Temperature response type broadband energy-saving all-solid-state electrochromic device and preparation method thereof

Abstract

The invention relates to a temperature response type broadband energy-saving all-solid-state electrochromic device and a preparation method thereof. The structure of the temperature response type broadband energy-saving all-solid-state electrochromic device comprises a glass substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a phase change layer, a second transparent electrode and a surface high-transmittance substrate which are sequentially stacked, or the glass substrate, the first transparent electrode, the electrochromic layer, the electrolyte layer, the phase change layer, the second transparent electrode and the surface high-transparency substrate are sequentially stacked.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromic functional materials and devices, and specifically relates to a temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device and a preparation method thereof. Background Art

[0002] Statistics show that buildings account for over 40% of total energy consumption. Current approaches to reducing building energy consumption include active and passive energy conservation. Active energy conservation improves energy efficiency and thereby reduces energy consumption by comprehensively optimizing HVAC systems. Passive energy conservation is achieved by enhancing the insulation between the building and the external heat exchange medium. For example, improving the insulation of building walls, roofs, doors, and windows reduces heat loss and dissipation, thereby reducing building energy consumption. Furthermore, due to lighting and design requirements, the proportion of glazing in doors and windows in a building structure has gradually increased. However, window glass has the poorest insulation performance in building structures. Statistical simulations show that heat exchange through windows accounts for 70% and 60% of a building's total heat exchange in summer and winter, respectively. Clearly, windows consume the majority of a building's energy. Therefore, reducing energy loss through windows and doors is key to improving building energy efficiency.

[0003] Window heat exchange involves heat conduction, convection, and radiation. Radiative heat exchange involves solar radiation in the visible (380–780 nm) and near-infrared (780–2500 nm) ranges, as well as spontaneous room-temperature radiation in the mid-infrared "atmospheric window" (8–14 μm). However, conventional windows generally have difficulty dynamically regulating visible and near-infrared solar radiation, and their ability to regulate room-temperature radiation is weak, resulting in significant energy losses in buildings. On the one hand, the transmittance of visible and near-infrared light is difficult to independently control, and the high natural light transmittance required for indoor lighting sacrifices some of the solar radiation regulation capability. On the other hand, window glass, primarily composed of silica, exhibits strong absorption (i.e., a highly emissive state) in wavelengths above 4 μm. Consequently, in summer, the outdoor ambient and window surface temperatures are higher than those in the room, causing the windows to continuously radiate heat into the room. In winter, the outdoor and window surface temperatures are lower, causing the windows to continuously radiate heat into the room, significantly increasing air conditioning energy consumption for both summer cooling and winter heating.

[0004] Electrochromism refers to the phenomenon that the optical properties of a material (reflectivity, transmittance, absorptivity, etc.) undergo stable and reversible changes under the action of an external electric field, which manifests itself in appearance as reversible changes in color and transparency. Electrochromic devices are generally composed of a transparent electrode, an electrochromic layer, an ion conduction layer (also called an electrolyte layer), an ion storage layer, and a transparent electrode. Among them, WO3 is the most widely used inorganic electrochromic material. The ion conduction layer provides an ion transmission channel between the electrochromic layer and the ion storage layer. It needs to be compatible with the film materials on both sides and have good electronic insulation and ionic conductivity. The electrochromic smart window prepared using electrochromic materials has a series of advantages such as continuous and precise adjustment of optical properties, strong resistance to environmental interference, good adaptability, low power consumption, and fast coloring / fading response speed. Therefore, compared with other stimulation methods, smart windows based on electrochromism have obvious advantages.

[0005] However, current research on electrochromic devices with wide-band regulation mainly revolves around the controllable deposition of metal ions, and uses the high emissivity and low reflection characteristics of the mid-infrared after metal deposition to construct devices with controllable emissivity. However, this type of device often uses liquid electrolytes, which have problems such as easy leakage, poor stability and insecurity, and also faces problems such as poor uniformity and low coloring rate during the amplification process. At the same time, all-solid-state electrochromic devices are often difficult to adjust over a wide band or have weak regulation capabilities. Usually, all-solid-state electrochromic devices can only regulate visible and near-infrared light (0.38-2.5μm) covered by sunlight, and it is difficult to use deep space cold energy to manage radiant heat through the "atmospheric window" (8-14m). Effective management of mid-infrared radiation heat will help further improve the energy efficiency of buildings. Summary of the Invention

[0006] In view of the above technical problems, the object of the present invention is to provide a temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device and a preparation method thereof.

[0007] In the first aspect, the present invention provides a temperature-responsive wide-band energy-saving all-solid-state electrochromic device, the structure of which includes: a glass substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a phase change layer, a second transparent electrode, and a surface high-transmittance substrate stacked in sequence; or, a glass substrate, a first transparent electrode, an electrochromic layer, an electrolyte layer, a phase change layer, a second transparent electrode, and a surface high-transmittance substrate stacked in sequence.

[0008] Preferably, the first transparent electrode material includes at least one of transparent conductive oxide, MXENE, and metal nanowires; preferably, the sheet resistance of the first transparent electrode is 10 to 400 Ω / cm 2, the sunlight transmittance in the 0.38-2.5μm band is ≥75%, and the mid-infrared reflectivity in the 8-14um band is ≥75%.

[0009] Preferably, the material of the second transparent electrode includes at least one of transparent conductive oxide, MXENE, and metal nanowires; preferably, the second transparent electrode has a solar transmittance of ≥75% in the 0.38-2.5 μm band and a mid-infrared transmittance of ≥75% in the 8-14 μm band.

[0010] Preferably, the material of the electrochromic layer includes WO 3-x 、MoO 3-x 、TiO 2-x , at least one of polythiophene, polypyrrole, polyaniline and Prussian blue; the thickness is 200 to 600 nm.

[0011] Preferably, the electrolyte layer is a cation conductive gel electrolyte layer based on organic resin, and the cations include Li + 、Al 3+ , K + and Na + At least one of; preferably, the thickness of the electrolyte layer is 0.6-5μm.

[0012] Preferably, the material of the phase change layer includes VO2, V2O3, La 0.825 Sr 0.175 MnO3 and La 0.7 Ca 0.3 One of MnO3, with a phase transition temperature of -80 to 100°C, a thickness of 10 to 40 nm, a mid-infrared transmittance before the phase transition of ≥75%, and a mid-infrared emissivity after the phase transition of ≥50%.

[0013] Preferably, the material of the surface high-transmittance substrate includes one of barium fluoride, calcium fluoride, magnesium fluoride, zinc sulfide, zinc selenide, sodium chloride, silicon, germanium, sapphire, polyethylene and poly (4-methyl-1-pentene); preferably, the surface high-transmittance substrate has a sunlight transmittance of ≥85% in the 0.38-2.5μm band and a transmittance of ≥85% in the 2.5-25um mid-infrared band.

[0014] In a second aspect, the present invention provides a method for preparing the above-mentioned temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device, the preparation method comprising the following steps: (1) preparing a first transparent electrode on the surface of a glass substrate, preparing a second transparent electrode on the surface of a high-transmittance substrate, and obtaining a phase change layer on the surface of the second transparent electrode by magnetron sputtering deposition; (2) preparing an electrochromic layer on the surface of the phase change layer, filling an electrolyte solution between the electrochromic layer and the first transparent electrode by a vacuum drip irrigation process and curing; or preparing an electrochromic layer on the surface of the first transparent electrode, filling an electrolyte solution between the electrochromic layer and the phase change layer by a vacuum drip irrigation process and curing, to obtain the temperature-responsive wide-band energy-saving all-solid-state electrochromic device.

[0015] Preferably, in step (1), the process parameters of the magnetron sputtering deposition phase change layer include: the target material is VO2, V2O3, La 0.825 Sr 0.175 MnO3 and La 0.7 Ca 0.3 MnO3; the sputtering gas is argon and oxygen, the total pressure is 0.5-2.0 Pa, the oxygen partial pressure is 0-50%, the distance between the target and the substrate is 10-20 cm, the initial substrate temperature is room temperature, and the DC power applied to the target is 70-400 W or the power density is 1.3-8.0 W / cm 2 , the pre-sputtering time is 0-5min, and the sputtering time is 5-50min.

[0016] Preferably, in step (1), the phase change layer is heat treated after being deposited; wherein, the heat treatment pressure is 1-10 Pa, and the heat treatment process includes: heating to 100-300°C for 40-150s and then keeping warm for 20-200s, then heating to 350-500°C for 5-200s again and keeping warm for 100-1000s, and naturally cooling to room temperature.

[0017] Beneficial effects (1) The present invention achieves wide-band control from visible light to mid- and far-infrared light by designing a simple all-solid-state electrochromic structure, which can achieve excellent energy-saving effects in major regions around the world; (2) The present invention introduces phase change materials into the device structure, which transforms high transmittance into partial reflection in the mid-infrared around the phase change temperature. The Fabry-Perot resonant cavity designed based on this characteristic transforms the mid-infrared from a high reflective state to a high absorption state before and after the phase change, thus achieving a large-scale adjustment of the "atmospheric window" mid-infrared (8-14 μm); (3) The device preparation method provided by the present invention is simple and easy to operate. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a schematic diagram of an exemplary structure of a temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device provided by the present invention; Figure 2 Schematic diagram of optical interference of multilayer structure. DETAILED DESCRIPTION

[0019] The present invention is further described below through the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, rather than to limit the present invention.

[0020] First, if Figure 1 As shown, the present invention provides a temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device. The structure of the temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device may include: a glass substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a phase change layer, a second transparent electrode, and a surface-high-transmittance substrate stacked in sequence; or a glass substrate, a first transparent electrode, an electrochromic layer, an electrolyte layer, a phase change layer, a second transparent electrode, and a surface-high-transmittance substrate stacked in sequence.

[0021] In some embodiments, the first transparent electrode material may include at least one of transparent conductive oxide, MXENE, and metal nanowires; preferably, the sheet resistance of the first transparent electrode may be 10 to 400 Ω / cm 2 , the sunlight transmittance in the 0.38-2.5μm band can be ≥75%, and the mid-infrared reflectivity in the 8-14um band can be ≥75%.

[0022] The first transparent electrode used in this invention has high transmittance in the solar wavelength band, facilitating solar control. Furthermore, its high limited infrared reflectivity promotes better infrared control performance in the resulting resonant cavity. However, if the resistance is too low, the device is susceptible to breakdown; if the resistance is too high, a higher voltage is required to drive the device to color. Furthermore, excessively high resistance can cause a significant surface voltage drop, resulting in uneven coloring.

[0023] In some embodiments, the material of the second transparent electrode may include at least one of a transparent conductive oxide, MXENE, or metal nanowires. Preferably, the second transparent electrode has a solar transmittance of ≥75% in the 0.38-2.5 μm band and a mid-infrared transmittance of ≥75% in the 8-14 μm band. Using a second transparent electrode with good transmittance in both the solar and mid-infrared bands helps improve the device's solar and infrared control capabilities.

[0024] The thickness of the first transparent electrode can be 100-500nm, and the thickness of the second transparent electrode can be 10-50nm. By limiting the thickness of the first electrode to this range, the requirements for resistance and infrared reflectivity can be met. If the thickness is too small, the resistance will be too high, making it difficult to drive the device to change color uniformly. If the thickness is too large, the resistance will be too low, which will easily cause device breakdown and reduce solar transmittance. In addition, if the thickness of the second transparent electrode is too large, the infrared transmittance will be insufficient. If the thickness is too small, the resistance will be too high, making it difficult to drive the device to change color uniformly.

[0025] In some embodiments, the material of the electrochromic layer may include WO 3-x 、MoO 3-x 、TiO 2-x The electrochromic layer may be at least one of polythiophene, polypyrrole, polyaniline, and Prussian blue; and may have a thickness of 200 to 600 nm. A too thick electrochromic layer may affect ion migration performance; a too thin layer may result in insufficient coloration.

[0026] In some embodiments, the electrolyte layer may be a cation conductive gel electrolyte layer based on an organic resin, and the cation may include Li + 、Al 3+ , K + and Na + At least one of the following; preferably, the thickness of the electrolyte layer can be 0.6-5 μm. If the electrolyte layer is too thick, the infrared transmittance will be reduced, affecting the infrared regulation capability of the device; if the thickness is too thin, it will be difficult to form a continuous electrolyte layer, which may easily cause internal short circuits.

[0027] In some embodiments, the material of the phase change layer may include VO2, V2O3, La 0.825 Sr 0.175 MnO3 and La 0.7 Ca 0.3 One of MnO3, the phase transition temperature can be -80 ~ 100 ° C, the thickness can be 10-40nm, the mid-infrared transmittance before the phase transition can be ≥75%, and the mid-infrared emissivity after the phase transition can be ≥50%.

[0028] Among them, if the phase change layer is too thick, it will affect the solar transmittance and regulation performance; if the thickness is too small, it will lead to insufficient infrared reflection ability, affect the construction of the resonant cavity, and cause the infrared regulation performance before and after the phase change to decrease.

[0029] In some embodiments, the material of the high-transmittance surface substrate may include one of barium fluoride, calcium fluoride, magnesium fluoride, zinc sulfide, zinc selenide, sodium chloride, silicon, germanium, sapphire, polyethylene, and poly(4-methyl-1-pentene) (TPX). Preferably, the high-transmittance surface substrate has a solar transmittance of 85% or greater in the 0.38-2.5 μm band and a transmittance of 85% or greater in the 2.5-25 μm mid-infrared band. Insufficient infrared transmittance of the high-transmittance surface substrate can easily lead to a decrease in the infrared regulation capability of the device.

[0030] In some embodiments, the solar energy regulation capability of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device can be ≥0.5 (the transmittance of the device in the solar band (0.38-2.5um) changes before and after the application of voltage, that is, the transmitted solar energy is regulated); the mid- and far-infrared emissivity regulation rate before and after the phase change (mid- and far-infrared regulation capability) is ≥0.35, and the mid-infrared regulation temperature point range can be -80 to 100°C for different application scenarios.

[0031] The present invention introduces phase change materials through structural design, which changes from high transmittance to partial reflection in the mid-infrared band above and below the phase change temperature. Based on this characteristic, a Fabry-Perot cavity (FP) is designed, and the mid-infrared changes from high reflection to high absorption before and after the phase change, achieving a large-scale adjustment of the "atmospheric window" mid-infrared (8-14um). Therefore, the electrochromic device designed in this patent can effectively regulate the energy of the sunlight band at low temperatures (the surface temperature of the device is lower than the phase change temperature, such as <30°C), while the mid-infrared maintains a low emission state (emissivity ≤ 0.2), which helps to reduce indoor and outdoor heat exchange; when the temperature rises (the surface temperature of the device is higher than the phase change temperature, such as >30°C), it can not only effectively regulate the energy of the sunlight band, but also the mid-infrared maintains a high emission state (emissivity ≥ 0.5), which helps to dissipate heat from indoors to outside.

[0032] The design of the FP resonant cavity ensures the successful creation of optically band-selective transparent conductive films. The two dielectric layers and the extremely thin metal layer can be considered a parallel structure, resulting in low resistivity. The high-refractive-index dielectric layer selectively transmits photons through interference, achieving band-selective transmission and reflection, thereby producing a film with a specific color.

[0033] Furthermore, if Figure 2As shown, when light strikes the surface of a multilayer thin film, some light undergoes total reflection according to the Fresnel principle, while another portion enters the film through the first film-substrate interface. As light passes through each film-substrate interface, it undergoes partial reflection based on differences in refractive index. Light reflected from each interface undergoes wavelength-dependent interference with light reflected from the next interface. If the optical path difference Δ between the two beams is an integer multiple of their wavelengths λ, i.e., Δ = mλ (m is a positive integer), the two beams undergo constructive interference, with their intensities additively enhanced. If the optical path difference Δ is a half-integer multiple of λ, i.e., Δ = (m + 1 / 2)λ, the two beams undergo destructive interference, with their intensities canceling each other out. By precisely designing the optical thickness and material of each thin film layer, light of specific wavelengths can primarily undergo constructive interference within the multilayer structure, while light of other wavelengths undergoes destructive interference. Consequently, only light within a certain wavelength range can pass through the multilayer thin film, while light of other wavelengths is reflected. The disclosed technical solution utilizes this characteristic to precisely control the thickness of each device component, concentrating the selectively regulated wavelength band within the "atmospheric window" (8-14μm). This is because the atmosphere within the "atmospheric window" has weak absorption and scattering of electromagnetic waves of different wavelengths, and the heat of the building can directly exchange heat with deep space (0k)j, achieving better zero-energy energy-saving efficiency.

[0034] It should also be noted that the structure of the resonant cavity is generally composed of a high-reflection layer, a transparent dielectric layer, and a low-reflection layer. In conventional device structure designs, although a resonant cavity structure is also used, the vanadium oxide and the like are generally used as a transparent layer and a metal as a high-infrared reflective layer at the bottom layer. In this patent, VO2 and the like are used as low-reflection layers, so the present invention is different from the conventional device structure design, and the role played by VO2 and the like is also different. In addition, from the perspective of the principle of device function realization, conventional structure devices generally use temperature-driven methods such as electrothermal conversion of thermoelectric devices to achieve thermal infrared regulation. However, the electrochromic structure designed in the present invention has dual electrothermal control capabilities and has good control performance for the solar band. That is, the electrochromic device designed in this patent can effectively regulate the energy of the sunlight band at low temperatures, while maintaining a low emission state in the mid-infrared (helping to reduce heat exchange between indoors and outdoors). When the temperature rises, it can not only effectively regulate the energy of the sunlight band, but also maintain a high emission state in the mid-infrared (helping to dissipate heat from indoors to outdoors). The present invention integrates a resonant cavity structure with an electrochromic device (which is initially transparent in the solar band and has good solar regulation capabilities), enabling it to achieve solar regulation and infrared selective regulation according to temperature.

[0035] The following is an exemplary description of the method for preparing the temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device provided by the present invention. The method may include the following steps: (1) preparing a first transparent electrode on the surface of a glass substrate, preparing a second transparent electrode on the surface of a high-transmittance substrate, and obtaining a phase change layer on the surface of the second transparent electrode by magnetron sputtering deposition; (2) preparing an electrochromic layer on the surface of the phase change layer, filling an electrolyte solution between the electrochromic layer and the first transparent electrode by a vacuum drip irrigation process and curing; or preparing an electrochromic layer on the surface of the first transparent electrode, filling an electrolyte solution between the electrochromic layer and the phase change layer by a vacuum drip irrigation process and curing, to obtain the temperature-responsive wide-band energy-saving all-solid-state electrochromic device.

[0036] In some embodiments, in step (1), the process parameters of the magnetron sputtering deposition phase change layer may include: the target material is VO2, V2O3, La 0.825 Sr 0.175 MnO3 and La 0.7 Ca 0.3 MnO3; the sputtering gas is argon and oxygen, the total pressure is 0.5-2.0 Pa, the oxygen partial pressure is 0-50%, the distance between the target and the substrate is 10-20 cm, the initial substrate temperature is room temperature, and the DC power applied to the target is 70-400 W or the power density is 1.3-8.0 W / cm 2 , the pre-sputtering time is 0-5min, and the sputtering time is 5-50min.

[0037] In some embodiments, in step (1), the phase change layer may be heat treated after being deposited; wherein, the heat treatment pressure may be 1-10 Pa, and the heat treatment process may include: heating to 100-300°C for 40-150s and then keeping warm for 20-200s, then heating to 350-500°C for 5-200s again and keeping warm for 100-1000s, and then naturally cooling to room temperature.

[0038] In some embodiments, in step (2), the method of preparing the electrochromic layer may include magnetron sputtering, spin coating or electrodeposition; preferably, the process parameters of magnetron sputtering deposition of the electrochromic layer may include: using metal tungsten, molybdenum or titanium as the target material, the sputtering gas is argon and oxygen, the total pressure is 0.5-2.0 Pa, the oxygen partial pressure is 0-50%, the distance between the target and the substrate is 10-20 cm, the initial substrate temperature is room temperature, the DC power applied to the target is 30-150 W or the power density is 0.6-3.0 W / cm 2 , the pre-sputtering time is 0-10min, and the sputtering time is 10-60min.

[0039] To be more specific, the DC magnetron sputtering system equipment used in the magnetron sputtering deposition of the present invention may include a deposition chamber, a sampling chamber, several target heads, a substrate plate, a DC current and a series of mechanical pumps and vacuum pumps, wherein the target head and the substrate plate are at a certain angle and a certain distance apart, and the DC power supply is connected to the target head. The substrate is ultrasonically cleaned, and the substrate is ultrasonically cleaned with acetone, anhydrous ethanol, and deionized water for 20 minutes each, and blown dry with compressed air. Cover a certain part of the conductive substrate with high-temperature tape as an electrode, and fix it on the substrate tray, put it into the sampling chamber, turn on the mechanical pump to pump it below 5Pa, and then open the baffle valve to send it into the vacuum degree (background vacuum degree) that has reached 10 -4 Pa and below in the sputtering room.

[0040] The specific sputtering deposition process is as follows: high-purity argon and oxygen are introduced into the sputtering chamber respectively, the purity of the argon and oxygen used is 99.99% or above, and the total pressure and oxygen partial pressure in the chamber are controlled to be in the range of 0.5-2.0 Pa and 0-50%, respectively, with the oxygen partial pressure preferably being 0-25%. The vertical distance between the target and the substrate is controlled to be 10-20 cm, and the initial substrate temperature is room temperature. Turn on the DC power supply, control the DC power supply power to 30-400 W, the pre-sputtering time is 0-30 min, the sputtering time is 5-60 min, and the substrate temperature is room temperature. After the sputtering is completed, wait until the substrate temperature drops to room temperature and remove the substrate.

[0041] In some embodiments, in step (2), the electrolyte solution can be obtained by mixing the solvent, photoresin, stabilizer, UV absorber, organic precursor and ion source solution in a mass ratio of (1-5):(0.5-5):(0.1-2):(0.01-0.2):(0.5-5):1.

[0042] Among them, the solvent may include propylene glycol methyl ether acetate PMA, N-methylpyrrolidone NMP and N,N-dimethylformamide DMF; the photoresist may be UV curable resin UC-935 (Xianmeite); the stabilizer may be ferrocene; the ultraviolet absorber may be photoinitiator 1173; and the organic precursor may be ethoxylated trimethylolpropane triacrylate ETPTA.

[0043] The ion source in the ion source solution may include at least one of chlorides, perchlorates and sulfates of Li, Na, Mg or Zn; preferably, the concentration of the ion source solution may be 0.1-2 mol / L.

[0044] In some embodiments, in step (2), the curing method can be ultraviolet curing (such as 100W) or thermal curing.

[0045] The preparation process involved in the present invention is simple, low in cost, and easy to promote. The high-performance electrochromic device developed by the present invention has broader application prospects.

[0046] This patent proposes a wide-band, all-solid-state electrochromic device based on WO3 electrochromic material, achieved through material innovation and structural design. The device's controllable capabilities within the "atmospheric window" are further enhanced through the FP resonant cavity structure. Therefore, the temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device designed and fabricated in this invention is expected to be applied to smart windows, significantly reducing cooling or insulation energy consumption in both summer and winter. According to Energyplus software simulations, this electrochromic smart window demonstrates superior energy efficiency compared to Low-E glass in major regions around the world.

[0047] The following examples are further given to illustrate the present invention in detail. It should be understood that the following examples are only used to further illustrate the present invention and cannot be interpreted as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention all fall within the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples within a suitable range, and those skilled in the art can make selections within a suitable range through the description herein, and are not limited to the specific numerical values ​​exemplified below. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.

[0048] Example 1

[0049] The method for preparing the temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device provided in this embodiment comprises the following steps: (1) First, glass is used as a transparent substrate, and a first transparent electrode with high sunlight transmittance (transmittance 78%) and high infrared reflectance (reflectance 75%) is prepared on its upper surface; secondly, a second transparent electrode with high sunlight transmittance and high infrared transmittance (wideband transmittance 80%) is prepared on a BaF2 substrate; a VO2 phase change layer is prepared on the surface of the second transparent electrode: V2O3 is used as a target material, the total pressure is 2 Pa, the oxygen partial pressure is 2%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power applied to the target material is 200 W or the power density is 4 W / cm 2 , a DC power supply is used to deposit 20nm on the surface; then, the phase change layer film is heat treated: heating to 150℃ for 120s and keeping it warm for 100s, then heating to 450℃ for another 120s and keeping it warm for 240s, and then naturally cooling to room temperature; (2) Depositing an inorganic electrochromic layer on the phase change layer by magnetron sputtering with tungsten, molybdenum or titanium as a target, argon and oxygen as the sputtering gas, a total pressure of 2.0 Pa, an oxygen partial pressure of 12%, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, a DC power of 70 W or a power density of 1.55 W / cm2 applied to the target. 2 , a 400nm electrochromic layer film is deposited on the surface using a DC power supply; secondly, according to the existing technology, an electrolyte solution prepared according to the mass ratio of PMA (propylene glycol methyl ether acetate), UC935 (Xianmei Te), ferrocene, photoinitiator 1173, ETPTA (ethoxylated trimethylolpropane triacrylate) and ion source solution is 1:1:1:0.1:2:1 is filled between the electrochromic layer and the first transparent electrode by vacuum drip irrigation; wherein, the ion source selected in the ion source solution is LiClO4, the solvent selected is propylene carbonate, and the concentration range of the ion source solution is 1 mol / L; a complete device is formed by ultraviolet curing; the thickness of the resin layer is controlled to be 1μm by the surface tension of the hard template and the resin solution; wherein the light curing is to place the device under a 100W ultraviolet lamp for uniform irradiation; after the device is cured, an organic solvent is used to remove excess organic matter on the surface of the device to obtain the temperature-responsive wide-band energy-saving all-solid-state electrochromic device.

[0050] Example 2

[0051] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), the thickness of the electrochromic layer film is 200 nm.

[0052] Example 3

[0053] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), the thickness of the electrochromic thin film is 600 nm.

[0054] Example 4

[0055] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), the thickness of the phase change layer is 10 nm.

[0056] Example 5

[0057] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), the thickness of the phase change layer is 40 nm.

[0058] Example 6

[0059] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), no heat treatment is performed after the phase change layer is deposited.

[0060] Example 7

[0061] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), the target material for depositing the phase change layer is La 0.825 Sr 0.175 MnO3(LSMO), the DC power applied to the target is 70W or the power density is 1.3W / cm 2 ; No heat treatment is performed after deposition of the phase change layer.

[0062] Example 8

[0063] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), the first transparent electrode has a solar light transmittance of 75% and an infrared reflectivity of 78%.

[0064] Example 9

[0065] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), the second transparent electrode has a sunlight and infrared broadband transmittance of 75%.

[0066] Example 10

[0067] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), the thickness of the resin layer is controlled to be 0.6 μm by the surface tension of the hard template and the resin solution.

[0068] Example 11

[0069] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), the thickness of the resin layer is controlled to be 5 μm by the surface tension of the hard template and the resin solution.

[0070] Example 12

[0071] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), an inorganic electrochromic layer is deposited on the surface of the first transparent electrode, and an electrolyte solution is filled between the electrochromic layer and the phase change layer and then solidified.

[0072] Example 13

[0073] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), TPX is selected as the surface high-transmittance substrate.

[0074] Example 14

[0075] The preparation method of the temperature-responsive wide-band energy-saving all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), polyethylene PE is selected as the surface high-transparency substrate.

[0076] Comparative Example 1

[0077] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (1), no phase change layer is prepared, and the inorganic electrochromic layer is directly deposited on the second transparent electrode.

[0078] Comparative Example 2

[0079] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (2), the inorganic electrochromic layer is not prepared, and the electrolyte solution is directly filled between the phase change layer and the first transparent electrode and solidified.

[0080] Comparative Example 3

[0081] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (2), the thickness of the resin layer is controlled to be 10 μm by the surface tension of the hard template and the resin solution.

[0082] Comparative Example 4

[0083] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (1), the thickness of the phase change layer is 50 nm.

[0084] Comparative Example 5

[0085] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (1), PET (polyethylene terephthalate) is selected as the surface high-transparency substrate.

[0086] Table 1 below compares the relevant parameters of the electrochromic devices prepared in Examples 1-14 and Comparative Examples 1-5:

[0087] Although the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description is not intended to limit the present invention. After reading the above description, various modifications and substitutions of the present invention will become apparent to those skilled in the art. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. A temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device, characterized in that: The structure of the temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device includes: a glass substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a phase change layer, a second transparent electrode, and a surface high-transmittance substrate stacked in sequence; or, a glass substrate, a first transparent electrode, an electrochromic layer, an electrolyte layer, a phase change layer, a second transparent electrode, and a surface high-transmittance substrate stacked in sequence.

2. The temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device according to claim 1, characterized in that: The first transparent electrode material includes at least one of transparent conductive oxide, MXENE, and metal nanowires; preferably, the sheet resistance of the first transparent electrode is 10 to 400 Ω / cm 2 , the sunlight transmittance in the 0.38-2.5μm band is ≥75%, and the mid-infrared reflectivity in the 8-14um band is ≥75%.

3. The temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device according to claim 1 or 2, characterized in that: The material of the second transparent electrode includes at least one of transparent conductive oxide, MXENE, and metal nanowires; preferably, the second transparent electrode has a sunlight transmittance of ≥75% in the 0.38-2.5 μm band and a mid-infrared transmittance of ≥75% in the 8-14 μm band.

4. The temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device according to any one of claims 1 to 3, characterized in that: The material of the electrochromic layer includes WO 3-x 、MoO 3-x 、TiO 2-x , at least one of polythiophene, polypyrrole, polyaniline and Prussian blue; the thickness is 200 to 600 nm.

5. The temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device according to any one of claims 1 to 4, characterized in that: The electrolyte layer is a cation conductive gel electrolyte layer based on organic resin, and the cations include Li + 、Al 3+ , K + and Na + At least one of; preferably, the thickness of the electrolyte layer is 0.6-5μm.

6. The temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device according to any one of claims 1 to 5, characterized in that: The materials of the phase change layer include VO2, V2O3, La 0.825 Sr 0.175 MnO3 and La 0.7 Ca 0.3 One of MnO3, with a phase transition temperature of -80 to 100°C, a thickness of 10 to 40 nm, a mid-infrared transmittance before the phase transition of ≥75%, and a mid-infrared emissivity after the phase transition of ≥50%.

7. The temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device according to any one of claims 1 to 6, characterized in that: The material of the surface high-transmittance substrate includes one of barium fluoride, calcium fluoride, magnesium fluoride, zinc sulfide, zinc selenide, sodium chloride, silicon, germanium, sapphire, polyethylene and poly (4-methyl-1-pentene); preferably, the surface high-transmittance substrate has a sunlight transmittance of ≥85% in the 0.38-2.5μm band and a transmittance of ≥85% in the 2.5-25um mid-infrared band.

8. A method for preparing a temperature-responsive, wide-band, energy-saving, all-solid-state electrochromic device according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: (1) preparing a first transparent electrode on the surface of a glass substrate, preparing a second transparent electrode on the surface of a high-transmittance substrate, and obtaining a phase change layer on the surface of the second transparent electrode by magnetron sputtering deposition; (2) preparing an electrochromic layer on the surface of the phase change layer, filling an electrolyte solution between the electrochromic layer and the first transparent electrode by a vacuum drip irrigation process and curing; or preparing an electrochromic layer on the surface of the first transparent electrode, filling an electrolyte solution between the electrochromic layer and the phase change layer by a vacuum drip irrigation process and curing, to obtain the temperature-responsive wide-band energy-saving all-solid-state electrochromic device.

9. The preparation method according to claim 8, characterized in that In step (1), the process parameters of the magnetron sputtering deposition phase change layer include: the target material is VO2, V2O3, La 0.825 Sr 0.175 MnO3 and La 0.7 Ca 0.3 MnO3; the sputtering gas is argon and oxygen, the total pressure is 0.5-2.0 Pa, the oxygen partial pressure is 0-50%, the distance between the target and the substrate is 10-20 cm, the initial substrate temperature is room temperature, and the DC power applied to the target is 70-400 W or the power density is 1.3-8.0 W / cm 2 , the pre-sputtering time is 0-5min, and the sputtering time is 5-50min.

10. The preparation method according to claim 8 or 9, characterized in that: In step (1), after the phase change layer is deposited, it is heat treated; wherein, the pressure of the heat treatment is 1-10Pa, and the heat treatment process includes: heating to 100-300°C for 40-150s and then keeping warm for 20-200s, then heating to 350-500°C for 5-200s again and keeping warm for 100-1000s, and naturally cooling to room temperature.

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