Electrolyte solution, all-solid-state electrolyte, flexible broadband regulation all-solid-state electrochromic device and preparation method of flexible broadband regulation all-solid-state electrochromic device

Abstract

The invention relates to an electrolyte solution, an all-solid-state electrolyte, a flexible broadband regulation all-solid-state electrochromic device and a preparation method of the flexible broadband regulation all-solid-state electrochromic device. The chemical components of the electrolyte solution comprise resin and hydroxymethyl cellulose; wherein the resin is polyurethane acrylate, preferably at least one of aliphatic polyurethane diacrylate, aliphatic polyurethane dimethyl acrylate and aromatic polyurethane diacrylate.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromic functional materials and devices, and specifically relates to an electrolyte solution, an all-solid-state electrolyte, a flexible 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 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.

[0006] Looking further ahead, there are currently two operating principles for broadband electrochromic devices: one based on reversible metal deposition in a liquid electrolyte, and the other using polyaniline-based organic electrochromic materials. However, both types of broadband electrochromic devices suffer from poor cycling stability or short operating lifespans. Summary of the Invention

[0007] In response to the above technical problems, the object of the present invention is to provide an electrolyte solution, an all-solid-state electrolyte, a flexible wide-band controlled all-solid-state electrochromic device and a preparation method thereof.

[0008] In a first aspect, the present invention provides an electrolyte solution, wherein the chemical components of the electrolyte solution include resin and hydroxymethyl cellulose; The resin is polyurethane acrylate, preferably at least one of aliphatic polyurethane diacrylate, aliphatic polyurethane dimethacrylate, and aromatic polyurethane diacrylate.

[0009] Preferably, the functionality of the resin is ≥2, and the viscosity (cps / 25°C) is ≤50,000 and ≤200,000.

[0010] Preferably, the electrolyte solution is prepared by mixing resin, solvent, co-solvent, ferrocene, cross-linking agent, ion source solution and hydroxymethyl cellulose (CMC) in a mass ratio of 1: (1-3): (0.1-0.5): (0.05-0.2): (0.5-2): (1-3): (0.03-0.05), and then adding 0.1-0.5% of the total mass of the mixture to the initiator and mixing again. Preferably, the co-solvent is isobornyl acrylate.

[0011] In a second aspect, the present invention provides an all-solid-state electrolyte, wherein the all-solid-state electrolyte is obtained by ultraviolet curing or thermal curing the electrolyte solution; Preferably, the elongation at break of the all-solid-state electrolyte is ≥300%.

[0012] Preferably, the power of the UV curing is 100W, and the illumination time is 1-60s.

[0013] Preferably, the heating temperature of the thermal curing is 50-150° C., and the holding time is 5-60 minutes.

[0014] In a third aspect, the present invention provides a flexible wide-band controlled all-solid-state electrochromic device, which comprises: a first transparent electrode, the above-mentioned all-solid-state electrolyte layer, an electrochromic layer and a second transparent electrode stacked in sequence.

[0015] Preferably, the thickness of the all-solid-state electrolyte layer in the flexible wide-band regulated all-solid-state electrochromic device is 0.6-5 μm.

[0016] In a fourth aspect, the present invention provides a method for preparing the above-mentioned flexible wide-band regulated all-solid-state electrochromic device, the preparation method comprising the following steps: preparing an electrochromic layer on the surface of the second transparent electrode according to the structure of the above-mentioned flexible wide-band regulated all-solid-state electrochromic device and performing heating annealing, and filling an electrolyte solution between the first transparent electrode and the electrochromic layer through a vacuum drip irrigation process and curing to prepare an all-solid electrolyte.

[0017] Preferably, the heating annealing process includes: heat treatment pressure 2-200torr; heat treatment process: heating to 100-350℃ for 10-40 seconds, keeping warm for 10-200s, heating to 150-450℃ for 5-20s, keeping warm for 100-300s, and naturally cooling to room temperature.

[0018] 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 device, which can achieve excellent energy-saving effects in major regions around the world; (2) The present invention designs an electrolyte with excellent flexibility by controlling the resin configuration and composition innovation, so that the device has excellent flexibility; (3) The preparation method provided by the present invention is simple in process, low in cost, and easy to promote, and the flexible wide-band controllable electrochromic device has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the exemplary structure of the flexible wide-band controlled all-solid-state electrochromic device provided by the present invention. DETAILED DESCRIPTION

[0020] 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.

[0021] First, if Figure 1 As shown, the present invention provides a flexible, broadband, all-solid-state electrochromic device. The structure of the flexible, broadband, all-solid-state electrochromic device may include: a base substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a second transparent electrode, and a surface high-transmittance substrate stacked in sequence.

[0022] In some embodiments, the base substrate may be made of a flexible material such as poly(4-methyl-1-pentene) (TPX) or polyethylene (PE), and may have a thickness of 10-100 μm.

[0023] In some embodiments, the material of the first transparent electrode may include at least one of transparent conductive oxide, MXENE, and metal nanowires, and the square resistance may be 10 to 400 Ω / cm. 2 Preferably, the first transparent electrode has a solar transmittance of ≥75% in the 0.38-2.5 μm band and a mid-infrared reflectivity of ≥75% in the 8-14 μm band. High solar transmittance ensures adequate solar regulation performance, while high mid-infrared reflectivity enhances the device's infrared regulation capabilities.

[0024] In some embodiments, the material of the second transparent electrode may include at least one of a 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. This ensures the device's solar and infrared regulation performance.

[0025] In some embodiments, the electrolyte layer may be a cationic gel conductive layer based on an organic resin, and the cations may include Li + 、Al 3+ , K + and Na + At least one of; preferably, the thickness of the electrolyte layer can be 0.6-5 μm, and the elongation at break is ≥300%.

[0026] The wide-band control device based on inorganic electrochromic materials provided by the present invention utilizes an elastic electrolyte based on hydroxymethyl cellulose and polyurethane acrylate prepolymer to enhance the device's flexibility. The molecular structure of the polyurethane acrylate prepolymer consists of a polyurethane chain in the middle, which provides flexibility and mechanical properties, and acrylates at both ends for the curing reaction. As a result, the cured electrolyte exhibits excellent flexibility and hardness. In particular, the introduction of cellulose further improves the device's overall performance, enhancing the electrolyte's flexibility and ion mobility.

[0027] To be more specific: First, the abundant hydroxyl groups (-OH) in cellulose form hydrogen bonds with the carbamate groups (-NHCOO-) in polyurethane or the polar groups of acrylates. This physical crosslinking not only improves the rigidity of the material, but also dissipates energy through a reversible fracture-recombination mechanism, thereby improving resilience. Second, cellulose is embedded in the elastic matrix of polyurethane acrylate as a rigid dispersed phase. During stretching, the cellulose phase bears stress and limits excessive deformation of the matrix, while the polyurethane acrylate matrix provides elastic recovery through chain segment movement, avoiding stress concentration fracture and improving elongation at break. Third, at the macroscale, polyurethane acrylate forms a continuous elastic network, and at the nanoscale, cellulose nanofibers form a secondary reinforcement network. The multi-level structure synergistically improves the elastic modulus and toughness.

[0028] In some embodiments, the material of the electrochromic layer may include WO 3-x 、MoO 3-x 、TiO 2-x At least one of the above can have a thickness of 200 to 600 nm. If it is too thick, the device response speed will change, thereby affecting the device's cycle stability; if it is too thin, the device's coloring performance will be insufficient, affecting its modulation performance.

[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 sunlight 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] In some embodiments, the flexible wide-band regulation all-solid-state electrochromic device has a solar regulation capability (%) ≥ 0.5, a mid- and far-infrared emissivity regulation rate / regulation capability (%) ≥ 0.35 before and after fading, a performance regulation performance attenuation of ≤ 1% after bending 1,000 times, and a performance regulation performance attenuation of ≤ 5% after bending 10,000 times.

[0031] The following is an exemplary description of the method for preparing a flexible, wide-band regulated, all-solid-state electrochromic device provided by the present invention. The method may include the following steps: (1) According to the structure of the flexible wide-band controlled all-solid-state electrochromic device, a first transparent electrode is prepared on the surface of the bottom substrate, and a second transparent electrode and an electrochromic layer are prepared on the surface of the high-transmittance substrate in sequence by magnetron sputtering; (2) Filling the electrolyte solution between the first transparent electrode and the electrochromic layer through a vacuum drip irrigation process and curing the electrolyte solution to obtain the flexible wide-band controllable all-solid-state electrochromic device.

[0032] In some embodiments, in step (1), the process parameters for preparing the electrochromic layer by magnetron sputtering 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 .

[0033] 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.

[0034] The specific sputtering deposition process is as follows: high-purity argon and oxygen gas are introduced into the sputtering chamber, with the purity of the argon and oxygen used being 99.99% or higher. The total pressure and oxygen partial pressure in the chamber are controlled within the ranges 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. The DC power supply is turned on and the power is controlled to be 30-200 W. The pre-sputtering time is 5-30 minutes, the sputtering time is 10-60 minutes, and the substrate temperature is room temperature. After the sputtering is completed, the substrate is removed after the substrate temperature cools to room temperature.

[0035] In some embodiments, step (1) may further include a process of heating and annealing the magnetron sputtered electrochromic layer; wherein the heating and annealing process may include: under an inert atmosphere, a heat treatment pressure of 2-200 torr, a heat treatment process of heating to 100-350°C for 10-40 seconds, keeping warm for 10-200 seconds, heating to 150-450°C for 5-20 seconds, keeping warm for 100-300 seconds, and then naturally cooling to room temperature.

[0036] Heat treatment can create an appropriate amount of oxygen vacancies in the electrochromic layer, increasing the electron concentration in the film and improving the electrochromic layer's infrared modulation performance. Excessively high temperatures can cause the flexible substrate to shrink or even decompose, leading to device failure. Insufficient annealing temperatures can affect the formation of oxygen vacancies in the electrochromic layer, resulting in insufficient infrared modulation performance.

[0037] In some embodiments, in step (2), the electrolyte solution can be obtained by mixing the resin, solvent, co-solvent, ferrocene, cross-linking agent, ion source solution and hydroxymethyl cellulose CMC in a mass ratio of 1: (1-3): (0.1-0.5): (0.05-0.2): (0.5-2): (1-3): (0.03-0.05), and then adding 0.1-0.5% of the total mass of the mixed solution initiator and mixing again.

[0038] The resin may be polyurethane acrylate, preferably at least one of aliphatic polyurethane diacrylate, aliphatic polyurethane dimethacrylate, and aromatic polyurethane diacrylate; preferably, the resin functionality is ≥2, 50000≤viscosity (cps / 25°C)≤200000.

[0039] Among them, the functionality and viscosity of the resin are directly related to the structure of the resin. In the present invention, by controlling the appropriate functionality and viscosity, coupling with other additives and auxiliary agents can be ensured, and an electrolyte with excellent elasticity is obtained after curing. In addition, if the viscosity is further increased, the cured electrolyte becomes brittle and the elastic properties decrease; if the viscosity is insufficient, the electrolyte is too dilute, resulting in insufficient bonding between the electrolyte layer and the upper film layer of the device, affecting the performance of the device. At the same time, the flexibility of the film-forming electrolyte can be improved by adding an appropriate amount of cellulose. If the resin content is too low, the toughness of the electrolyte film is insufficient; if the resin content is too high, the proportion of other materials is reduced, affecting the coloring performance of the device. Insufficient addition of cellulose will lead to insufficient elasticity of the electrolyte film, and excessive addition will easily cause the film to crack.

[0040] If the functionality of the polyurethane acrylate group is 1, the viscosity of the resin is low, the formed electrolyte layer has poor bonding strength with the interface, the resulting electrochromic device has a solar band adjustment capability of 0.52, a mid- and far-infrared emissivity adjustment rate before and after fading of 0.36, a performance adjustment performance attenuation of 60% after bending 1,000 times, and a performance adjustment performance attenuation of 100% after bending 10,000 times.

[0041] Without cellulose, the electrochromic device had a solar band adjustment capability of 0.54, a mid- and far-infrared emissivity adjustment rate of 0.37 before and after fading, a 10% decrease in performance after 1,000 bends, and a 50% decrease after 10,000 bends. When the cellulose addition ratio was too high, such as 0.1, the electrochromic device had a solar band adjustment capability of 0.48, a mid- and far-infrared emissivity adjustment rate of 0.26 before and after fading, a 13% decrease in performance after 1,000 bends, and a 75% decrease after 10,000 bends.

[0042] To be more specific: First, the abundant hydroxyl groups (-OH) in cellulose form hydrogen bonds with the carbamate groups (-NHCOO-) in polyurethane or the polar groups of acrylates. This physical crosslinking not only improves the rigidity of the material, but also dissipates energy through a reversible fracture-recombination mechanism, thereby improving resilience. Second, cellulose is embedded in the elastic matrix of polyurethane acrylate as a rigid dispersed phase. During stretching, the cellulose phase bears stress and limits excessive deformation of the matrix, while the polyurethane acrylate matrix provides elastic recovery through chain segment movement, avoiding stress concentration fracture and improving elongation at break. Third, at the macroscale, polyurethane acrylate forms a continuous elastic network, and at the nanoscale, cellulose nanofibers form a secondary reinforcement network. The multi-level structure synergistically improves the elastic modulus and toughness.

[0043] Wherein, the solvent may be PMA propylene glycol methyl ether acetate; the co-solvent may be IBOA (isobornyl acrylate); 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 chloride, perchlorate and sulfate 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, in step (2), the curing method can be ultraviolet curing (such as 100W) or thermal curing; preferably, the ultraviolet curing time can be 1-60s; the heating temperature of the thermal curing is 50-150°C, and the holding time is 5-60min.

[0046] In summary, this invention proposes a fully solid-state, broadband-controllable electrochromic device based on inorganic electrochromic materials such as WO3, through material innovation and structural design. This patent develops an elastic electrolyte based on a polyurethane acrylate prepolymer to enhance the device's flexibility. Its molecular structure consists of a polyurethane chain in the middle, which provides flexibility and mechanical properties, and acrylates at both ends for the curing reaction. As a result, the device exhibits excellent flexibility and hardness after UV light curing.

[0047] The flexible, wide-band, energy-saving electrochromic device designed and fabricated in 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 flexible wide-band controlled all-solid-state electrochromic device provided in this embodiment comprises the following steps: (1) First, TPX was used as the bottom substrate, and a first transparent electrode with high sunlight transmittance (transmittance 78%) and high infrared reflectivity (reflectivity 75%) was prepared on its upper surface; secondly, a second transparent electrode with high sunlight transmittance and high infrared transmittance (wideband transmittance 80%) was prepared on the TPX surface high-transmittance substrate, and metal tungsten was used as the target, the sputtering gas was argon and oxygen, the total pressure was 2.0 Pa, the oxygen partial pressure was 6%, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, and the DC power applied to the target was 70 W or the power density was 1.4 W / cm 2 A 400nm thick electrochromic layer was deposited on the surface using a DC power supply. Subsequently, the electrochromic layer 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. (2) According to the existing technology, an electrolyte solution prepared by vacuum drip irrigation according to a mass ratio of aliphatic polyurethane diacrylate, solvent (PMA propylene glycol methyl ether acetate), co-solvent IBOA (isobornyl acrylate), ferrocene, ETPTA, PC (propylene carbonate) solution of LiClO4 and CMC (hydroxymethyl cellulose) of 1:2:0.25:0.1:1:1:0.04 is filled between the first transparent electrode and the electrochromic layer; wherein the concentration of the ion source solution is 1 mol / L; a complete device is formed by ultraviolet curing or thermal 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 light curing 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 flexible wide-band controllable all-solid-state electrochromic device.

[0051] Example 2

[0052] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the polyurethane acrylate is aliphatic polyurethane dimethacrylate.

[0053] Example 3

[0054] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the polyurethane acrylate is aromatic polyurethane diacrylate.

[0055] Example 4

[0056] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the thickness of the electrochromic layer is 200 nm.

[0057] Example 5

[0058] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the thickness of the electrochromic layer is 600 nm.

[0059] Example 6

[0060] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the heat treatment pressure of the electrochromic layer during heating and annealing is 2 Torr.

[0061] Example 7

[0062] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the heat treatment pressure of the electrochromic layer during heating and annealing is 200 torr.

[0063] Example 8

[0064] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers 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.

[0065] Example 9

[0066] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), 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 flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the bottom substrate material is PE.

[0069] Example 11

[0070] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the ratio of the components of the electrolyte solution is 1:2:0.25:0.1:1:1:0.03.

[0071] Example 12

[0072] The preparation method of the flexible broadband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the ratio of the components of the electrolyte solution is 1:2:0.25:0.1:1:1:0.05.

[0073] Comparative Example 1

[0074] The preparation method of the electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), no polyurethane acrylate is added to the electrolyte solution.

[0075] Comparative Example 2

[0076] The preparation method of the electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the polyurethane acrylate in the electrolyte solution is aliphatic polyurethane acrylate.

[0077] Comparative Example 3

[0078] The preparation method of the electrochromic device provided in this embodiment refers to that of Example 1, with the main difference being that in step (2), hydroxymethyl cellulose is not added to the electrolyte solution.

[0079] Table 1 below shows the relevant parameters of the electrochromic devices prepared in Examples 1-12 and Comparative Examples 1-3:

[0080] 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. An electrolyte solution, characterized in that The chemical components of the electrolyte solution include resin and hydroxymethyl cellulose; wherein the resin is polyurethane acrylate, preferably at least one of aliphatic polyurethane diacrylate, aliphatic polyurethane dimethacrylate, and aromatic polyurethane diacrylate.

2. The electrolyte solution according to claim 1, characterized in that The functionality of the resin is ≥2, 50000≤viscosity (cps / 25°C)≤200000.

3. The electrolyte solution according to claim 1 or 2, characterized in that The electrolyte solution is prepared by mixing resin, solvent, co-solvent, ferrocene, cross-linking agent, ion source solution and hydroxymethyl cellulose (CMC) in a mass ratio of 1: (1-3): (0.1-0.5): (0.05-0.2): (0.5-2): (1-3): (0.03-0.05), and then adding 0.1-0.5% of the total mass of the mixture to the initiator and mixing again. Preferably, the co-solvent is isobornyl acrylate.

4. An all-solid-state electrolyte, characterized in that The all-solid-state electrolyte is obtained by UV curing or thermal curing the electrolyte solution according to any one of claims 1 to 3; Preferably, the elongation at break of the all-solid-state electrolyte is ≥300%.

5. The all-solid-state electrolyte according to claim 4, characterized in that The power of the ultraviolet curing is 100W, and the illumination time is 1-60s.

6. The all-solid electrolyte according to claim 4 or 5, characterized in that The heating temperature of the thermal curing is 50-150° C., and the heat preservation time is 5-60 minutes.

7. A flexible wide-band controlled all-solid-state electrochromic device, characterized in that: The electrochromic device comprises: a first transparent electrode, an all-solid electrolyte layer according to any one of claims 4 to 6, an electrochromic layer, and a second transparent electrode, which are stacked in sequence.

8. The flexible broadband controllable all-solid-state electrochromic device according to claim 7, characterized in that: The thickness of the all-solid-state electrolyte layer in the flexible wide-band regulated all-solid-state electrochromic device is 0.6-5 μm.

9. A method for preparing a flexible wide-band controlled all-solid-state electrochromic device according to claim 7 or 8, characterized in that: The preparation method includes the following steps: preparing an electrochromic layer on the surface of the second transparent electrode according to the structure of the above-mentioned flexible wide-band controllable all-solid-state electrochromic device and performing heating annealing; and filling an electrolyte solution between the first transparent electrode and the electrochromic layer through a vacuum drip irrigation process and curing to prepare an all-solid electrolyte.

10. The preparation method according to claim 9, characterized in that The heating annealing process includes: heat treatment pressure 2-200torr; heat treatment process: heating to 100-350℃ for 10-40 seconds, keeping warm for 10-200s, heating to 150-450℃ for 5-20s, keeping warm for 100-300s, and naturally cooling to room temperature.

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