All-solid-state broadband regulation and control laminated electrochromic device with transferable electrolyte and preparation method of all-solid-state broadband regulation and control laminated electrochromic device

Abstract

The invention relates to an all-solid-state broadband regulation and control laminated electrochromic device with a transferable electrolyte and a preparation method of the all-solid-state broadband regulation and control laminated electrochromic device. The all-solid-state broadband regulation and control laminated electrochromic device with the transferable electrolyte structurally comprises a glass substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a second transparent electrode and a surface high-transparency substrate which are sequentially stacked.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromic functional materials and devices, and particularly relates to an electrolyte-migratable all-solid-state wide-band controllable laminated 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] Broadband electrochromic devices typically operate on two principles: one based on reversible metal deposition in a liquid electrolyte, and the other using polyaniline-based organic electrochromic materials. However, these two types of broadband electrochromic devices often suffer from poor cycling stability or short operating lifespans. Summary of the Invention

[0007] In view of the above technical problems, the object of the present invention is to provide an all-solid-state wide-band controllable laminated electrochromic device with transferable electrolyte and a preparation method thereof.

[0008] In the first aspect, the present invention provides an electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device. The structure of the electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device may include: a glass substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a second transparent electrode and a surface high-transmittance substrate stacked in sequence.

[0009] Preferably, the electrolyte layer is an organic resin cation gel conductive layer based on polyethylene mesoporous membrane, and the cations include Li + 、Al 3+ , K + and Na + At least one of; preferably, the thickness of the electrolyte layer is 1-20 μm.

[0010] Preferably, the material of the electrochromic layer includes WO 3-x 、MoO 3-x 、TiO 2-x At least one of the above has a thickness of 200 to 600 nm.

[0011] Preferably, the electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device has a control range covering 0.38-2.5μm sunlight and 2.5-25μm mid-infrared bands; the solar energy control capability (%) is ≥0.5, the mid- and far-infrared emissivity control rate before and after fading (%) is ≥0.31, and the interface bonding strength is ≥0.1MPa.

[0012] In a second aspect, the present invention provides a method for preparing the above-mentioned all-solid-state wide-band controllable laminated electrochromic device with electrolyte migration, the preparation method comprising the following steps: (1) using magnetron sputtering to prepare a first transparent electrode on the surface of a glass substrate, and sequentially preparing a second transparent electrode and an electrochromic layer on the surface of a high-transmittance substrate; (2) forming a mesoporous membrane of high-density polyethylene by a biaxial stretching process and immersing the membrane in an electrolyte precursor solution, and curing the membrane after immersion to obtain a mobile electrolyte layer; (3) Placing the migrated electrolyte layer between the first transparent electrode and the electrochromic layer and applying pressure to obtain the electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device.

[0013] Preferably, step (1) further includes a process of heating and annealing the magnetron sputtered electrochromic layer; wherein the heating and annealing process includes: under an inert atmosphere, the heat treatment pressure is 2-200 torr, the heat treatment process is: heating to 200-400°C for 10-40s and then keeping warm for 50-200s, then heating to 300-500°C for 5-50s, keeping warm for 100-500s, and naturally cooling to room temperature.

[0014] Preferably, in step (2), the molecular weight of the high-density polyethylene is 3000-9000.

[0015] Preferably, in step (2), the process parameters of the biaxial stretching process include: a preheating temperature of 100-130°C; a longitudinal stretching force of 50-500 MPa, and a temperature range of 120-140°C; and a transverse stretching force of 50-500 MPa, and a temperature range of 130-150°C.

[0016] Preferably, in step (2), the electrolyte precursor solution can be obtained by mixing a photocurable resin, a solvent, ferrocene, a crosslinking agent, an ion source solution and a coupling agent in a mass ratio of 1:1-3:0.05-0.2:0.5-2:1-3:0.02-0.1, and then adding an initiator of 0.1-0.5% of the total mass of the mixture and mixing again.

[0017] Beneficial effects (1) The present invention achieves wide-band control from visible light to mid- and far-infrared light by designing a simple laminated all-solid-state electrochromic device, which can achieve excellent energy-saving effects in major regions around the world; (2) The present invention designs a transferable laminated electrolyte by adjusting the resin configuration and composition innovation. The laminated electrolyte can be cut into corresponding shapes according to the shape of the electrodes and directly sandwiched between the upper and lower electrodes to obtain a complete device. (3) The preparation method provided by the present invention has simple process, low cost and is easy to promote. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a schematic diagram of the exemplary structure of the all-solid-state wide-band controllable laminated electrochromic device with transferable electrolyte provided by the present invention. 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 an electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device. The structure of the electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device may include: a glass substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a second transparent electrode, and a surface-high-transmittance substrate stacked in sequence.

[0021] 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 sunlight transmittance of the first transparent electrode in the 0.38-2.5μm band can be ≥75%, and the mid-infrared reflectivity in the 8-14um band can be ≥75%.

[0022] By controlling the first transparent electrode to have high solar transmittance and mid-infrared reflectivity, its infrared reflectivity can be adjusted before and after fading, thereby adjusting the device's emissivity. At the same time, by controlling the sheet resistance of the electrode material within an appropriate range, the color change of the device can be better driven.

[0023] In some embodiments, the material of the second transparent electrode may include at least one of a transparent conductive oxide, MXENE, and a metal nanowire; preferably, the second transparent electrode may have 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.

[0024] By controlling the solar light transmittance and mid-infrared transmittance of the second transparent electrode, the device's solar and infrared control performance can be guaranteed. If the second transparent electrode's broadband transmittance is insufficient, the device's infrared emissivity control performance will deteriorate.

[0025] In some embodiments, the electrolyte layer may be an organic resin cation gel conductive layer based on a polyethylene mesoporous membrane, and the cation may include Li + 、Al 3+ , K + and Na + At least one of; preferably, the thickness of the electrolyte layer may be 1-20 μm.

[0026] If the electrolyte thickness is too low, there will be less electrolyte, and the steep adjustment ability will be insufficient, resulting in the deterioration of comprehensive performance such as solar energy adjustment ability, infrared emissivity adjustment ability, and interface bonding strength; then, if the thickness is too large, it will lead to excessive absorption of infrared, which will also cause the device's comprehensive performance such as solar energy adjustment ability, infrared emissivity adjustment ability, and interface bonding strength to be poor.

[0027] 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-mentioned materials may have a thickness of 200 to 600 nm.

[0028] 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.

[0029] By controlling the solar transmittance and mid-infrared transmittance of the high-transmittance substrate, the device's solar and infrared control performance can be guaranteed. If the broadband transmittance of the high-transmittance substrate is insufficient, the device's infrared emissivity control performance will deteriorate.

[0030] In some embodiments, the electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device has a control range covering 0.38-2.5 μm sunlight and 2.5-25 μm mid-infrared band; the solar energy control capability (%) is ≥0.5, the mid- and far-infrared emissivity control rate before and after fading / mid- and far-infrared emissivity control capability (%) is ≥0.31, and the interface bonding strength is ≥0.1 MPa.

[0031] The following is an exemplary description of the preparation method of the electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device provided by the present invention. The preparation method may include the following steps: (1) using magnetron sputtering to prepare a first transparent electrode on the surface of a glass substrate, and sequentially preparing a second transparent electrode and an electrochromic layer on the surface of a high-transmittance substrate; (2) forming a mesoporous membrane of high-density polyethylene by a biaxial stretching process and immersing the membrane in an electrolyte precursor solution, and curing the membrane after immersion to obtain a mobile electrolyte layer; (3) Placing the migrated electrolyte layer between the first transparent electrode and the electrochromic layer and applying pressure to obtain the electrolyte-migratable all-solid-state wide-band controllable laminated 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: heating to 200-400°C for 10-40s and then keeping warm for 50-200s, then heating to 300-500°C for 5-50s, keeping warm for 100-500s, and naturally cooling to room temperature.

[0036] Among them, if the heat treatment temperature is too high or the time is too long, the oxygen vacancy content in the surface layer of the electrochromic layer will be too high, which will reduce the cycle stability of the device; if the heat treatment temperature is too low or the time is too short, the oxygen vacancy content in the surface layer of the electrochromic layer will be too low, which will make the infrared adjustment ability of the device insufficient.

[0037] In some embodiments, in step (2), the molecular weight of the high-density polyethylene can be 3000-9000. The present invention aims to develop a portable and tailorable electrolyte. The molecular weight of the polyethylene determines its plasticity and porosity during stretching. If the molecular weight is too small, the porosity of the film after stretching is too low, and the subsequent adsorption of electrolyte content is too low, affecting the color change control performance of the device; if the molecular weight is too large, the plasticity of the film is low, and the film is prone to tearing during the stretching process.

[0038] In some embodiments, in step (2), the process parameters of the biaxial stretching process may include: a preheating temperature of 100-130°C; a longitudinal stretching force of 50-500 MPa, and a temperature range of 120-140°C; and a transverse stretching force of 50-500 MPa, and a temperature range of 130-150°C. Excessively high temperatures or excessive forces can easily cause the film to crack; conversely, insufficient porosity in the film can result, insufficient electrolyte adsorption, and reduced regulatory capacity.

[0039] In some embodiments, in step (2), the thickness of the mesoporous membrane (thickness of the electrolyte layer) after the biaxial stretching process can be 1-20 μm.

[0040] In some embodiments, in step (2), the electrolyte precursor solution can be prepared by mixing a photocurable resin, a solvent, ferrocene, a crosslinking agent, an ion source solution, and a coupling agent in a mass ratio of 1:1-3:0.05-0.2:0.5-2:1-3:0.02-0.1, and then adding an initiator in an amount of 0.1-0.5% of the total mass of the mixture and mixing again. Adding an appropriate amount of coupling agent can improve the bonding strength between the electrolyte layer, the first transparent electrode, and the electrochromic layer.

[0041] Among them, the photocurable resin can be Xianmeite (UC-935); the solvent can be PMA propylene glycol methyl ether acetate; the cross-linking agent can be ETPTA; the coupling agent can be γ-aminopropyltriethoxysilane; and the initiator can be initiator 1173.

[0042] 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.

[0043] In some embodiments, in step (2), the soaking time may be 30-50° C. and the temperature may be 1-12 h.

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

[0045] In summary, the present invention proposes a broadband-controllable, all-solid-state electrochromic device with a mobile electrolyte based on inorganic electrochromic materials such as WO3. This innovative, ultra-thin, robust mobile electrolyte, developed using in-situ curing technology, takes into account the need for broadband transmittance. The electrolyte is primarily composed of a nanofibrous, ultra-strong polyethylene diaphragm. The pores of the diaphragm are filled with an ionic dispersion and counter electrode materials (electrolyte additives). A suitable amount of silane coupling agent is added to enhance the bonding strength between the electrolyte and the upper and lower layers. The prepared electrolyte is directly sandwiched between the upper and lower electrodes, and a certain amount of pressure is applied to form a complete device.

[0046] The electrolyte-migrating laminated 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.

[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 electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment comprises the following steps: (1) First, glass was used as a substrate, and a first transparent electrode with high sunlight transmittance (transmittance 78%) and high infrared reflectivity (reflectivity 75%) was prepared on its surface; secondly, a second transparent electrode with high sunlight transmittance and high infrared transmittance (wideband transmittance 80%) was prepared on a BaF2 substrate, and metal tungsten was used as a 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 a power density of 1.4 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. (2) According to the prior art, an electrolyte precursor solution is prepared with a mass ratio of 1:2:0.1:1:1:0.05 between a photocurable resin (Xianmet), a solvent (PMA propylene glycol methyl ether acetate), ferrocene, ETPTA, a PC (propylene carbonate) solution of LiClO4 and γ-aminopropyltriethoxysilane, wherein the concentration range of the ion source solution is 1 mol / L; a high-density polyethylene (molecular weight 5000) is stretched into a 5 μm thick mesoporous membrane by biaxial stretching, with a longitudinal stretching temperature of 130°C and a transverse stretching temperature of 140°C, and the membrane is immersed in the above-mentioned precursor solution; after photocuring, the device is placed under a 100W ultraviolet lamp for uniform irradiation to obtain a mobile electrolyte layer; (3) The obtained transferable electrolyte layer is sandwiched between the first transparent electrode and the electrochromic layer, and corresponding pressure is applied to obtain the electrolyte transferable all-solid-state wide-band controllable laminated electrochromic device.

[0050] Example 2

[0051] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated 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 electrochromic layer is 200 nm.

[0052] Example 3

[0053] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated 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 electrochromic layer is 600 nm.

[0054] Example 4

[0055] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), the pressure of the electrochromic layer during heating and annealing is 2 Torr.

[0056] Example 5

[0057] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (1), the pressure of the electrochromic layer during heating and annealing is 200 torr.

[0058] Example 6

[0059] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), high-density polyethylene is stretched into a 1 μm mesoporous membrane.

[0060] Example 7

[0061] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), high-density polyethylene is stretched into a 20 μm mesoporous membrane.

[0062] Example 8

[0063] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), the longitudinal stretching temperature of the high-density polyethylene during biaxial stretching is 120°C, and the transverse stretching temperature is 130°C.

[0064] Example 9

[0065] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), the longitudinal stretching temperature of the high-density polyethylene during biaxial stretching is 140°C, and the transverse stretching temperature is 150°C.

[0066] Example 10

[0067] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), the molecular weight of the high-density polyethylene is 3000.

[0068] Example 11

[0069] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), the molecular weight of the high-density polyethylene is 9000.

[0070] Example 12

[0071] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), the mass ratio of the components of the electrolyte precursor solution is 1:2:0.1:1:1:0.02.

[0072] Example 13

[0073] The preparation method of the electrolyte-migratable all-solid-state broadband controllable laminated electrochromic device provided in this embodiment is similar to that in Example 1, with the following main differences: In step (2), the mass ratio of the components of the electrolyte precursor solution is 1:2:0.1:1:1:0.1.

[0074] Comparative Example 1

[0075] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (2), γ-aminopropyltriethoxysilane is not added to the electrolyte precursor solution.

[0076] Comparative Example 2

[0077] 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 molecular weight of the high-density polyethylene is 1000.

[0078] Comparative Example 3

[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 molecular weight of the high-density polyethylene is 10,000.

[0080] Comparative Example 4

[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 electrolyte precursor solution is directly vacuum-filled between the electrodes, and a complete device is obtained after photocuring.

[0082] Comparative Example 5

[0083] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (2), PVB powder is added to the prepared electrolyte precursor solution in a weight ratio of 1:1, and stirred at room temperature for 2 hours to obtain a mixed slurry; then, the slurry is filled between the electrochromic layer and the first transparent electrode, placed in a vacuum oven at 60°C and heated for 10 minutes, and cooled to room temperature to obtain a quasi-solid-state lithium-containing organic polymer PVB film and a corresponding electrochromic device.

[0084] After testing, the solar energy regulation capability of the electrochromic device is 0.2, the mid- and far-infrared emissivity regulation rate before and after fading is 0.02, and the interface bonding strength is 0.5 MPa.

[0085] Comparative Example 6

[0086] The preparation method of the electrochromic device provided in this comparative example refers to comparative example 5, with the main differences being: In step (2), the PVB powder is replaced with high-density polyethylene powder, and finally a quasi-solid lithium-containing organic polymer PE film and a corresponding electrochromic device are obtained.

[0087] After testing, the solar energy regulation capability of the electrochromic device is 0.3, the mid- and far-infrared emissivity regulation rate before and after fading is 0.2, and the interface bonding strength is 0.7 MPa.

[0088] Table 1 below shows the relevant parameters of the electrochromic devices prepared in Examples 1-13 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. An all-solid-state, wide-band, controllable, laminated electrochromic device with electrolyte migration, characterized in that: The structure of the electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device may include: a glass substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a second transparent electrode and a surface high-transmittance substrate stacked in sequence.

2. The electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device according to claim 1, characterized in that: The electrolyte layer is an organic resin cation gel conductive layer based on polyethylene mesoporous membrane, and the cations include Li + 、Al 3+ , K + and Na + At least one of; preferably, the thickness of the electrolyte layer is 1-20 μm.

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

4. The all-solid-state wide-band controllable laminated electrochromic device with electrolyte migration according to any one of claims 1 to 3, characterized in that: The electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device has a control range covering 0.38-2.5 μm sunlight and 2.5-25 μm mid-infrared bands; the solar energy control capability (%) is ≥0.5, the mid- and far-infrared emissivity control rate before and after fading (%) is ≥0.31, and the interface bonding strength is ≥0.1 MPa.

5. A method for preparing an all-solid-state wide-band controllable laminated electrochromic device with electrolyte migration according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: (1) using magnetron sputtering to prepare a first transparent electrode on the surface of a glass substrate, and sequentially preparing a second transparent electrode and an electrochromic layer on the surface of a high-transmittance substrate; (2) forming a mesoporous membrane of high-density polyethylene by a biaxial stretching process and immersing the membrane in an electrolyte precursor solution, and curing the membrane after immersion to obtain a mobile electrolyte layer; (3) Placing the migrated electrolyte layer between the first transparent electrode and the electrochromic layer and applying pressure to obtain the electrolyte-migratable all-solid-state wide-band controllable laminated electrochromic device.

6. The preparation method according to claim 5, characterized in that Step (1) also includes a process of heating and annealing the magnetron sputtered electrochromic layer; wherein the heating and annealing process includes: under an inert atmosphere, the heat treatment pressure is 2-200 torr, the heat treatment process is: heating to 200-400°C for 10-40s and then keeping warm for 50-200s, then heating to 300-500°C for 5-50s, keeping warm for 100-500s, and naturally cooling to room temperature.

7. The preparation method according to claim 5 or 6, characterized in that: In step (2), the molecular weight of the high-density polyethylene is 3000-9000.

8. The preparation method according to any one of claims 5 to 7, characterized in that In step (2), the process parameters of the biaxial stretching process include: a preheating temperature of 100-130°C; a longitudinal stretching force of 50-500 MPa, and a temperature range of 120-140°C; and a transverse stretching force of 50-500 MPa, and a temperature range of 130-150°C.

9. The preparation method according to any one of claims 5 to 8, characterized in that In step (2), the electrolyte precursor solution can be obtained by mixing a photocurable resin, a solvent, ferrocene, a crosslinking agent, an ion source solution and a coupling agent in a mass ratio of 1:1-3:0.05-0.2:0.5-2:1-3:0.02-0.1, and then adding an initiator of 0.1-0.5% of the total mass of the mixture and mixing again.

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