Electrochromic device and method of manufacturing the same

Abstract

The application relates to the technical field of electrochromic technology, in particular to an electrochromic device and a preparation method thereof. The preparation method of the electrochromic device comprises the following steps: depositing a first material on one side of a first substrate to form a first transparent conductive layer; depositing a second material on the side of the first transparent conductive layer away from the first substrate, and then performing air thermal oxidation on the second material to form an electrochromic layer; depositing the first material on one side of a second substrate to form a second transparent conductive layer; and forming an electrolyte layer between the electrochromic layer and the second transparent conductive layer. The electrochromic device obtained through the preparation method can realize the partition adjustment of the visible light wave band and the near-infrared light wave band, and has excellent partition modulation effects of visible light and infrared light.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electrochromic technology, and particularly relates to an electrochromic device and a preparation method thereof. BACKGROUND

[0002] Under the background of rapid increase of world population and industrial modernization, building energy consumption is increasing, and the proportion of global total energy consumption has risen to more than 40%. Compared with static windows, electrochromic windows are active electrochromic devices that can independently and selectively adjust visible light and near-infrared light to achieve large-scale solar radiation modulation.

[0003] In 2013, D. J. Milliron et al. studied glass nanocrystal composites based on indium tin oxide (ITO) nanocrystals and amorphous niobium oxide (NbOx). The indium tin oxide nanocrystals modulate near-infrared light through free carrier density and localized surface plasmon resonance (LSPR) absorption, while the polarization absorption of amorphous niobium oxide adjusts visible light. Since then, some nanocomposites have been proved to have dual-band electrochromic modulation characteristics, but the preparation process is too complex. WO3 as a single-component material has special tunneling and excellent carrier capacity. Studies have shown that the oxygen vacancy WO 3-x Nanocrystals or nanowires can simultaneously achieve controllable regulation of visible light and near-infrared light, thus opening up a research boom in single-component dual-band electrochromic materials. Related studies at home and abroad have shown that the performance of single-component dual-band electrochromic materials depends largely on the preparation process and the microstructure of the final film. Currently, the synthesis and preparation of the electrochromic layer of the electrochromic device mainly use chemical synthesis methods such as liquid phase method, chemical bath deposition method, electrochemical deposition method, spray pyrolysis method, sol-gel method, hydrothermal method and solvothermal synthesis method, so that the electrochromic device prepared finally usually has the problems of low full-band optical contrast, poor partition modulation effect of visible light and infrared light, which seriously hinders the development and application of electrochromic devices. SUMMARY

[0004] Therefore, the present application aims to provide an electrochromic device and a preparation method thereof. The electrochromic device obtained by the preparation method can achieve partition adjustment of visible light and near-infrared light, and has excellent partition modulation effect of visible light and infrared light.

[0005] To achieve the above-mentioned purpose, the technical scheme of the present application is as follows:

[0006] A preparation method of an electrochromic device, comprising the following steps:

[0007] depositing a first material on one side of a first substrate to form a first transparent conductive layer;

[0008] depositing a second material on the side of the first transparent conductive layer away from the first substrate, and performing air thermal oxidation on the second material to form an electrochromic layer;

[0009] depositing a first material on one side of a second substrate to form a second transparent conductive layer;

[0010] forming an electrolyte layer between the electrochromic layer and the second transparent conductive layer.

[0011] Further, the method of depositing a first material on one side of a first substrate to form a first transparent conductive layer comprises:

[0012] placing the first material and the first substrate in an electron beam evaporation device, vacuumizing the interior of the electron beam evaporation device until the pressure in the interior reaches a first set pressure, and raising the temperature in the interior of the electron beam evaporation device until the temperature of the first substrate reaches a first set temperature; and evaporating the first material on one side of the first substrate by electron beam to form the first transparent conductive layer; wherein the first set pressure is 2.5x10 -3 Pa~2.8x10 -3 Pa; and the first set temperature is 180℃~200℃.

[0013] Further, the method of evaporating the first material on one side of the first substrate by electron beam to form the first transparent conductive layer comprises:

[0014] adjusting the electron beam to maintain the evaporation rate of the first material at a first set rate, and continuing to evaporate for a first set time; wherein the first set rate is 0.2nm / s~0.4nm / s; and the first set time is greater than or equal to 25 min.

[0015] Further, the method of depositing a second material on the side of the first transparent conductive layer away from the first substrate comprises:

[0016] placing the second material and the first substrate on which the first transparent conductive layer is deposited in an electron beam evaporation device, vacuumizing the interior of the electron beam evaporation device until the pressure in the interior reaches a second set pressure, and evaporating the second material on the side of the first transparent conductive layer away from the first substrate by electron beam at room temperature to form a first crystalline electrochromic layer; wherein the second set pressure is 2.5x10 -3 Pa~2.8x10 -3 Pa.

[0017] Further, the method of evaporating the second material on the side of the first transparent conductive layer away from the first substrate by electron beam to form a first crystalline electrochromic layer comprises:

[0018] The electron beam is shot on the second material, and the electron beam is adjusted so that the rate of evaporating the second material is maintained at a second set rate, and the evaporation of the second material is continued for a second set time; wherein the second set rate is 0.1 nm / s~0.5 nm / s; and the second set time is greater than or equal to 30 min.

[0019] Further, the air thermal oxidation is further performed on the same to form an electrochromic layer, including:

[0020] The first transparent conductive layer and the first substrate on which the first crystalline state electrochromic layer is deposited are heated in an air atmosphere at a second set temperature for a third set time to perform air thermal oxidation; and after the air thermal oxidation, the first transparent conductive layer and the first substrate are taken out and cooled to room temperature to form a second crystalline state electrochromic layer; wherein the second set temperature is 400℃~450℃; and the third set time is 30 min~1000 min.

[0021] Further, an electrolyte layer is formed between the electrochromic layer and the second transparent conductive layer, including:

[0022] A reserved space is left between the electrochromic layer and the second transparent conductive layer, and the two are solidified and connected;

[0023] An electrolyte solution is prepared, the electrolyte solution is injected into the reserved space and sealed to form the electrolyte layer.

[0024] Further, the preparation of the electrolyte solution includes:

[0025] The third material is dissolved in a solvent, and stirred at a third set temperature for a fourth set time at a set stirring speed, so that the third material is completely dissolved in the solvent to form an electrolyte solution.

[0026] Further, the first material is cerium-doped indium oxide; and / or

[0027] The second material is tungsten trioxide.

[0028] An electrochromic device is prepared by using the preparation method of the electrochromic device as described above.

[0029] Compared with the prior art, the present application can achieve the following beneficial effects: the preparation method of the electrochromic device provided by the embodiments of the present application can effectively improve the optical transmittance of infrared light and expand the light modulation range to 2500 nm. The electrochromic layer prepared by the method is deposited with the second material on the side of the first transparent conductive layer away from the first substrate by electron beam thermal evaporation to form a first crystalline electrochromic layer, making the prepared electrochromic layer more uniform and firm. The first transparent conductive layer and the first substrate deposited with the first crystalline electrochromic layer are subjected to air thermal oxidation, so that the size, microstructure and crystal system of the first crystalline electrochromic layer can be adjusted to change the first crystalline electrochromic layer into a second crystalline electrochromic layer. The method of preparing the second crystalline electrochromic layer by air thermal oxidation is simpler. The first substrate, the first transparent conductive layer and the electrochromic layer prepared by the preparation method form a layer group. The obtained layer group has an optical contrast of 76.3% at a wavelength of 680 nm in the visible light band and an optical contrast of 95% at a wavelength of 1300 nm in the near-infrared light band, which exceeds the current maximum infrared optical contrast. At the same time, the prepared electrochromic device can realize three light-heat independent regulation modes of "bright", "cool" and "dark" under different potential control, can realize the partition adjustment of the visible light band and the near-infrared light band, and has excellent partition modulation effect of visible light and infrared light. BRIEF DESCRIPTION OF DRAWINGS

[0030] The accompanying drawings, which form a part of the present application, are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification. The illustrations, together with the description, serve to explain the application offered by the embodiments of the present application, and do not constitute an improper limitation of the present application. In the drawings:

[0031] Figure 1 a schematic diagram of the electrochromic device described in the embodiments of the present application;

[0032] Figure 2 a flowchart of the preparation method of the electrochromic device described in the embodiments of the present application;

[0033] Figure 3 a TEM image of the electrochromic layer of the electrochromic device described in the embodiments of the present application;

[0034] Figure 4 a schematic diagram of the average response time of coloring and the average response time of fading of the electrochromic layer of the electrochromic device described in the embodiments of the present application under visible light and near-infrared light;

[0035] Figure 5Schematic diagram of coloration efficiency value of electrochromic layer of electrochromic device according to the embodiments of the present invention;

[0036] Figure 6 Schematic diagram of transmittance comparison of layer group of electrochromic device according to the embodiments of the present invention and layer group of comparative example under different potential control;

[0037] Figure 7 Further flow chart of preparation method of electrochromic device according to the embodiments of the present invention;

[0038] Figure 8 Graph of test results of light control and heat control ability of electrochromic device according to the embodiments of the present invention under different light and heat control modes.

[0039] Explanation of reference signs:

[0040] Electrochromic device 10; first substrate 11; first transparent conductive layer 12; electrochromic layer 13; second substrate 14; second transparent conductive layer 15; electrolyte layer 16; layer group 17. DETAILED DESCRIPTION

[0041] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention will be further described in detail below in combination with the drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, and do not constitute a limitation on the present invention. Similar element numbers are used for associated similar elements in different embodiments. In the following embodiments, many details are described in order to make the present invention better understood. However, those skilled in the art can easily recognize that some features can be omitted in different cases, or can be replaced by other elements, materials or methods. In some cases, some operations related to the present invention are not shown or described in the specification in order to avoid the core part of the present invention being overwhelmed by too much description, and it is not necessary for those skilled in the art to describe these related operations in detail according to the description in the specification and general technical knowledge in the art.

[0042] It should be noted that the embodiments in the present invention and the features in the embodiments can be combined with each other to form various embodiments without conflict. Meanwhile, each step or action in the method description can also be sequentially adjusted or adjusted in a manner that is obvious to those skilled in the art. Therefore, the various orders in the specification and the drawings are only for the purpose of clearly describing a certain embodiment, and do not mean that the order is necessary, unless otherwise stated that a certain order must be followed.

[0043] In the description of the present application, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first", "second" and the like are only for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined with "first", "second" and the like can explicitly or implicitly include one or more of the features. In the description of the present application, unless otherwise stated, the meaning of "a plurality of" is two or more.

[0044] In the description of the present application, it should be noted that unless otherwise explicitly specified and limited, the terms "mounting", "connecting", "connecting" should be understood broadly, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium, or it can be connected inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0045] The present application will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.

[0046] Referring to Figure 1 and Figure 2 As shown in the drawings, the preparation method of the electrochromic device 10 includes steps S101-S104. Among them, the electrochromic device 10 can be an electrochromic window.

[0047] In step S101, a first material is deposited on one side of a first substrate 11 to form a first transparent conductive layer 12. The first material can be cerium-doped indium oxide (ICO), which includes cerium oxide (CeO2) and indium oxide (In2O3), wherein the molar ratio of cerium oxide in cerium-doped indium oxide is 10mol%-20mol%. The material of the first substrate 11 can be glass, such as K9 glass, quartz glass, etc. The thickness of the first transparent conductive layer 12 formed can be greater than or equal to 100nm. The thickness of the first transparent conductive layer 12 can be 300nm-320nm.

[0048] In one embodiment, step S101 comprises: placing the first material and the first substrate 11 in an electron beam evaporation device, vacuumizing the interior of the electron beam evaporation device until the pressure in the interior reaches a first set pressure. The first set pressure is 2.5 x 10 -3 Pa~2.8 x 10 -3 Pa. The temperature in the interior of the electron beam evaporation device is raised until the temperature of the first substrate 11 reaches a first set temperature. The first set temperature is 180~200℃. The interior of the electron beam evaporation device can be vacuumized, and the temperature in the interior of the electron beam evaporation device is raised after the pressure in the interior reaches 8 Pa. The vacuumizing is continuously performed during the raising of the temperature in the interior of the electron beam evaporation device until the pressure in the interior reaches the first set pressure. The first material is evaporated by electron beam onto one side of the first substrate 11 to form the first transparent conductive layer 12.

[0049] In one embodiment, the first material is evaporated by electron beam onto one side of the first substrate 11 to form the first transparent conductive layer 12, which comprises: firing an electron beam at the first material, adjusting the electron beam so that the evaporation rate of the first material is maintained at a first set rate, and continuously evaporating for a first set time. The firing of the electron beam at the first material can form a spot on the first material, and the adjusting of the electron beam can refer to adjusting the size and position of the spot so that the evaporation rate of the first material is maintained at the first set rate. The first set rate is 0.2~0.4 nm / s. The first set time is greater than or equal to 25 min.

[0050] In this embodiment, cerium-doped indium oxide and the first substrate 11 are placed in an electron beam evaporation device, the interior of the electron beam evaporation device is vacuumized, and the temperature in the interior of the electron beam evaporation device is raised until the temperature of the first substrate 11 reaches 200℃ when the pressure in the interior reaches 8 Pa. The vacuumizing is continuously performed during the raising of the temperature in the interior of the electron beam evaporation device until the pressure in the interior reaches 2.8 x 10 -3 Pa. An electron beam is fired at the cerium-doped indium oxide, the electron beam is adjusted so that the evaporation rate of the cerium-doped indium oxide is maintained at 0.2 nm / s, and the evaporation is continuously performed for 25 min. The cerium-doped indium oxide is deposited on one side of the first substrate 11 to form the first transparent conductive layer 12. The thickness of the formed first transparent conductive layer 12 is 300 nm. The real-time deposition thickness of the first transparent conductive layer 12 can be continuously detected by a quartz crystal microbalance during the deposition of the first transparent conductive layer 12.

[0051] In step S102, the second material is deposited on the side of the first transparent conductive layer 12 away from the first substrate 11, and air thermal oxidation is performed to form the electrochromic layer 13. The second material is tungsten trioxide (WO3). The electrochromic layer 13 described hereinafter is a second crystal state electrochromic layer 13, and the thickness is 100 nm to 1000 nm.

[0052] In one embodiment, the second material is deposited on the side of the first transparent conductive layer 12 away from the first substrate 11, including: placing the second material and the first substrate 11 on which the first transparent conductive layer 12 is deposited in an electron beam evaporation device, and vacuumizing the inside of the electron beam evaporation device until the pressure inside reaches a second set pressure. The inside of the electron beam evaporation device is vacuumized until the pressure inside the electron beam evaporation device reaches the second set pressure. The second set pressure is 2.5 x 10 -3 Pa to 2.8 x 10 -3 Pa. The second material is evaporated on the side of the first transparent conductive layer 12 away from the first substrate 11 by electron beam evaporation at room temperature to form a first crystal state electrochromic layer 13.

[0053] In one embodiment, the second material is evaporated on the side of the first transparent conductive layer 12 away from the first substrate 11 by electron beam evaporation to form a first crystal state electrochromic layer 13, including: firing an electron beam on the second material, adjusting the electron beam to maintain the evaporation rate of the second material at a second set rate, and continuing evaporation for a second set time. The electron beam fired on the second material can form a light spot on the second material, and adjusting the electron beam can refer to adjusting the size and position of the light spot to maintain the evaporation rate of the second material at a second set rate. The second set rate is 0.1 nm / s to 0.5 nm / s. The second set time is greater than or equal to 30 min. The thickness of the first crystal state electrochromic layer 13 deposited on the side of the first transparent conductive layer 12 away from the first substrate 11 can be 110 nm to 1010 nm. When the electrochromic material used is WO3, the deposited electrochromic layer 13 is an amorphous electrochromic layer 13, i.e., the first crystal state is amorphous. 3-x

[0054] ​In one embodiment, the air thermal oxidation is performed again to form the electrochromic layer 13, comprising: heating the first transparent conductive layer 12 and the first substrate 11, on which the first crystalline state of the electrochromic layer 13 is deposited, in an air atmosphere at a second set temperature for a third set time to perform the air thermal oxidation. A vacuum tube furnace can be selected, the temperature inside the vacuum tube furnace is raised until the second set temperature, and then the first transparent conductive layer 12 and the first substrate 11, on which the first crystalline state of the electrochromic layer 13 is deposited, are placed in the inside of the vacuum tube furnace, which can be accommodated in a high-temperature-resistant ceramic crucible, and then placed at the center of the inside of the vacuum tube furnace. The second set temperature is 400-450°C. The third set time is 30-1000 min. After the air thermal oxidation, the first transparent conductive layer 12 and the first substrate 11 are taken out and cooled to room temperature to form the second crystalline state of the electrochromic layer 13. The thickness of the second crystalline state of the electrochromic layer 13 after cooling can be 100-1000 nm. When the electrochromic material used is WO3, the amorphous WO3 3-x electrochromic layer 13 becomes high-purity monoclinic WO 3-x nanocrystalline electrochromic layer 13, i.e., the second crystalline state is high-purity monoclinic nanocrystalline. The high-purity monoclinic WO 3-x nanocrystalline has a grain size of 7-10 nm on average.

[0055] In this embodiment, the tungsten trioxide powder and the first substrate 11, on which the first transparent conductive layer 12 is deposited, are placed in the inside of an electron beam evaporation device, the inside of the electron beam evaporation device is vacuumed to 2.8 x 10 -3 Pa, and the electron beam is shot on the tungsten trioxide at room temperature, the electron beam is adjusted to maintain the evaporation rate of the tungsten trioxide at 0.2 nm / s, and the evaporation is continued for 30 min to form the amorphous WO 3-x electrochromic layer 13. The temperature inside the vacuum tube furnace is raised until the temperature at the center of the inside of the vacuum tube furnace is 450°C, and then the first transparent conductive layer 12 and the first substrate 11, on which the first crystalline state of the electrochromic layer 13 is deposited, are placed at the center of the inside of the vacuum tube furnace, and heated in an air atmosphere for 30 min to perform the air thermal oxidation. After the air thermal oxidation, the first transparent conductive layer 12 and the first substrate 11 are taken out and cooled to room temperature to form the second crystalline state of the electrochromic layer 13. The amorphous WO 3-x electrochromic layer 13 becomes high-purity monoclinic WO 3-x nanocrystalline electrochromic layer 13, thereby forming the electrochromic layer 13 with a thickness of 400 nm.

[0056] Referring to FIG. 1, Figure 3 Figure 3 ​A TEM (Transmission Electron Microscope) image of the electrochromic layer 13 formed by the preparation method of the present embodiment is shown. It can be seen from Figure 3 the left graph (a) that the high-purity monoclinic WO 3-x The grain size of the nanocrystals is 10 nm on average. It can be seen from Figure 3 the right graph (b) that the preparation method of the present embodiment can be used to prepare the electrochromic layer 13 of high-purity monoclinic WO 3-x nanocrystals, and only monoclinic crystal phase exists, with a lattice constant of 0.42 nm. The lattice constant refers to the distance between two adjacent lattice points in a crystal.

[0057] As shown in Figure 4 , Figure 4 A schematic diagram of the average response time of coloring and the average response time of bleaching of the electrochromic layer 13 formed by the preparation method of the present embodiment under visible light (wavelength band: 380 nm~780 nm) and near-infrared light (wavelength band: 780 nm~2500 nm) is shown. Bleaching refers to the process of recovering from a certain color to transparent and colorless after applying a proper voltage to the electrochromic layer 13. Coloring refers to the process of presenting a certain color after applying a proper voltage to the electrochromic layer 13. The response time is the time required for the change amount of transmittance to be 90%. Figure 4 The horizontal coordinate is time, and the vertical coordinate is transmittance. Figure 4 The process from 0 s to 35 s is the coloring process, and the transmittance gradually decreases with time. The process from 35 s to 70 s is the bleaching process, and the transmittance gradually increases with time. It can be seen that, at a wavelength of 680 nm, the average response time of coloring is 24.1 s, and the average response time of bleaching is 16.3 s. At a wavelength of 1000 nm, the average response time of coloring is 15.9 s, and the average response time of bleaching is 18.5 s. The average response times of coloring and bleaching are relatively short. In related technologies, the average response times of coloring and bleaching of some electrochromic layers are long, and the average response time of bleaching is particularly long. For example, the average response time of coloring of amorphous WO 3-x prepared by the solution colloidal method is 22 s, and the average response time of bleaching is 75 s. The average response time of bleaching of triclinic WO 3-x nanocrystals in the near-infrared light region can even reach 105 s. It can be seen that, compared with the electrochromic layers in related technologies, the electrochromic layer 13 formed by the preparation method of the present embodiment can maintain a relatively short average response time of coloring while greatly shortening the average response time of bleaching.

[0058] As shown in Figure 5 ,Figure 5 A schematic diagram is shown of the coloration efficiency (CE) value of the electrochromic layer 13 prepared by the method of this embodiment. Coloration efficiency refers to the change in optical density caused by the amount of charge injected per unit area at a fixed wavelength, and is a performance indicator of the electrochromic layer 13. Higher coloration efficiency indicates stronger light modulation capability. Figure 5 The horizontal axis represents the charge injected per unit area (ΔQ), and the vertical axis represents the change in optical density at a fixed wavelength (ΔOD). The shading efficiency is expressed by the formula: It can be seen that at a wavelength of 680nm, the coloring efficiency is 110.8cm. 2 / C. At a wavelength of 1000 nm, the coloring efficiency is 284.2 cm⁻¹. 2 / C. Therefore, the electrochromic layer 13 prepared by the method of this embodiment has strong light modulation capability in both visible and near-infrared light bands.

[0059] The first substrate 11, the first transparent conductive layer 12, and the electrochromic layer 13 prepared by the above method constitute a layer group 17. A comparative experiment is set up to obtain a comparative example layer group. The difference between the preparation method of the comparative experiment and the preparation method of this embodiment is that the electrochromic layer of the comparative example layer group is not subjected to air thermal oxidation.

[0060] See Figure 6 As shown, Figure 6 A schematic diagram showing the transmittance comparison between layer 17 prepared by the preparation method of this embodiment and the comparative layer under different potential controls is shown. Figure 7 The horizontal axis represents wavelength, and the vertical axis represents transmittance. The left figure (a) shows layer 17 prepared using the method of this embodiment, and the right figure (b) shows a comparative layer. It can be seen that layer 17 prepared using the method of this embodiment exhibits three photothermal modulation modes in the visible and near-infrared light bands of 380nm~2500nm under different driving potentials: bright mode (high transmittance of both visible and near-infrared light), cold mode (high transmittance of visible light but blocking of near-infrared light), and dark mode (blocking of both visible and near-infrared light). Figure 6In the illustrated embodiment, the driving potential of the bright mode is 0.8 V. The driving potential of the cold mode is -0.3 V and -0.4 V, and the driving potential of the dark mode is -0.8 V. The optical contrast at a wavelength of 680 nm in the visible light band is 76.3%, and the optical contrast at a wavelength of 1300 nm in the near-infrared light band is 95%, i.e., the difference in transmittance between the bright mode and the dark mode is as high as 95%, which exceeds the current maximum infrared optical contrast, so the optical contrasts of visible light and near-infrared light are high. The optical contrast refers to the maximum optical transmittance difference of the layer group 17 at a specific wavelength. The layer group 17 prepared in this way can exhibit three light-heat regulation modes of bright, cold, and dark at different driving potentials. It can also achieve zoning regulation of the visible light band and the near-infrared light band of 380 nm to 2500 nm, has good zoning modulation capability, a large optical regulation range, and high optical contrast.

[0061] The comparative example layer group prepared by the preparation method of the comparative experiment cannot achieve high transmittance of visible light and blocking of near-infrared light, i.e., it cannot achieve the cold mode in the regulation mode. The optical contrast of the comparative example layer group is relatively low.

[0062] Therefore, compared with the comparative example layer group, the layer group prepared by the preparation method of the embodiment achieves a great improvement in the optical contrast of the near-infrared light band and an improvement in the zoning modulation capability of the visible light band and the near-infrared light band.

[0063] In step S103, the first material is deposited on one side of the second substrate 14 to form the second transparent conductive layer 15. The specific preparation method of forming the second transparent conductive layer 15 on one side of the second substrate 14 is the same as that of forming the first transparent conductive layer 12 on the first substrate 11. The structure, thickness, and material of the first substrate 11 and the second substrate 14 are the same. The structure, thickness, and material of the first transparent conductive layer 12 and the second transparent conductive layer 15 are the same.

[0064] In step S104, the electrolyte layer 16 is formed between the electrochromic layer 13 and the second transparent conductive layer 15. The material of the electrolyte layer 16 is an inorganic ion electrolyte, and the inorganic ion is a lithium ion. The thickness of the electrolyte layer 16 can be 1 mm to 2 mm.

[0065] Referring to Figure 7 In one embodiment, step S104 includes steps S1041-S1042.

[0066] In step S1041, a reserved space is left between the electrochromic layer 13 and the second transparent conductive layer 15, and the two are solidified and connected. The edges between the electrochromic layer 13 and the second transparent conductive layer 15 can be adhered and connected by ultraviolet curing glue. The reserved space can be formed by surrounding the electrochromic layer 13, the second transparent conductive layer 15, and the ultraviolet curing glue.

[0067] In step S1042, an electrolyte solution is prepared, the electrolyte solution is injected into the reserved space and sealed to form the electrolyte layer 16. The electrolyte solution can be injected into the reserved space through a glue injection hole that is in communication with the outside through a pipette, and the glue injection hole can be sealed with ultraviolet curing glue.

[0068] In one embodiment, preparing the electrolyte solution includes: dissolving a third material in a solvent, and stirring at a third set temperature for a fourth set time at a set stirring speed, so that the third material is completely dissolved in the solvent to form the electrolyte solution. The stirring can be performed by a magnetic stirrer. The third material can be lithium perchlorate (LiClO4), and the solvent can be a propylene carbonate (PC) solvent. The concentration of the electrolyte solution is 0.9 mol / L to 1 mol / L. The lithium perchlorate can be weighed and dissolved in a corresponding volume of propylene carbonate solvent, wherein the corresponding volume of propylene carbonate solvent refers to 1.06392 g of lithium perchlorate powder corresponding to 10 ml of propylene carbonate solvent, 2.12784 g of lithium perchlorate powder corresponding to 20 ml of propylene carbonate solvent, and so on, when the concentration of the electrolyte solution is 1 mol / L. A magnetic stirrer is placed in the solvent and placed on a magnetic stirrer, and stirring is performed by the magnetic stirrer. The third set temperature is 80°C to 100°C. The set stirring speed is 600 r / min to 800 r / min. The fourth set time is 2 h to 3 h. The third material is completely dissolved in the solvent to form the electrolyte solution in liquid form.

[0069] In this embodiment, a reserved space is left between the electrochromic layer 13 and the second transparent conductive layer 15, and the edges of the two are adhered and connected by ultraviolet curing glue. 1.06392 g of lithium perchlorate is dissolved in 10 ml of propylene carbonate solvent, a magnetic stirrer is placed in the solvent and placed on a magnetic stirrer, and stirring is performed at a temperature of 80°C and a stirring speed of 800 r / min for 2 h to form an electrolyte solution. The electrolyte solution is injected into the reserved space, the reserved space is filled, and the reserved space is sealed with ultraviolet curing glue. After complete curing, the electrochromic device 10 is obtained.

[0070] Referring to Figure 8 as shown, Figure 8The diagram shows the test results of the dimming and heating capabilities of the electrochromic device 10 prepared by the preparation method of this embodiment under different photothermal control modes. Figure 8 Figure (a) above shows the dimming capability of the electrochromic device 10 under different photothermal control modes. As can be seen from the figure, the electrochromic device 10 can exhibit a certain color after applying an appropriate voltage (e.g., -6V). It can also revert from a certain color to transparent and colorless after applying an appropriate voltage (e.g., 6V). Figure 8 Figure (b) below shows the heat regulation capability of the electrochromic device 10 under different photothermal control modes. As can be seen from the figure, it can effectively reduce the temperature by 16℃ in the cold mode and by 18.5℃ in the dark mode. Figure 8 As can be seen from this, the electrochromic device 10 can realize three photothermal control modes—bright mode, cold mode, and dark mode—under different driving potentials, thus achieving the effect of dynamic dimming and heating.

[0071] The method for fabricating the electrochromic device 10 provided in this invention provides a first transparent conductive layer 12 that effectively improves the optical transmittance of infrared light and expands the light modulation range to 2500 nm. The electrochromic layer 13 prepared by this method involves depositing a second material onto the side of the first transparent conductive layer 12 away from the first substrate 11 using electron beam thermal evaporation, forming a first crystalline electrochromic layer 13, resulting in a more uniform and robust electrochromic layer 13. Further air thermal oxidation is then performed on the first transparent conductive layer 12 and the first substrate 11 to which the first crystalline electrochromic layer 13 is deposited. This allows for adjustment of the size, microstructure, and crystal system of the first crystalline electrochromic layer 13, transforming it into a second crystalline electrochromic layer 13. The use of air thermal oxidation simplifies the preparation of the second crystalline electrochromic layer 13. The first substrate 11, the first transparent conductive layer 12, and the electrochromic layer 13 prepared by this method constitute a layer group 17. The obtained layer group 17 has an optical contrast ratio of 76.3% at a wavelength of 680 nm in the visible light band and 95% at a wavelength of 1300 nm in the near-infrared light band, surpassing the current maximum infrared optical contrast ratio. Simultaneously, the prepared electrochromic device 10 can achieve three independent photothermal control modes—"bright," "cool," and "dark"—under different potential control, enabling zoned modulation of the visible and near-infrared light bands, and exhibiting excellent zoned modulation effects for visible and infrared light.

[0072] See you again Figure 1As shown, the embodiment of the present application further provides an electrochromic device 10 prepared according to the preparation method of the electrochromic device 10 as described above. The electrochromic device 10 comprises a first substrate 11, a first transparent conductive layer 12, an electrochromic layer 13, an electrolyte layer 16, a second transparent conductive layer 15 and a second substrate 14 which are sequentially stacked.

[0073] It should be understood that the various forms of flow shown above can be used to reorder, add or delete steps. For example, the steps described in the present disclosure can be performed in parallel, sequentially or in a different order, as long as the desired results of the technical solutions of the present disclosure can be achieved, which is not limited herein.

[0074] The above detailed description does not constitute a limitation on the scope of protection of the present application. Those skilled in the art should understand that various modifications, combinations, sub-combinations and substitutions can be made according to design requirements and other factors. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A method for preparing an electrochromic device, characterized in that, include: A first material is deposited on one side of a first substrate to form a first transparent conductive layer; including: The first material and the first substrate are placed inside an electron beam deposition apparatus. The apparatus is evacuated until the internal pressure reaches a first set pressure. The internal temperature of the apparatus is then increased until the temperature of the first substrate reaches a first set temperature. The first material is deposited onto one side of the first substrate using electron beam evaporation to form the first transparent conductive layer. The first set pressure is 2.5 × 10⁻⁶. -3 Pa ~ 2.8 × 10 -3 Pa; The first set temperature is 180℃~200℃; First, a second material is deposited on the side of the first transparent conductive layer opposite to the first substrate, and then subjected to air thermal oxidation to form an electrochromic layer; wherein depositing the second material on the side of the first transparent conductive layer opposite to the first substrate includes: The second material and the first substrate on which the first transparent conductive layer is deposited are placed in an electron beam deposition apparatus. The interior of the electron beam deposition apparatus is evacuated until the internal pressure reaches a second predetermined pressure. At room temperature, the second material is deposited onto the side of the first transparent conductive layer opposite to the first substrate by electron beam evaporation to form a first crystalline electrochromic layer; wherein the second predetermined pressure is 2.5 × 10⁻⁶. -3 Pa ~ 2.8 × 10 -3 Pa; A first material is deposited on one side of a second substrate to form a second transparent conductive layer; An electrolyte layer is formed between the electrochromic layer and the second transparent conductive layer.

2. The method for preparing the electrochromic device according to claim 1, characterized in that, The step of depositing the first material onto one side of the first substrate by electron beam evaporation to form the first transparent conductive layer includes: An electron beam is directed onto the first material, and the electron beam is adjusted to maintain the deposition rate of the first material at a first set rate, and deposition is continued for a first set time; wherein, the first set rate is 0.2 nm / s to 0.4 nm / s; and the first set time is greater than or equal to 25 min.

3. The method for preparing the electrochromic device according to claim 1, characterized in that, The step of depositing the second material onto the side of the first transparent conductive layer opposite to the first substrate by electron beam evaporation to form a first crystalline electrochromic layer includes: An electron beam is directed onto the second material, and the electron beam is adjusted to maintain the deposition rate of the second material at a second set rate, and deposition is continued for a second set time; wherein, the second set rate is 0.1 nm / s to 0.5 nm / s; and the second set time is greater than or equal to 30 min.

4. The method for preparing the electrochromic device according to claim 1, characterized in that, The further air-thermal oxidation to form an electrochromic layer includes: At a second set temperature, the first transparent conductive layer and the first substrate, on which the first crystalline electrochromic layer is deposited, are heated in an air atmosphere for a third set time to perform air thermal oxidation; and after air thermal oxidation, they are removed and cooled to room temperature to form a second crystalline electrochromic layer; wherein, the second set temperature is 400℃~450℃; and the third set time is 30min~1000min.

5. The method for preparing the electrochromic device according to claim 1, characterized in that, The formation of an electrolyte layer between the electrochromic layer and the second transparent conductive layer includes: A reserved space is left between the electrochromic layer and the second transparent conductive layer, and the two are then cured and connected. An electrolyte solution is prepared, injected into the reserved space, and sealed to form the electrolyte layer.

6. The method for preparing the electrochromic device according to claim 5, characterized in that, The preparation of the electrolyte solution includes: The third material is dissolved in a solvent and stirred at a set stirring speed for a set time at a set temperature for a set time to ensure that the third material is completely dissolved in the solvent, thereby forming the electrolyte solution.

7. The method for preparing the electrochromic device according to claim 1, characterized in that, The first material is cerium-doped indium oxide; and / or The second material is tungsten trioxide.

8. An electrochromic device, characterized in that, It is prepared by the method for preparing an electrochromic device as described in any one of claims 1-7.

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