Low-voltage-driven broadband regulation and control all-solid-state electrochromic device and preparation method thereof

Abstract

The invention relates to a low-voltage-driven broadband regulation and control all-solid-state electrochromic device and a preparation method thereof. The structure of the low-voltage-driven broadband regulation and control all-solid-state electrochromic device comprises a substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a photoelectric effect layer, a second transparent electrode and a surface high-transmittance substrate which are sequentially stacked, or the substrate, the first transparent electrode, the electrochromic layer, the electrolyte layer, the photoelectric effect 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 low-voltage driven wide-band controlled 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 takes advantage of the high emissivity and low reflectivity 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, low coloring rate and high driving voltage 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 radiation heat through the "atmospheric window" (8-14m). The effective management of mid-infrared radiation heat is of great significance to further improve energy saving efficiency. Summary of the Invention

[0006] In response to the above technical problems, the object of the present invention is to provide a low-voltage driven wide-band controlled all-solid-state electrochromic device and a preparation method thereof.

[0007] In the first aspect, the present invention provides a low-voltage driven wide-band regulated all-solid-state electrochromic device, the structure of which includes: a substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a photoelectric effect layer, a second transparent electrode and a surface high-transmittance substrate stacked in sequence; or, a substrate, a first transparent electrode, an electrochromic layer, an electrolyte layer, a photoelectric effect layer, a second transparent electrode and a surface high-transmittance substrate stacked in sequence.

[0008] Preferably, the thickness of the electrolyte layer is 0.6-5 μm.

[0009] Preferably, the material of the electrochromic layer includes WO 3-x 、MoO 3-x and TiO 2-xAt least one of the above has a thickness of 200 to 600 nm.

[0010] Preferably, the material of the photoelectric effect layer includes one of TiO2, ZnO, BiVO4, Fe2O3, SrTiO3 and SnWO4, and the thickness is 50 to 200 nm.

[0011] In a second aspect, the present invention provides a method for preparing the above-mentioned low-voltage driven wide-band regulated all-solid-state electrochromic device, the preparation method comprising the following steps: depositing a photoelectric effect layer and an electrochromic layer on the surface of a second transparent electrode by magnetron sputtering according to the structure of the low-voltage driven wide-band regulated all-solid-state electrochromic device, filling an electrolyte solution between the electrochromic layer and the first transparent electrode and curing the electrolyte solution; or, An electrochromic layer is deposited on the surface of the first transparent electrode by magnetron sputtering, and a photoelectric effect layer is deposited on the surface of the second transparent electrode by magnetron sputtering; an electrolyte solution is filled between the electrochromic layer and the photoelectric effect layer and solidified.

[0012] Preferably, the preparation method further comprises an annealing process after magnetron sputtering deposition of the electrochromic layer; wherein the annealing process is a heat treatment under an inert atmosphere; and the gas pressure of the heat treatment is 2-200 torr.

[0013] Preferably, the electrolyte solution is obtained by mixing the resin, solvent, cosolvent, ferrocene, crosslinker and ion source solution in a mass ratio of 1: (1-3): (0.1-0.5): (0.05-0.2): (0.5-2): (1-3), and then adding 0.1-0.5% of the total mass of the mixed solution initiator and mixing again.

[0014] Preferably, the co-solvent comprises at least one of ethyl trifluoroacetate, methyl trifluoroacetate, ethyl trifluoroacetoacetate, ethyl pentafluoroacetate, ethyl acetate, ethyl propionate, ethyl acetoacetate and diethyl malonate.

[0015] Beneficial effects (1) The present invention has a simple all-solid-state electrochromic device that can achieve wide-band control from visible light to mid- and far-infrared, and can achieve excellent energy-saving effects in major regions around the world; (2) The present invention designs a composite thin film and utilizes the electrons generated by the photoelectric effect of the semiconductor thin film to achieve wide-band control of the device at low voltage; (3) The patented preparation method of this patented design is simple. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic diagram of the exemplary structure of the low-voltage driven wide-band regulated all-solid-state electrochromic device provided by the present invention. DETAILED DESCRIPTION

[0017] 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.

[0018] First, if Figure 1 As shown, the present invention provides a low-voltage driven, wide-band regulated, all-solid-state electrochromic device. The structure of the low-voltage driven, wide-band regulated, all-solid-state electrochromic device may include: a substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a photoelectric effect layer, a second transparent electrode, and a surface-high-transmittance substrate stacked in sequence; or a substrate, a first transparent electrode, an electrochromic layer, an electrolyte layer, a photoelectric effect layer, a second transparent electrode, and a surface-high-transmittance substrate stacked in sequence.

[0019] In some embodiments, the substrate may be made of glass and may have a thickness of 0.05-2 mm.

[0020] In some embodiments, the material of the first transparent electrode 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 is ≥75%, and the mid-infrared reflectivity in the 8~14um band is ≥75%.

[0021] In some embodiments, the material of the second transparent electrode may include at least one of transparent conductive oxide, MXENE, and metal nanowires; preferably, the square resistance of the second transparent electrode may be 50-500Ω / cm 2 , the sunlight transmittance in the 0.38~2.5μm band is ≥75%, and the mid-infrared transmittance in the 8~14um band is ≥75%.

[0022] By controlling the solar transmittance and mid-infrared reflectivity / transmittance of the first and second transparent electrodes within a set range, the fabricated device achieves both excellent solar and infrared regulation capabilities. Insufficient solar transmittance of the first and second electrodes directly impacts the overall solar regulation capability of the device. Insufficient infrared reflectivity of the first transparent electrode or insufficient infrared transmittance of the second transparent electrode also results in insufficient infrared regulation. The resistance of an electrode is directly related to its transmittance.

[0023] In some embodiments, the electrolyte layer may be a cation-conducting gel electrolyte layer based on an organic resin; preferably, the cation may include Li + 、Al 3+ , K + and Na+ At least one of the following: The electrolyte layer may have a thickness of 0.6-5 μm. The electrolyte itself absorbs infrared light to a certain extent. If the thickness is too great, the initial infrared transmittance of the device will decrease, affecting the overall regulation capability. If the thickness is too small, it will be difficult to form a continuous thin film, affecting the color uniformity of the device.

[0024] In some embodiments, the material of the electrochromic layer may include WO 3-x 、MoO 3-x and TiO 2-x At least one of; the thickness can be 200 to 600 nm.

[0025] In some embodiments, the material of the photoelectric effect layer may include one of TiO2, ZnO, BiVO4, Fe2O3, SrTiO3 and SnWO4; preferably, the thickness may be 50 to 200 nm.

[0026] The conduction band of the photoelectric effect layer used in the present invention must be higher than that of the electrochromic layer material to facilitate the formation of a heterojunction and facilitate electron transfer. Furthermore, if the photoelectric effect layer is too thin, the number of electrons generated is small, with a limited impact on reducing the driving voltage. If the photoelectric effect layer is too thick, the voltage distribution across the device layers is affected, increasing the partial voltage of the photoelectric effect layer and thus the overall driving voltage of the device.

[0027] It should be noted that the working principles of wide-band control electrochromic devices are mainly divided into two types: one is the reversible deposition of metals based on liquid electrolytes; the other is polyaniline-based organic electrochromic materials. These two types of wide-band control electrochromic devices often have problems with poor cycle stability or short working life. The device provided by the present invention innovatively adopts a photoelectric effect layer, which uses the photovoltaic effect to introduce a semiconductor film to generate electron-hole pairs under light, and can enter the electrochromic layer under external low-voltage drive. At the same time, in order to improve the coordinated low-voltage driven ion migration, the present invention also optimizes the electrolyte composition, and significantly improves the ion migration efficiency by adding additives that improve the cation solvation environment, ultimately achieving the low-voltage drive and wide-band control functions of the electrochromic device.

[0028] Specifically, the auxiliary agent introduced in the present invention is a fluorinated solvent. The F atom gives it strong electron absorption and low polarizability, which not only makes it highly oxidizable and non-flammable, but also has a unique solvation sheath. Compared with conventional solvents such as propylene carbonate, it has better salt dissociation degree and lower ion binding energy, which is conducive to ion migration.

[0029] In some embodiments, the material of the surface high-transmittance 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 surface high-transmittance substrate has a solar transmittance of ≥85% in the 0.38-2.5 μm band and a mid-infrared transmittance of ≥85% in the 2.5-25 μm band.

[0030] The material of the substrate with a high surface transmittance must have good transmittance from the visible to the mid- and far-infrared. Only with high solar and infrared transmittance can devices based on it have excellent regulation capabilities. If the transmittance is insufficient, the device's regulation performance will be significantly reduced.

[0031] In some embodiments, the thickness of the highly transparent surface substrate may be 0.05-2 mm.

[0032] In some embodiments, the low voltage driven wide band controlled all-solid-state electrochromic device has a solar regulation capability of ≥0.5, a mid- and far-infrared emissivity regulation rate / mid- and far-infrared emissivity regulation capability of ≥0.35, and a power consumption of 100 mW / cm 2 The driving voltage is ≤0.8V under the light intensity.

[0033] The following is an exemplary description of the method for preparing a low-voltage driven, wide-band regulated, 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 substrate, and preparing a second transparent electrode on the surface of a highly transparent substrate; (2) depositing a photoelectric effect layer and an electrochromic layer on the surface of the second transparent electrode by magnetron sputtering; (3) filling the electrolyte solution between the electrochromic layer and the first transparent electrode by a vacuum drip irrigation process and curing the electrolyte solution to obtain the low-voltage driven wide-band controlled all-solid-state electrochromic device; or (1) preparing a first transparent electrode on the surface of a substrate, and preparing a second transparent electrode on the surface of a highly transparent substrate; (2) depositing an electrochromic layer on the surface of the first transparent electrode by magnetron sputtering, and depositing a photoelectric effect layer on the surface of the second transparent electrode by magnetron sputtering; (3) Filling the electrolyte solution between the electrochromic layer and the photoelectric effect layer through a vacuum drip irrigation process and curing the electrolyte solution to obtain the low-voltage driven wide-band regulated all-solid-state electrochromic device.

[0034] In some embodiments, the process parameters of the magnetron sputtering deposition of the photoelectric effect layer may include: using metal Ti 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 100-400 W or the power density is 2-8.0 W / cm 2 .

[0035] The magnetron sputtering time determines the deposition thickness, while the oxygen partial pressure and power together determine the composition of the resulting material. If the parameters are not properly controlled, the photoelectric effect layer material with photoelectric response capability cannot be obtained.

[0036] In some embodiments, the process parameters for magnetron sputtering deposition of the electrochromic layer may include: using metal tungsten, molybdenum or titanium as the target, 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 .

[0037] Magnetron sputtering time determines the deposition thickness, while oxygen partial pressure and power together determine the composition of the resulting material. Improper control of these parameters will result in an electrochromic material. Excessive electrochromic thickness results in a high driving voltage, while too small a thickness results in insufficient controllability.

[0038] To be more specific, the DC magnetron sputtering system equipment used in the magnetron sputtering deposition in 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.

[0039] 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, the total pressure and oxygen partial pressure in the chamber are controlled to be in the range of 0.5-2.0Pa and 0-50%, respectively, and the oxygen partial pressure is preferably 0-25%; the vertical distance between the target material and the substrate is controlled to be 10-20cm, and the initial substrate temperature is room temperature; turn on the DC power supply, control the DC power supply power to 30-400W, the pre-sputtering time is 5-30min, the sputtering time is 10-60min, and the substrate temperature is room temperature; after the sputtering is completed, wait for the substrate temperature to drop to room temperature and take out the substrate.

[0040] In some embodiments, the preparation method further includes an annealing process after magnetron sputtering deposition of the electrochromic layer; wherein the annealing process can be a heat treatment under an inert atmosphere, wherein the inert atmosphere includes N2 and Ar; the heat treatment pressure can be 2-200 torr; the heat treatment process can be: heating to 200-400°C (such as 350°C) for 5-30s (such as 20s) and then keeping warm for 50-200s (such as 100s), then heating to 400-600°C (such as 450°C) for 5-30s (such as 10s) and then keeping warm for 100-300s (such as 200s), and naturally cooling to room temperature.

[0041] Annealing can be used to control the crystallinity of the film, specifically the energy band position, to facilitate electron migration from the photoelectric effect layer. Only when the conduction band of the electrochromic layer is lower than that of the photoelectric effect layer can photogenerated electrons enter the electrochromic layer. Excessive annealing temperature or prolonged annealing results in excessive crystallinity, impairing ion mobility. Conversely, insufficient crystallinity can lead to a mismatch in energy band positions.

[0042] In some embodiments, the electrolyte solution can be prepared by mixing a resin, a solvent, a cosolvent, ferrocene, a crosslinker, and an ion source solution in a mass ratio of 1:(1-3):(0.1-0.5):(0.05-0.2):(0.5-2):(1-3), followed by adding an initiator at a mass ratio of 0.1-0.5% of the total mass of the mixture and mixing again. Excessive cosolvent affects the composition of the electrolyte, reducing the proportion of cationic content; insufficient cosolvent has limited improvement in ion migration capacity.

[0043] In which, the resin may include one of aliphatic polyurethane diacrylate, aliphatic polyurethane dimethacrylate, and aromatic polyurethane diacrylate; the solvent may include PMA propylene glycol methyl ether acetate; the co-solvent may include at least one of ETFA (ethyl trifluoroacetate), methyl trifluoroacetate, ethyl trifluoroacetoacetate, ethyl pentafluoroacetate, ethyl acetate, ethyl acetate, ethyl propionate, ethyl acetoacetate, and diethyl malonate; the cross-linking agent may be ETPTA; and the initiator may be initiator 1173.

[0044] The ion source in the ion source solution may include at least one of chlorides, perchlorates and sulfates of Li, Na, Mg or Zn, and the solvent in the ion source solution may be propylene carbonate (PC); preferably, the concentration of the ion source solution may be 0.1-2 mol / L.

[0045] In some embodiments, the curing method can be ultraviolet curing (such as a 100W ultraviolet lamp) or thermal curing.

[0046] It should also be noted that the present invention uses inorganic electrochromic materials. The electrochromic process of organic electrochromic materials is the injection and removal of electrons, that is, a single redox process, while the electrochromic process of inorganic electrochromic materials is a dual injection process of ions and electrons. To achieve low-voltage drive of inorganic electrochromic materials, this patent not only designs a photoelectric response layer to reduce the electron migration barrier, but also improves the ion migration ability through electrolyte solvation modification, resulting in a synergistic improvement in the low-voltage migration ability of ions and electrons.

[0047] The preparation process involved in this invention is simple, low-cost, and easily scalable. The high-performance electrochromic device developed by this invention has broad application prospects. Therefore, the low-voltage-driven, wide-band-controlled, all-solid-state electrochromic device prepared using the preparation method provided by this patent 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 better energy efficiency than Low-E glass in major regions around the world.

[0048] 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.

[0049] Example 1

[0050] The method for preparing a low-voltage driven wide-band controlled all-solid-state electrochromic device provided in this embodiment comprises the following steps: (1) First, glass was used as a transparent electrode, and a first transparent electrode with high sunlight transmittance (transmittance 78%) and high infrared reflectance (reflectance 75%) was prepared on its upper surface. Then, a second transparent electrode with high sunlight transmittance and high infrared transmittance (broadband transmittance 80%) was prepared on a BaF2 substrate; (2) Preparing a photoelectric effect layer on the surface of the second transparent electrode: using metal Ti as the target, the sputtering gas is argon and oxygen, the total pressure is 1.5 Pa, the oxygen partial pressure is 6%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power applied to the target is 100 W or the power density is 2 W / cm 2 , a DC power supply is used to deposit 100 nm on the surface; then, an inorganic electrochromic layer is deposited thereon: by magnetron sputtering, using metal tungsten, molybdenum or titanium as a target, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 12%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, the DC power applied to the target is 70 W or the power density is 1.55 W / cm 2 A 400nm thick electrochromic layer was deposited on the surface using a DC power supply. Subsequently, the film was rapidly annealed and rapidly heat-treated in an inert atmosphere at a pressure of 50 torr. The heat treatment process involved heating to 350°C for 20 seconds, holding for 100 seconds, heating to 450°C for 10 seconds, holding for 200 seconds, and then naturally cooling to room temperature. (3) According to the existing technology, an electrolyte solution prepared by weighing a photocurable resin, a solvent (PMA propylene glycol methyl ether acetate), a co-solvent ETFA (ethyl trifluoroacetate), ferrocene, ETPTA and a propylene carbonate solution of LiClO4 in a ratio of 1:2:0.3:0.1:1:1 is filled between the above-mentioned electrochromic layer and the first transparent electrode by vacuum drip irrigation; wherein 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 1 μm by the surface tension of the hard template and the resin solution; wherein the photocuring is to place the device under a 100W ultraviolet lamp for uniform irradiation, and after the device is cured, an organic solvent is used to remove excess organic matter on the surface of the device to obtain the low-voltage driven wide-band controlled all-solid-state electrochromic device.

[0051] Example 2

[0052] The preparation method of the low-voltage driven wide-band controlled 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 is 200 nm.

[0053] Example 3

[0054] The preparation method of the low-voltage driven wide-band controlled 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 is 600 nm.

[0055] Example 4

[0056] The preparation method of the low-voltage driven wide-band controlled 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 photoelectric effect layer is 50 nm.

[0057] Example 5

[0058] The preparation method of the low-voltage driven wide-band controlled 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 photoelectric effect layer is 200 nm.

[0059] Example 6

[0060] The preparation method of the low-voltage driven wide-band controlled all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (3), the mass ratio of the substances in the electrolyte solution is 1:2:0.1:0.1:1:1.

[0061] Example 7

[0062] The preparation method of the low-voltage driven wide-band controlled all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (3), the mass ratio of the substances in the electrolyte solution is 1:2:0.5:0.1:1:1.

[0063] Example 8

[0064] The preparation method of the low-voltage driven wide-band controlled all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (3), 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.

[0065] Example 9

[0066] The preparation method of the low-voltage driven wide-band controlled all-solid-state electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (3), the thickness of the resin layer is controlled to be 5 μm by the surface tension of the hard template and the resin solution.

[0067] Example 10

[0068] The preparation method of the low-voltage driven wide-band controlled 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 heat treatment pressure is 2 torr.

[0069] Example 11

[0070] The preparation method of the low-voltage driven wide-band controlled 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 heat treatment pressure is 200 torr.

[0071] Comparative Example 1

[0072] The preparation method of the electrochromic device provided in this comparative example refers to that in Example 1, with the following main differences: In step (2), no photoelectric effect layer is prepared.

[0073] Comparative Example 2

[0074] The preparation method of the electrochromic device provided in this comparative example refers to that in Example 1, with the following main differences: In step (3), the electrolyte solution does not contain the co-solvent ETFA (ethyl trifluoroacetate).

[0075] Comparative Example 3

[0076] The preparation method of the electrochromic device provided in this comparative example refers to that in Example 1, with the following main differences: The device was tested with standard sunlight (50 mW / cm 2 ).

[0077] Comparative Example 4

[0078] The preparation method of the electrochromic device provided in this comparative example refers to that in Example 1, with the following main differences: In step (2), the atmosphere for the annealing treatment is air.

[0079] Comparative Example 5

[0080] The preparation method of the electrochromic device provided in this comparative example refers to that in Example 1, with the following main differences: In step (2), the material of the photoelectric effect layer is selected as SnO2.

[0081] After testing, the device has a solar regulation capability of 0.52, a mid-infrared and far-infrared emissivity regulation capability of 0.31, and a 100mW / cm 2 The driving voltage is 2.5V under the light intensity.

[0082] Comparative Example 6

[0083] The preparation method of the electrochromic device provided in this comparative example refers to that in Example 1, with the following main differences: In step (3), the mass ratio of the substances in the electrolyte solution is 1:2:0.01:0.1:1:1.

[0084] After testing, the device has a solar regulation capability of 0.62, a mid- and far-infrared emissivity regulation capability of 0.33, and a 100mW / cm 2 The driving voltage is 2V under the light intensity of .

[0085] Comparative Example 7

[0086] The preparation method of the electrochromic device provided in this comparative example refers to that in Example 1, with the following main differences: In step (3), the mass ratio of the substances in the electrolyte solution is 1:2:1:0.1:1:1.

[0087] After testing, the device has a solar regulation capability of 0.35, a mid- and far-infrared emissivity regulation capability of 0.13, and a 100mW / cm 2 The driving voltage is 2V under the light intensity of .

[0088] The following are the relevant preparation processes and performance parameters of the electrochromic devices in Examples 1-11 and Comparative Examples 1-4:

[0089] 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 low-voltage driven wide-band controlled all-solid-state electrochromic device, characterized in that: The structure of the low-voltage driven wide-band regulated all-solid-state electrochromic device includes: a substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a photoelectric effect layer, a second transparent electrode and a surface high-transmittance substrate stacked in sequence; or, a substrate, a first transparent electrode, an electrochromic layer, an electrolyte layer, a photoelectric effect layer, a second transparent electrode and a surface high-transmittance substrate stacked in sequence.

2. The low-voltage driven wide-band controlled all-solid-state electrochromic device according to claim 1, characterized in that: The thickness of the electrolyte layer is 0.6-5 μm.

3. The low-voltage driven wide-band controlled all-solid-state electrochromic device according to claim 1 or 2, characterized in that: The material of the electrochromic layer includes WO 3-x 、MoO 3-x and TiO 2-x At least one of the above has a thickness of 200 to 600 nm.

4. The low-voltage driven wide-band controlled all-solid-state electrochromic device according to any one of claims 1 to 3, characterized in that: The material of the photoelectric effect layer includes one of TiO2, ZnO, BiVO4, Fe2O3, SrTiO3 and SnWO4, and the thickness is 50-200nm.

5. A method for preparing a low-voltage driven wide-band controlled all-solid-state electrochromic device according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: depositing a photoelectric effect layer and an electrochromic layer on the surface of a second transparent electrode by magnetron sputtering according to the structure of the low-voltage driven wide-band controlled all-solid-state electrochromic device, filling an electrolyte solution between the electrochromic layer and the first transparent electrode and curing the electrolyte solution; or An electrochromic layer is deposited on the surface of the first transparent electrode by magnetron sputtering, and a photoelectric effect layer is deposited on the surface of the second transparent electrode by magnetron sputtering; an electrolyte solution is filled between the electrochromic layer and the photoelectric effect layer and solidified.

6. The preparation method according to claim 5, characterized in that The preparation method further includes an annealing process after magnetron sputtering deposition of the electrochromic layer; wherein the annealing process is a heat treatment in an inert atmosphere; and the gas pressure of the heat treatment is 2-200 torr.

7. The preparation method according to claim 5 or 6, characterized in that: The electrolyte solution is prepared by mixing resin, solvent, cosolvent, ferrocene, crosslinking agent and ion source solution in a mass ratio of 1:(1-3):(0.1-0.5):(0.05-0.2):(0.5-2):(1-3), and then adding 0.1-0.5% of the total mass of the mixed solution initiator and mixing again.

8. The preparation method according to any one of claims 5 to 7, characterized in that The cosolvent includes at least one of ethyl trifluoroacetate, methyl trifluoroacetate, ethyl trifluoroacetoacetate, ethyl pentafluoroacetate, ethyl acetate, ethyl propionate, ethyl acetoacetate and diethyl malonate.

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