the parameters of the annealing treatment are: the annealing treatment temperature is 70-90°C, and the annealing treatment time is 45-90 min.

[0017] Further, in step (3), the specific preparation process of the polyacrylamide / 2-acrylamido-2-methylpropanesulfonic acid / acrylic acid / lithium chloride hydrogel electrolyte layer is as follows: acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, and lithium chloride are dissolved in a solvent, and then polyvinylpyrrolidone-K30, N,N'-methylenebisacrylamide, and ammonium persulfate are added and mixed and stirred until clear and transparent. The obtained precursor solution is transferred to a mold and heated for polymerization to obtain; wherein, the dosage ratio of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, lithium chloride, solvent, polyvinylpyrrolidone-K30, N,N'-methylenebisacrylamide, and ammonium persulfate is 5-15 g: 1.23-3.69 g: 2.84-8.52 g: 2.95-8.85 g: 20-60 mL: 0.34-1.02 g: 25-75 mg: 36-108 mg, preferably 5 g: 1.23 g: 2.84 g: 2.95 g: 20-60 mL: 0.34 g: 25 mg: 36 mg. Among them, polyvinylpyrrolidone-K30 can help form a stable gel network structure, N,N'-methylenebisacrylamide is used as a cross-linking agent, and ammonium persulfate is used as an initiator; the conditions for the heating polymerization are: first heat at 60±5 °C for 60-80 min, and then heat at 80±5 °C for 30-40 min;

[0018] Further, in step (4), the process parameters of the thermal transfer are: the thermal transfer temperature is 60-80 °C, and the thermal transfer time is 5-10 min.

[0019] Application of the dynamically tunable photo-electrochromic dual-responsive device described in the present invention as an intelligent window in energy-saving buildings.

[0020] Principle of the invention: In the bleached state of the dual-responsive device of the present invention, lithium ions in the polyacrylamide / 2-acrylamido-2-methylpropanesulfonic acid / acrylic acid / lithium chloride (PAAAL) hydrogel migrate to the dual-responsive functional layer through thermal diffusion. Under visible light irradiation, the photochromic and electrochromic functional layers are photoexcited to generate an electron-rich environment, which promotes the adsorption and insertion of lithium ions. At the same time, the inserted hydrogen ions during the irradiation process will also induce lattice expansion in H y W / MoO x , thereby enhancing the migration of lithium ions. In the case of the combination of light and ionic activity, hydrogen ions may be replaced by lithium ions to form Li y W / MoO x , W 6 + / Mo 6+ is reduced to W 5+ / Mo 5+, the color turns blue. After removing the light source, applying an external voltage of 1.5 V can cause the lithium ions in the photochromic and electrochromic functional layers to escape, and W 5+ / Mo 5+ returns to W 6+ / Mo 6+ state, and the device returns to the bleached state.

[0021] Advantages: Compared with the prior art, the present invention has the following remarkable effects: (1) The present invention uses molybdenum-doped tungsten oxide quantum dots to compound the conductive polymer poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid solution to prepare a photochromic and electrochromic dual-responsive functional material. By compounding it with a hydrogel electrolyte and indium tin oxide conductive glass to prepare a device, it breaks through the limitation of single-mode response and realizes ultra-fast bidirectional reversible dynamic regulation of photochromism and electrochromism; (2) The dynamically adjustable photochromic and electrochromic dual-responsive device prepared by the present invention can be used as a new type of smart window, realizing dynamic regulation of optical transmittance and showing excellent heat insulation performance; Therefore, as a smart window, the device shows potential application prospects in improving user living comfort and building energy conservation. Description of the Drawings

[0022] Figure 1 is a schematic structural diagram of the dynamically adjustable photo-electrochromic dual-responsive device in Example 1;

[0023] Figure 2 is a preparation flow chart of the dynamically adjustable photo-electrochromic dual-responsive device described in Example 1;

[0024] Figure 3 is a transmission electron microscope image and particle size distribution diagram of molybdenum-doped tungsten oxide quantum dots in Example 1;

[0025] Figure 4 are optical pictures and scanning electron microscope cross-sectional diagrams of the photo- and electro-dual-responsive functional layers prepared by annealing the molybdenum-doped tungsten oxide quantum dots / poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite solution coated with different volumes;

[0026] Figure 5 are transmittance and optical contrast diagrams before and after electrochromism of the dual-responsive functional layers prepared by coating different volumes of solution;

[0027] Figure 6 is an optical diagram of the electrochromism of the dual-responsive device;

[0028] Figure 7 are optical pictures and transmittance curve diagrams of the photochromic process of the dual-responsive device;

[0029] Figure 8Optical photograph of the synergistic regulation of the photoinduced and electrochromic dual responses of a dual-response device;

[0030] Figure 9 Optical diagram of the dual-response device as an intelligent color-changing window in practical applications. Specific implementation manners

[0031] The present invention will be further described in detail below in conjunction with embodiments and the accompanying drawings.

[0032] The raw materials and molds used in the following embodiments are existing products, and the specific preparation operations and performance tests are conventional technologies. Among them, the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid solution (mass concentration of 1-1.3%) is the PH1000 type reagent produced by Heraeus Electronic Materials Company. Transmittance and optical contrast tests: The transmittance of the photoinduced and electrochromic layers and the transmittance difference of the device in the colored and faded states at a wavelength of 550 nm are measured using a UV-visible spectrophotometer.

[0033] Example 1: As Figure 1 shown, the dynamically regulated photoinduced-electrochromic dual-response device provided in this embodiment includes a lower electrode (ITO glass), a photoinduced (EC) and electrochromic (PC) dual-response functional layer, an electrolyte layer (hydrogel), and an upper electrode (ITO glass).

[0034] As Figure 2 shown, the manufacturing method of the above dual-response device includes the following steps:

[0035] (1) Preparation of molybdenum-doped tungsten oxide quantum dot solution: Dissolve 8.25 g of sodium tungstate dihydrate and 0.3090 g of ammonium molybdate tetrahydrate in 20 mL of deionized water, stir and mix until clear and transparent, then slowly add concentrated hydrochloric acid with a mass fraction of 36-38% until precipitation is complete, and then centrifuge at a speed of 10000 r / min for 7 min. Remove the supernatant and wash the precipitate with deionized water until the pH is 2-3. Add the washed precipitate to 30 mL of ethylene glycol, heat and stir at 90 °C to form a clear and transparent solution, and then transfer it to a 100 mL polytetrafluoroethylene reaction kettle and heat and react at a constant temperature in an oven at 180 °C for 48 h. Cool to room temperature to obtain the molybdenum-doped tungsten oxide quantum dot solution. Figure 3 It is the transmission electron microscope image and particle size distribution diagram of molybdenum-doped tungsten oxide quantum dots. It can be seen that in this embodiment, molybdenum-doped tungsten oxide quantum dots are successfully prepared by a one-step hydrothermal method, and the prepared molybdenum-doped tungsten oxide quantum dots can be evenly dispersed in deionized water, and their average particle size is 3.45 ± 0.68 nm.

[0036] (2) Preparation of molybdenum-doped tungsten oxide quantum dot / poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid photo- and electrochromic dual-responsive functional layer: Weigh 1.12 g of molybdenum-doped tungsten oxide quantum dot solution, 6.88 g of deionized water, and 4 g of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid solution, stir and mix them evenly, add 0.01 g of Triton-X100, and stir and mix for 12 h to prepare a molybdenum-doped tungsten oxide quantum dot / poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite photo- and electrochromic dual-responsive functional layer solution. Then, ultrasonically clean the indium tin oxide conductive glass substrate with acetone, ethanol, and deionized water for 20 min in sequence and place it in an oven to dry. Put the dried glass sheet into a plasma cleaner with a working power of 100 W and a working pressure of 60 Pa for 5 min of hydrophilic treatment. After that, uniformly coat 150 μL of the photo- and electrochromic dual-responsive functional layer solution on the glass substrate, and anneal it in a vacuum drying oven at 80 °C for 30 min to form a molybdenum-doped tungsten oxide quantum dot solution / poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite photo- and electrochromic dual-responsive functional layer.

[0037] (3) Preparation of polyacrylamide / 2-acrylamido-2-methylpropane sulfonic acid / acrylic acid / lithium chloride hydrogel electrolyte layer: Weigh 5 g of acrylamide, 1.23 g of 2-acrylamido-2-methylpropane sulfonic acid, 2.84 g of acrylic acid, and 2.95 g of lithium chloride, dissolve them in 20 mL of deionized water, stir to form a homogeneous mixed solution, then add 25 mg of N,N-methylenebisacrylamide, 36 mg of ammonium persulfate, and 0.34 g of polyvinylpyrrolidone, stir for 30 min to obtain a clear and transparent precursor solution. After that, transfer the precursor solution to a mold, keep it in an oven at 60 °C for 60 min, then raise the temperature to 80 °C and heat for 30 min, and let it cool naturally to room temperature to obtain polyacrylamide / 2-acrylamido-2-methylpropane sulfonic acid / acrylic acid / lithium chloride hydrogel electrolyte;

[0038] (4) Preparation of photo- and electrochromic dual-responsive functional layer / polyacrylamide / 2-acrylamido-2-methylpropane sulfonic acid / acrylic acid / lithium chloride hydrogel composite: Attach the polyacrylamide / 2-acrylamido-2-methylpropane sulfonic acid / acrylic acid / lithium chloride hydrogel to the photo- and electrochromic dual-responsive functional layer to make the two layers in close contact, place it in an oven at 80 °C for 5 min, and completely transfer the photo- and electrochromic dual-responsive functional layer to the surface of the polyacrylamide / 2-acrylamido-2-methylpropane sulfonic acid / acrylic acid / lithium chloride hydrogel through thermal transfer.

[0039] (5) Preparation of a Dynamically Tunable Photochromic and Electrochromic Dual-Response Device: Two indium tin oxide conductive glasses were respectively attached to both sides of the composite to prepare a dynamically tunable photochromic and electrochromic dual-response device.

[0040] As can be seen from Figure 4 , for the photochromic and electrochromic dual-response functional layer prepared by coating 150 μL of the photochromic and electrochromic composite solution, its thickness is 2.73 μm. As can be seen from Figure 5 , for the photochromic and electrochromic dual-response functional layer prepared by coating 150 μL of the photochromic and electrochromic composite solution, the optical contrast of the device is 33.2%.

[0041] Example 2: On the basis of Example 1, the coating amount of the molybdenum-doped tungsten oxide quantum dot / poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite solution in step (2) was changed to 50 μL, and the rest remained the same, to obtain a dynamically tunable photochromic and electrochromic dual-response device.

[0042] As can be seen from Figure 4 , for the photochromic and electrochromic dual-response functional layer prepared by coating 50 μL of the photochromic and electrochromic composite solution, its thickness is 0.67 μm. As can be seen from Figure 5 , for the photochromic and electrochromic dual-response functional layer prepared by coating 50 μL of the photochromic and electrochromic composite solution, the optical contrast of the device is 27.64%.

[0043] Example 3: On the basis of Example 1, the coating amount of the molybdenum-doped tungsten oxide quantum dot / poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite solution in step (2) was changed to 100 μL, and the rest remained the same, to obtain a dynamically tunable photochromic and electrochromic dual-response device.

[0044] Figure 4 As can be seen, for the photochromic and electrochromic dual-response functional layer prepared by coating 100 μL of the photochromic and electrochromic composite solution, its thickness is 1.61 μm. Figure 5 As can be seen, for the photochromic and electrochromic dual-response functional layer prepared by coating 100 μL of the photochromic and electrochromic composite solution, the optical contrast of the device is 24.04%.

[0045] Example 4: On the basis of Example 1, the coating amount of the molybdenum-doped tungsten oxide quantum dot / poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite solution in step (2) was changed to 200 μL, and the rest remained the same, to obtain a dynamically tunable photo-electrochromic dual-response device.

[0046] Figure 4 As can be seen, for the photo-electrochromic dual-response functional layer prepared by coating 200 μL of the photochromic and electrochromic composite solution, its thickness is 3.79 μm. Figure 5It can be seen that for the photo- and electrochromic dual-responsive functional layer prepared by coating 200 μL of the photo- and electrochromic composite solution, the optical contrast of the device is 28.31%.

[0047] Example 5: On the basis of Example 1, change the coating amount of the molybdenum-doped tungsten oxide quantum dot / poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite solution in step (2) to 250 μL, and the rest remains the same, to obtain a dynamically tunable photo- and electrochromic dual-responsive device.

[0048] Figure 4 It can be seen that for the photo- and electrochromic dual-responsive functional layer prepared by coating 250 μL of the photo- and electrochromic composite solution, its thickness is 4.93 μm. Figure 5 It can be seen that for the photo- and electrochromic dual-responsive functional layer prepared by coating 250 μL of the photo- and electrochromic composite solution, the optical contrast of the device is 25.62%.

[0049] From Figure 6 From the optical pictures of the dual-responsive device before and after electrochromism, it can be seen that after electrochromism, the color of the dual-responsive device changes to dark blue.

[0050] From Figure 7 From the optical pictures and transmittance curves of the photochromic process of the dual-responsive device, it can be seen that within 30 s of visible light irradiation, the color of the dual-responsive device gradually deepens from light blue to dark blue, and the transmittance decreases from 46.5% to 18.47%.

[0051] From Figure 8 From the optical pictures of the photo- and electrochromic dual-responsive co-regulation, it can be seen that the dual-responsive device realizes photochromism. After applying a voltage of 3 V, the color further deepens to dark blue. After applying a bias voltage of -1.5 V, the device realizes a rapid fading process within 3 s; and after photochromism of the dual-responsive device, applying a bias voltage of -1.5 V realizes fading within 3 s.

[0052] From Figure 9 From the optical pictures of the application of the intelligent color-changing window, it can be seen that the photochromic intelligent color-changing window can be further electrochromic under an external voltage, realizing the co-regulation of photo- and electrochromism and deepening the color of the intelligent color-changing window.

[0053] In summary, the present invention uses molybdenum-doped tungsten oxide quantum dots and poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid to construct a photo / electric dual-responsive functional layer, transfers it to the surface of a high ionic conductivity hydrogel by thermal transfer technology to form a composite, and then composites the composite with two indium tin oxide conductive glasses to form a photo- and electrochromic dual-responsive device. The device exhibits fast and reversible photo- and electrochromic synergy, realizes two-way dynamic regulation of optical transmittance, and has broad application prospects in intelligent color-changing windows and optical camouflage devices, etc.

Claims

1. A dynamically adjustable photo - electrochromic dual - response device, characterized in that, It includes a lower electrode, a photo- and electrochromic dual-response functional layer, an electrolyte layer, and an upper electrode. Among them, the raw materials of the photo- and electrochromic dual-response functional layer are composed of molybdenum-doped tungsten oxide quantum dots and poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid.

2. The photo - electrochromic dual - response device according to claim 1, characterized in that, The thickness of the photo- and electrochromic dual-response functional layer is 0.5 - 5 μm.

3. The photoelectrically - electrochromic dual - response device according to claim 1, wherein Both the upper electrode and the lower electrode are indium tin oxide conductive glasses.

4. The photo - electrochromic dual - response device according to claim 1, wherein, The electrolyte layer is composed of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, and lithium chloride with a mass ratio of (4 - 6):(1 - 2):(2 - 4):(2 - 4), and its thickness is 2 - 5 mm.

5. A method for manufacturing the photo-electrochromic dual-responsive device according to any one of claims 1-4, characterized in that, It includes the following steps: (1) Using sodium tungstate dihydrate, ammonium molybdate tetrahydrate, a solvent, an acid solution, and ethylene glycol as raw materials, a molybdenum-doped tungsten oxide quantum dot solution is prepared by a hydrothermal method. (2) The molybdenum-doped tungsten oxide quantum dot solution is mixed evenly with a poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid solution, a solvent, and a surfactant to obtain a photo- and electrochromic dual-response functional layer solution, which is coated on the surface of indium tin oxide conductive glass and annealed to form a photo- and electrochromic dual-response functional layer. (3) Using acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, and lithium chloride as raw materials, a polyacrylamide / 2-acrylamido-2-methylpropanesulfonic acid / acrylic acid / lithium chloride hydrogel electrolyte layer is prepared. (4) The photo- and electrochromic dual-response functional layer is transferred to the surface of the polyacrylamide / 2-acrylamido-2-methylpropanesulfonic acid / acrylic acid / lithium chloride hydrogel electrolyte layer by a thermal transfer technique to form a composite. (5) The composite is sandwiched between the upper electrode and the lower electrode to form a sandwich structure, and a dynamically tunable photo- and electrochromic dual-response device is prepared.

6. The manufacturing method according to claim 5, wherein In step (1), the specific preparation process of the molybdenum-doped tungsten oxide quantum dot solution is as follows: Sodium tungstate dihydrate and ammonium molybdate tetrahydrate are completely dissolved in a solvent, an acid solution is slowly added dropwise and stirred until precipitation is complete, the supernatant is removed by centrifugation, and the precipitate is washed with the solvent until the pH is 2 - 3. The washed precipitate is added to an ethylene glycol solution, heated and stirred to form a clear and transparent solution, and a molybdenum-doped tungsten oxide quantum dot solution is prepared by a hydrothermal reaction; among them, the molar ratio of sodium tungstate dihydrate to ammonium molybdate tetrahydrate is 10 - 100:1, and the dosage ratio of sodium tungstate dihydrate to the solvent is 0.025 - 0.05 mol:20 - 30 mL; the acid solution is hydrochloric acid with a mass fraction of 36 - 38%, the temperature of the heating and stirring is 90 ± 5 °C, and the parameters of the hydrothermal reaction are: the hydrothermal reaction temperature is 160 - 200 °C, and the hydrothermal reaction time is 40 - 56 h.

7. The manufacturing method according to claim 5, characterized in that, In step (2), the mass ratio of the molybdenum-doped tungsten oxide quantum dot solution, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid solution, solvent, and surfactant is (0.56 - 2.24):(2 - 4):(5.76 - 7.44):(0.005 - 0.01); the mass concentration of the polystyrene sulfonic acid solution is 1 - 1.3%, the solvent is deionized water, and the surfactant is Triton-X100; the area of the indium tin oxide conductive glass is 4 - 12 cm 2 When it is, the coating volume of the photoinduced and electrochromic dual-responsive functional layer solution used is 50 - 250 μL, and the parameters of the annealing treatment are: the annealing treatment temperature is 70 - 90 °C, and the annealing treatment time is 45 - 90 min.

8. The manufacturing method according to claim 5, characterized in that, In step (3), the specific preparation process of the polyacrylamide / 2-acrylamido-2-methylpropanesulfonic acid / acrylic acid / lithium chloride hydrogel electrolyte layer is as follows: acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, and lithium chloride are dissolved in a solvent, and then polyvinylpyrrolidone-K30, N,N'-methylenebisacrylamide, and ammonium persulfate are added and mixed and stirred until clear and transparent. The obtained precursor solution is transferred to a mold for heat polymerization to obtain the product. Among them, the dosage ratio of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, lithium chloride, solvent, polyvinylpyrrolidone-K30, N,N'-methylenebisacrylamide, and ammonium persulfate is 5-15 g: 1.23-3.69 g: 2.84-8.52 g: 2.95-8.85 g: 20-60 mL: 0.34-1.02 g: 25-75 mg: 36-108 mg; the conditions for the heat polymerization are: first heat at 60±5 °C for 60-80 min, and then heat at 80±5 °C for 30-40 min.

9. The manufacturing method according to claim 5, wherein, In step (4), the process parameters of the thermal transfer are: the thermal transfer temperature is 60-80 °C, and the thermal transfer time is 5-10 min.

10. Use of a dynamically adjustable photo-electrochromic dual-response device according to any one of claims 1-4 as an intelligent window in an energy-saving building.

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