Electrochromic device capable of dynamically adjusting visible high-transmittance infrared and preparation method of electrochromic device

Abstract

The invention relates to a visible high-transmittance infrared dynamic adjustable electrochromic device and a preparation method thereof. The electrochromic device capable of dynamically adjusting the visible high-transmittance infrared comprises an electrolyte layer, an electrochromic layer and an electrode which are arranged in a stacked mode. Wherein anions of an ion source in the electrolyte layer comprise nitrate NO3 <->, and a solvent comprises ethylene glycol dimethyl ether DME; a unit cell structure of the electrochromic layer is provided with octahedral and tetrahedral ion migration channels; the carrier mobility of the electrode is 10 <-70 > cm < 2 > / Vs.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromic functional materials and devices, and particularly relates to a dynamically adjustable electrochromic device with high visible infrared transmittance 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 broadband electrochromic devices primarily focuses on the controlled deposition of metal ions, leveraging the high emissivity and low reflectivity of deposited metals in the mid-infrared to construct devices with controllable emissivity. However, these devices often utilize liquid electrolytes, which present issues such as leakage, poor stability, and safety concerns.

[0006] Looking further, the working principles of wide-band control electrochromic devices are currently divided into two types: one is the reversible deposition of metals based on liquid electrolytes, and the other is polyaniline-based organic electrochromic materials. However, the electrochromic devices based on the above two working principles usually have the problem of coupling the control process of sunlight and infrared light, that is, the transmittance of visible light also decreases significantly when the infrared light is controlled, especially for wide-band control devices based on reversible basic deposition. As the infrared band is controlled, the visible light part changes from a transmittance state to a reflective state. Therefore, for application scenarios with high visible light transmittance requirements or high lighting requirements (such as solar photovoltaic cells, car windshields, etc.), the application of such devices will have greater limitations. Summary of the Invention

[0007] In view of the above technical problems, the object of the present invention is to provide a highly visible infrared transmittance dynamically adjustable electrochromic device and a preparation method thereof.

[0008] In a first aspect, the present invention provides a dynamically adjustable electrochromic device with high visible infrared transmittance, comprising: a stacked electrolyte layer, an electrochromic layer, and electrodes; wherein: The anions of the ion source in the electrolyte layer include nitrate NO3 - , the solvent includes ethylene glycol dimethyl ether DME; The unit cell structure of the electrochromic layer has octahedral and tetrahedral ion migration channels; The carrier mobility of the electrode is 10-70 cm 2 / V s.

[0009] Preferably, the cations of the ion source in the electrolyte layer include Cs + .

[0010] Preferably, the diameter of the octahedral ion migration channel of the unit cell structure of the electrochromic layer is 0.35-0.8 nm, and the diameter of the tetrahedral ion migration channel is 0.3-0.5 nm.

[0011] In a second aspect, the present invention provides a method for preparing the above-mentioned visible high-transmittance infrared dynamically adjustable electrochromic device, the preparation method comprising the following steps: preparing electrodes according to the structure of the electrochromic device and performing electrode heating annealing, and preparing an electrochromic layer on the surface of the electrode and performing heating annealing of the electrochromic layer.

[0012] Preferably, the electrode heating annealing process includes: in an inert atmosphere, the heat treatment pressure is 2-200 torr; the heat treatment process is heating to 300-400°C for 10-30s, keeping warm for 50-200s, heating to 400-500°C for 1-20s, keeping warm for 100-300s, and naturally cooling to room temperature.

[0013] Preferably, the heat treatment process of the electrode heating annealing is heating to 350° C. for 20 seconds, keeping warm for 100 seconds, heating to 450° C. for 10 seconds, keeping warm for 200 seconds, and then naturally cooling to room temperature.

[0014] Preferably, the process of heating and annealing the electrochromic layer includes: in an air atmosphere, the heat treatment pressure is 2-200 torr; the heat treatment process is heating to 300-400°C for 10-30 seconds, keeping warm for 50-200 seconds, heating to 400-600°C for 1-20 seconds, keeping warm for 100-300 seconds, and then naturally cooling to room temperature.

[0015] Preferably, the heat treatment process of the electrochromic layer heating annealing is heating to 350° C. for 20 seconds, keeping warm for 100 seconds, heating to 500° C. for 20 seconds, keeping warm for 200 seconds, and then naturally cooling to room temperature.

[0016] Beneficial effects (1) The present invention achieves dynamic regulation of the infrared band with high visible light transmittance through coordinated regulation of ion migration process control, crystal structure control, and electrode mobility control; decoupling of visible light and infrared light through ion migration process control, crystal structure control, and electrode mobility control enables the device to controllably adjust the transmittance of near-infrared (0.78-2.5μm) and the emissivity of mid-infrared (2.5-25μm) while maintaining high transmittance. (2) The present invention achieves high visible light transmittance and wide infrared band regulation by designing a simple all-solid-state electrochromic structure, which can produce excellent energy-saving effects in fields with high lighting requirements, such as solar cells and airport windows; (3) The preparation method provided by this patent is simple in process, low in cost, and easy to promote. The high-performance electrochromic device prepared has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a schematic diagram of the exemplary structure of the electrochromic device with high visible infrared transmittance and dynamic adjustment provided by the present invention. DETAILED DESCRIPTION

[0018] 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.

[0019] First, if Figure 1 As shown, the present invention provides a dynamically adjustable electrochromic device with high visible infrared transmittance. The structure of the dynamically adjustable electrochromic device with high visible infrared transmittance may include: a substrate, a first transparent electrode, an electrolyte layer, an electrochromic layer, a second transparent electrode, and a highly transparent substrate stacked in sequence.

[0020] In some embodiments, the substrate may be made of glass, PMMA, or polycarbonate, and may have a thickness of 0.1-5 mm.

[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 first transparent electrode has a solar transmittance of 75% or more in the range of 0.38-2.5 μm and a mid-infrared reflectance of 75% or more in the range of 2.5-25 μm. This ensures the transmittance in the solar band and the infrared regulation capability.

[0022] In some embodiments, the anion of the ion source in the electrolyte layer may include nitrate NO3 - , cations may include Cs + , the solvent may include ethylene glycol dimethyl ether DME; preferably, the thickness may be 0.5-6 μm.

[0023] In the present invention, the anion of the ion source in the electrolyte layer adopts nitrate ion, which has lower activation energy than ions such as perchlorate, can weaken the solvation environment of the cations and improve the migration efficiency of the ions. At the same time, the solubility of the ion salt can be improved by introducing a suitable cosolvent DME (ethylene glycol dimethyl ether). The polar part of the DME molecule is mainly provided by the oxygen atom in the molecule and the carbon-oxygen bond (CO bond) connected to the oxygen atom. The electronegativity of the oxygen atom is large, and it has a stronger ability to attract electrons than carbon atoms and hydrogen atoms; in the CO bond, the electron cloud will be biased towards the oxygen atom side, so that the oxygen atom has a partial negative charge, and the carbon atom connected to it has a partial positive charge, thereby generating polarity. In DME, each methoxy group (-OCH3) has a certain polarity, and the polarity of the two methoxy groups interacts in the molecule, so that the molecule has obvious polarity characteristics.

[0024] 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.

[0025] Preferably, the unit cell structure of the electrochromic layer may have octahedral and tetrahedral ion migration channels; wherein the diameter of the octahedral ion migration channel may be 0.35-0.8 nm, and the diameter of the tetrahedral ion migration channel may be 0.3-0.5 nm.

[0026] The electrochromic layer thin film of the device provided by the present invention has a unique unit cell structure formed through a heat treatment described below. The unit cell structure has octahedral and tetrahedral ion migration channels. Through the ion migration process, the large octahedral ion migration channels are filled with large Cs ions, and the small tetrahedral cavities are filled with mobile lithium ions. When different ions enter the electrochromic film, different small polaron resonances are generated, and the energy bands undergo different degrees of shift. The larger the ion size, the more red-shifted the band edge, thereby enhancing infrared absorption and maintaining high visible light transmittance.

[0027] In some embodiments, the material of the second transparent electrode may include at least one of ITO, FTO, AZO, and ATO; preferably, the second transparent electrode may have a 0.38-2.5 μm sunlight transmittance of ≥75%, a 2.5-25 μm mid-infrared transmittance of ≥75%, and a carrier mobility of 10-70 cm 2 / V s.

[0028] The current carrier mobility of the electrode directly affects the migration efficiency of electrons driven by the electric field. By regulating the carrier mobility of the second transparent electrode through heat treatment, its electron migration efficiency can be matched with the ion migration efficiency of the electrolyte layer, thereby indirectly regulating the migration process of cations. Ultimately, the device can always maintain high transmittance while controllably adjusting the transmittance of the near-infrared (0.78-2.5μm) and the emissivity of the mid-infrared (2.5-25μm).

[0029] In the present invention, the carrier mobility of the electrode is regulated by heat treatment. If the mobility is too high, the carrier concentration is too low, resulting in excessive electrode resistance and insufficient device response performance; if the mobility is too low, the carrier concentration is too high, resulting in low infrared transmittance of the electrode.

[0030] In some embodiments, the material of the 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% or greater in the 0.38-2.5 μm range and a mid-infrared transmittance of 75% or greater in the 2.5-25 μm range. This ensures both solar transmittance and infrared regulation capabilities.

[0031] In some embodiments, the visible light transmittance of the highly infrared transmittance dynamically adjustable electrochromic device is ≥39%, the near-infrared transmittance adjustment rate / near-infrared transmittance regulation / near-infrared transmittance adjustment rate / near-infrared adjustment capability is ≥0.4, the mid- and far-infrared emissivity adjustment rate / mid-infrared adjustment capability is ≥0.3, and the stable cycle performance is ≥10,000 times.

[0032] The present invention decouples visible light and infrared light through ion migration process control, crystal structure control and electrode mobility control, so that the device can always maintain high transmittance while controllably adjusting the transmittance of near-infrared (0.78-2.5μm) and the emissivity of mid-infrared (2.5-25μm).

[0033] The following is an exemplary description of the method for preparing a highly visible infrared transmittance dynamically adjustable electrochromic device provided by the present invention. The method may include the following steps: (1) According to the structure of the visible high-transmittance infrared dynamically adjustable electrochromic device, a first transparent electrode is prepared on the surface of the substrate, and a second transparent electrode and an electrochromic layer are prepared in sequence on the surface of the high-transmittance substrate 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 electrochromic device with high visible infrared transmittance and dynamic adjustment.

[0034] In some embodiments, step (1) may further include a process of performing electrode heating annealing after magnetron sputtering the second transparent electrode; wherein the electrode heating annealing process may include: a heat treatment pressure of 2-200 torr under an inert atmosphere; a heat treatment process of heating to 300-400°C for 10-30 seconds, holding for 50-200 seconds, heating to 400-500°C for 1-20 seconds, holding for 100-300 seconds, and naturally cooling to room temperature; preferably, heating to 350°C for 20 seconds, holding for 100 seconds, heating to 450°C for 10 seconds, holding for 200 seconds, and naturally cooling to room temperature. The oxygen vacancies in the electrode are regulated by heat treatment. Improper temperature and time control will affect the distribution of oxygen vacancies, thereby affecting the carrier mobility of the film.

[0035] 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 .

[0036] 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.

[0037] 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.

[0038] In some embodiments, step (1) may further include a process of heating and annealing the electrochromic layer after magnetron sputtering the electrochromic layer; wherein the process of heating and annealing the electrochromic layer may include: in an air atmosphere, a heat treatment pressure of 2-200 torr, a heat treatment process of heating to 300-400°C for 10-30 seconds, holding for 50-200 seconds, heating to 400-600°C for 1-20 seconds, holding for 100-300 seconds, and naturally cooling to room temperature; preferably, heating to 350°C for 20 seconds, holding for 100 seconds, heating to 500°C for 20 seconds, holding for 200 seconds, and naturally cooling to room temperature. Insufficient temperature makes it difficult to form the corresponding structure, affecting the migration channel of ions and thus affecting the regulation performance of the device; excessive temperature results in excessive crystallinity of the device and excessive ion migration barrier, which also affects the performance of the device. For the electrochromic layer, the present invention adopts a rapid temperature rise annealing process. The rapid temperature rise helps to make the grain size in the film uniform, and the higher annealing temperature can promote the regulation of vacancy distribution in the grains.

[0039] In some embodiments, in step (2), the electrolyte solution can be obtained by mixing a photocurable resin, a solvent, ferrocene, a crosslinking agent, and an ion source solution in a mass ratio of 1:(1-3):(0.05-0.2):(0.5-2):(1-3), and then adding an initiator in an amount of 0.1-0.5% of the total mass of the mixture and mixing again.

[0040] Among them, the photocurable resin can be at least one of aliphatic polyurethane diacrylate, aliphatic polyurethane dimethacrylate, and aromatic polyurethane diacrylate; the solvent can be PMA propylene glycol methyl ether acetate; the crosslinker can be ETPTA; and the initiator can be initiator 1173.

[0041] Among them, the solute mass ratio in the ion source solution can be LiClO4:LiNO3:CsNO3=1:(0.1-0.3):(0.1-0.4), and the solvent mass ratio is PC (propylene carbonate):DME (ethylene glycol dimethyl ether)=1:(0.2-0.5); the solution concentration of the ion source can be 1 mol / L.

[0042] In some embodiments, in step (2), the curing method can be ultraviolet curing (such as 100W) or thermal curing.

[0043] The electrochromic device, with high visible infrared transmittance and dynamic tunability, fabricated by this invention can significantly reduce cooling or insulation energy consumption in both summer and winter for applications requiring high light intensity. Simulations using Energyplus software have shown that this electrochromic smart window demonstrates superior light-transmitting performance and energy efficiency compared to Low-E glass in major regions around the world.

[0044] 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.

[0045] Example 1

[0046] The method for preparing a highly visible infrared transmittance dynamically adjustable electrochromic device provided by the present invention comprises the following steps: (1) First, a glass substrate was used to prepare a first transparent electrode with high sunlight transmittance and high infrared reflectance on its surface; secondly, a second transparent electrode with high sunlight transmittance and high infrared reflectance was prepared on the infrared high transmittance substrate by magnetron sputtering. The second transparent electrode film was rapidly heat-treated in an inert atmosphere. The heat treatment pressure was 100 torr. The heat treatment process was heated to 350°C in 20 seconds, kept warm for 100 seconds, heated to 450°C in 10 seconds, kept warm for 200 seconds, and then naturally cooled to room temperature. The carrier mobility was 40 cm 2 / Vs; Subsequently, an inorganic electrochromic layer was prepared by magnetron sputtering with tungsten as the target, argon and oxygen as the sputtering gases, a total pressure of 2.0 Pa, an oxygen partial pressure of 12%, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, and a DC power supply of 70 W or a power density of 1.5 W / cm2 applied to the target. 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 the atmosphere. The heat treatment process was heating to 350°C for 20 seconds, holding for 100 seconds, heating to 500°C for 20 seconds, holding for 200 seconds, and then naturally cooling to room temperature. (2) A 1 mol / L ion source solution is prepared according to a solute mass ratio of LiClO4:LiNO3:CsNO3 of 1:0.2:0.3 and a solvent mass ratio of PC (propylene carbonate):DME (ethylene glycol dimethyl ether) of 1:0.3; an electrolyte solution prepared by weighing a photocurable resin, a solvent (PMA propylene glycol methyl ether acetate), ferrocene, ETPTA and an ion source solution in a mass ratio of 1:2:0.1:1:2 is filled between the above-mentioned first transparent electrode and the electrochromic layer by vacuum drip irrigation; a complete device is formed by ultraviolet light 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 photocuring is to place the device under a 100 W 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 above-mentioned visible high-transmittance infrared dynamically adjustable electrochromic device.

[0047] Example 2

[0048] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment 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.

[0049] Example 3

[0050] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment 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.

[0051] Example 4

[0052] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the ratio of LiClO4:LiNO3:CsNO3 is 1:0.1:0.4.

[0053] Example 5

[0054] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the ratio of LiClO4:LiNO3:CsNO3 is 1:0.3:0.1.

[0055] Example 6

[0056] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the ratio of PC (propylene carbonate) to DME (ethylene glycol dimethyl ether) is 1:0.2.

[0057] Example 7

[0058] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the ratio of PC (propylene carbonate) to DME (ethylene glycol dimethyl ether) is 1:0.5.

[0059] Example 8

[0060] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the electrode heating annealing heat treatment pressure is 2 Torr, and the carrier mobility is 10 cm 2 / V s.

[0061] Example 9

[0062] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the electrode heating annealing heat treatment pressure is 200 torr, and the carrier mobility is 70 cm 2 / V s.

[0063] Example 10

[0064] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the heat treatment process of the electrochromic layer heating annealing is heating to 350° C. for 20 seconds, keeping warm for 100 seconds, heating to 450° C. for 20 seconds, keeping warm for 200 seconds, and then naturally cooling to room temperature.

[0065] Example 11

[0066] The preparation method of the electrochromic device with high visible infrared transmittance and dynamic adjustment provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the heat treatment process of the electrochromic layer heating annealing is heating to 350° C. for 20 seconds, keeping warm for 100 seconds, heating to 550° C. for 20 seconds, keeping warm for 200 seconds, and then naturally cooling to room temperature.

[0067] Comparative Example 1

[0068] 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 ion source solution does not contain LiNO 3 and CsNO 3 .

[0069] Comparative Example 2

[0070] 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 ion source solution does not contain solvent DME.

[0071] Comparative Example 3

[0072] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (1), the electrode heating annealing heat treatment pressure is atmospheric pressure, and the carrier mobility is 100cm 2 / V s.

[0073] Comparative Example 4

[0074] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (1), the heat treatment process of the electrochromic layer heating annealing is heating to 500° C. for 40 seconds, keeping the temperature for 300 seconds, and then naturally cooling to room temperature.

[0075] Comparative Example 5

[0076] 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 solute mass ratio in the ion source solution is LiClO4:LiNO3:CsNO3 is 1:0.01:0.01.

[0077] After testing, the visible light transmittance of the device after coloring is 0.2, the near-infrared transmittance is adjusted to 0.31, the mid- and far-infrared emissivity adjustment rate is 0.12, and the stable cycle performance is 2000 times.

[0078] Comparative Example 6

[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 solute mass ratio in the ion source solution is LiClO4:LiNO3:CsNO3 is 1:0.5:0.5.

[0080] After testing, the visible light transmittance of the device after coloring is 0.7, the near-infrared transmittance is adjusted to 0.06, the mid- and far-infrared emissivity adjustment rate is 0.09, and the stable cycle performance is 3,000 times.

[0081] Comparative Example 7

[0082] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (1), the carrier mobility of the second transparent electrode is 5cm 2 / V s.

[0083] After testing, the visible light transmittance of the obtained device is 0.68, the near-infrared transmittance control is 0.13, the mid- and far-infrared emissivity adjustment rate is 0.01, and the stable cycle performance is 10,000 times.

[0084] Table 1 below shows the relevant parameters of the electrochromic devices prepared in Examples 1-11 and Comparative Examples 1-3:

[0085] 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 highly visible infrared transmittance dynamically adjustable electrochromic device, characterized in that: include: An electrolyte layer, an electrochromic layer, and electrodes are stacked; wherein: The anions of the ion source in the electrolyte layer include nitrate NO3 - , the solvent includes ethylene glycol dimethyl ether DME; The unit cell structure of the electrochromic layer has octahedral and tetrahedral ion migration channels; The carrier mobility of the electrode is 10-70 cm 2 / V s.

2. The electrochromic device with high visible infrared transmittance and dynamic adjustment according to claim 1, characterized in that: The cations of the ion source in the electrolyte layer include Cs + .

3. The electrochromic device with high visible infrared transmittance and dynamic adjustment according to claim 1 or 2, characterized in that: The diameter of the octahedral ion migration channel of the unit cell structure of the electrochromic layer is 0.35-0.8 nm, and the diameter of the tetrahedral ion migration channel is 0.3-0.5 nm.

4. A method for preparing a highly visible infrared transmittance dynamically adjustable electrochromic device according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: preparing an electrode according to the structure of the electrochromic device and performing heating annealing on the electrode, and preparing an electrochromic layer on the surface of the electrode and performing heating annealing on the electrochromic layer.

5. The preparation method according to claim 4, characterized in that The electrode heating annealing process includes: in an inert atmosphere, the heat treatment gas pressure is 2-200 torr; the heat treatment process is heating to 300-400°C for 10-30s, keeping warm for 50-200s, heating to 400-500°C for 1-20s, keeping warm for 100-300s, and naturally cooling to room temperature.

6. The preparation method according to claim 4 or 5, characterized in that The heat treatment process of the electrode heating annealing is heating to 350° C. for 20 seconds, keeping the temperature for 100 seconds, heating to 450° C. for 10 seconds, keeping the temperature for 200 seconds, and then naturally cooling to room temperature.

7. The preparation method according to any one of claims 4 to 6, characterized in that The electrochromic layer heating annealing process includes: in an air atmosphere, a heat treatment pressure of 2-200 torr; the heat treatment process is heating to 300-400°C for 10-30 seconds, keeping warm for 50-200 seconds, heating to 400-600°C for 1-20 seconds, keeping warm for 100-300 seconds, and naturally cooling to room temperature.

8. The preparation method according to any one of claims 4 to 7, characterized in that The heat treatment process of the electrochromic layer heating annealing is heating to 350° C. for 20 seconds, keeping the temperature for 100 seconds, heating to 500° C. for 20 seconds, keeping the temperature for 200 seconds, and then naturally cooling to room temperature.

Images