Electrochromic device and preparation method thereof

Abstract

The invention relates to the technical field of electrochromism, in particular to an electrochromism device and a preparation method thereof.The preparation method of the electrochromism device comprises the steps that a first material is deposited on one side of a first substrate to form a first transparent conductive layer; a second material is deposited on the side, away from the first substrate, of the first transparent conductive layer, and then air thermal oxidation is carried out on the first transparent conductive layer to form the electrochromic layer. A first material is deposited on one side of the second substrate to form a second transparent conductive layer. And an electrolyte layer is formed between the electrochromic layer and the second transparent conductive layer, so that the electrochromic device obtained by the preparation method can realize zoning adjustment of a visible light wave band and a near-infrared light wave band, and has an excellent zoning modulation effect of visible light and infrared light.

Description

Technical Field

[0001] The invention belongs to the technical field of electrochromic technology, and in particular relates to an electrochromic device and a preparation method thereof. Background Art

[0002] Against the backdrop of a rapidly growing world population and industrial modernization, building energy consumption continues to increase, accounting for more than 40% of the world's total energy consumption. Compared with static windows, electrochromic windows are active electrochromic devices that can independently and selectively adjust visible light and near-infrared light to achieve a wide range of solar radiation modulation.

[0003] In 2013, DJ Milliron et al. studied glass nanocrystalline composites based on indium tin oxide (ITO) nanocrystals and amorphous niobium oxide (NbOx). Indium tin oxide nanocrystals modulate near-infrared light through free carrier density and localized surface plasmon resonance (LSPR) absorption, while amorphous niobium oxide modulates visible light through polarization absorption. Since then, some nanocomposites have been shown to have dual-band electrochromic modulation properties, but the preparation process is too complicated. WO3, as a single-component material, has special tunneling and excellent current carrying capacity. Studies have shown that oxygen vacancy WO prepared by liquid phase method 3-x Nanocrystals or nanowires can simultaneously achieve controllable regulation of visible light and near-infrared light, which has opened up a research boom in single-component dual-band electrochromic materials. Relevant 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. At present, the synthesis and preparation of the electrochromic layer of electrochromic devices mainly adopt chemical synthesis methods such as liquid phase method, chemical bath deposition method, electrochemical deposition method, spray pyrolysis method, sol-gel method, hydrothermal method and solvent thermal synthesis method, so that the electrochromic devices finally prepared usually have low full-band optical contrast and poor partition modulation effect of visible light and infrared light, which seriously hinders the development and application of electrochromic devices. Summary of the invention

[0004] In view of this, the present invention aims to provide an electrochromic device and a preparation method thereof. The electrochromic device obtained by the preparation method can achieve zoned regulation of the visible light band and the near-infrared light band, and has excellent zoned modulation effect of visible light and infrared light.

[0005] To achieve the above object, the technical solution created by the present invention is implemented as follows: A method for preparing an electrochromic device, comprising: Depositing a first material on one side of the first substrate to form a first transparent conductive layer; Firstly, a second material is deposited on a side of the first transparent conductive layer away from the first substrate, and then subjected to air thermal oxidation to form an electrochromic layer; Depositing the first material on one side of the second substrate to form a second transparent conductive layer; An electrolyte layer is formed between the electrochromic layer and the second transparent conductive layer.

[0006] Further, depositing a first material on one side of the first substrate to form a first transparent conductive layer includes: The first material and the first substrate are placed in an electron beam coating device, the interior of the electron beam coating device is evacuated until the pressure inside the device reaches a first set pressure, and the internal temperature of the electron beam coating device is increased until the temperature of the first substrate reaches a first set temperature; the first material is deposited on one side of the first substrate by electron beam evaporation to form a first transparent conductive layer; wherein the first set pressure is 2.5×10 -3 Pa~2.8×10 -3 Pa; the first set temperature is 180℃~200℃.

[0007] Furthermore, a first material is deposited on one side of the first substrate by electron beam evaporation to form a first transparent conductive layer, comprising: The electron beam is directed onto the first material, and the electron beam is adjusted so that the rate of evaporating the first material is maintained at a first set rate, and the evaporation is continued 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 minutes.

[0008] Furthermore, the second material is first deposited on a side of the first transparent conductive layer away from the first substrate, comprising: The second material and the first substrate on which the first transparent conductive layer is deposited are placed in an electron beam coating device, and the interior of the electron beam coating device is evacuated until the pressure inside the device reaches a second set pressure. At room temperature, the second material is deposited on the side of the first transparent conductive layer away from the first substrate by electron beam evaporation to form a first crystalline electrochromic layer; wherein the second set pressure is 2.5×10 -3 Pa~2.8×10 -3 Pa.

[0009] Furthermore, a second material is deposited on a side of the first transparent conductive layer away from the first substrate by electron beam evaporation to form a first crystalline electrochromic layer, comprising: The electron beam is directed onto 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 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 minutes.

[0010] Further, the electrochromic layer is formed by air thermal oxidation, including: 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 the air thermal oxidation, they are taken out and cooled to room temperature to form a second crystalline electrochromic layer; wherein the second set temperature is 400°C~450°C; and the third set time is 30min~1000min.

[0011] Furthermore, an electrolyte layer is formed between the electrochromic layer and the second transparent conductive layer, comprising: A reserved space is left between the electrochromic layer and the second transparent conductive layer, and the two are connected by curing; An electrolyte solution is prepared, injected into the reserved space and sealed to form an electrolyte layer.

[0012] Further, preparing the electrolyte solution comprises: The third material is dissolved in the solvent, and stirred at a third set temperature and a set stirring speed for a fourth set time, so that the third material is completely dissolved in the solvent to form an electrolyte solution.

[0013] Further, the first material is cerium-doped indium oxide; and / or The second material is tungsten trioxide.

[0014] An electrochromic device is prepared by using the above-mentioned method for preparing the electrochromic device.

[0015] Compared with the prior art, the invention can achieve the following beneficial effects: the preparation method of the electrochromic device provided by the embodiment of the invention, the first transparent conductive layer prepared by the method can effectively improve the optical transmittance of infrared light, and can expand the range of light modulation to 2500nm. The electrochromic layer prepared by the method uses electron beam thermal evaporation to deposit the second material on the side of the first transparent conductive layer away from the first substrate to form a first crystalline electrochromic layer, so that the prepared electrochromic layer is more uniform and firm. Then, 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, so that the first crystalline electrochromic layer is changed into the second crystalline electrochromic layer, and the air thermal oxidation method is adopted to make the method for preparing the second crystalline electrochromic layer simpler. The first substrate, the first transparent conductive layer and the electrochromic layer formed by the preparation method form a layer group. The obtained layer group has an optical contrast of 76.3% at a wavelength of 680nm in the visible light band and an optical contrast of 95% at a wavelength of 1300nm in the near-infrared light band, surpassing the current maximum infrared optical contrast. At the same time, the prepared electrochromic device can realize three independent photothermal control modes of "bright", "cold" and "dark" under different potential control, and can realize the partition adjustment of the visible light band and the near-infrared light band, with excellent visible light and infrared light partition modulation effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The drawings constituting part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments and descriptions of the present invention are used to explain the present invention and do not constitute an improper limitation on the present invention. In the drawings: Figure 1 A schematic diagram of an electrochromic device according to an embodiment of the present invention; Figure 2 A flow chart of a method for preparing an electrochromic device according to an embodiment of the present invention; Figure 3 A TEM image of the electrochromic layer of the electrochromic device described in the embodiment of the present invention; 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 according to the embodiment of the present invention under visible light and near-infrared light; Figure 5 A schematic diagram of the coloring efficiency value of the electrochromic layer of the electrochromic device according to the embodiment of the present invention; Figure 6A schematic diagram showing the comparison of transmittance of the layer group of the electrochromic device according to the embodiment of the present invention and the layer group of the comparative example under different potential control; Figure 7 A further flow chart of the method for preparing the electrochromic device described in the embodiment of the present invention; Figure 8 This is a graph showing the dimming and heat regulation capabilities test results of the electrochromic device described in the embodiment of the present invention under different light and heat regulation modes.

[0017] Description of reference numerals: 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

[0018] In order to make the purpose, technical scheme and advantages of the invention clearer, the invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the invention and do not constitute a limitation to the invention. Similar components in different embodiments use associated similar component numbers. In the following embodiments, many detailed descriptions are to enable the invention to be better understood. However, those skilled in the art can easily recognize that some of the features can be omitted in different situations, or can be replaced by other components, materials, and methods. In some cases, some operations related to the invention are not shown or described in the specification, in order to avoid the core part of the invention being overwhelmed by too much description, and for those skilled in the art, it is not necessary to describe these related operations in detail, and they can fully understand the related operations according to the description in the specification and the general technical knowledge in the art.

[0019] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other to form various implementation methods. At the same time, the steps or actions in the method description can also be interchanged or adjusted in a manner that is obvious to those skilled in the art. Therefore, the various sequences in the specification and the drawings are only for the purpose of clearly describing a certain embodiment and are not meant to be a necessary sequence, unless otherwise specified that a certain sequence must be followed.

[0020] In the description of the invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", etc., indicating the orientation or position relationship, are based on the orientation or position relationship shown in the drawings, and are only for the convenience of describing the invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the invention. In addition, the terms "first", "second", etc. are only used 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 as "first", "second", etc. may explicitly or implicitly include one or more of the features. In the description of the invention, unless otherwise specified, the meaning of "multiple" is two or more.

[0021] In the description of the invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installation", "connection" and "connection" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the invention can be understood according to specific circumstances.

[0022] The present invention will be described in detail below with reference to the accompanying drawings and in combination with embodiments.

[0023] See also Figure 1 and Figure 2 As shown, the method for preparing the electrochromic device 10 includes steps S101 to S104. The electrochromic device 10 may be an electrochromic window.

[0024] In step S101, a first material is deposited on one side of the first substrate 11 to form a first transparent conductive layer 12. The first material may be cerium-doped indium oxide (ICO), which includes cerium oxide (CeO2) and indium oxide (In2O3), wherein the molar ratio of cerium oxide to cerium-doped indium oxide is 10 mol% to 20 mol%. The material of the first substrate 11 may be glass, such as K9 glass, quartz glass, etc. The thickness of the formed first transparent conductive layer 12 may be greater than or equal to 100 nm. The thickness of the first transparent conductive layer 12 may be 300 nm to 320 nm.

[0025] In one embodiment, step S101 includes: placing the first material and the first substrate 11 in an electron beam coating device, and evacuating the interior of the electron beam coating device until the pressure inside the device reaches a first set pressure. The first set pressure is 2.5×10 -3 Pa~2.8×10 -3 Pa. And the internal temperature of the electron beam coating device is increased until the temperature of the first substrate 11 reaches the first set temperature. The first set temperature is 180°C~200°C. The interior of the electron beam coating device can be evacuated, and after the internal pressure of the electron beam coating device reaches 8Pa, the internal temperature of the electron beam coating device is increased, wherein the evacuation is continued in this process until the internal pressure of the electron beam coating device reaches the first set pressure. The first material is deposited on one side of the first substrate 11 by electron beam evaporation to form a first transparent conductive layer 12.

[0026] In one embodiment, the first transparent conductive layer 12 is formed by electron beam evaporation of the first material on one side of the first substrate 11, including: striking the electron beam on the first material, adjusting the electron beam so that the rate of evaporation of the first material is maintained at a first set rate, and continuing the evaporation for a first set time. The electron beam strikes the first material to form a light spot on the first material, and adjusting the electron beam may refer to adjusting the size and position of the light spot so that the rate of evaporation of the first material is maintained at the first set rate. The first set rate is 0.2nm / s~0.4nm / s. The first set time is greater than or equal to 25 min.

[0027] In this embodiment, cerium-doped indium oxide and the first substrate 11 are placed in an electron beam coating device, and the interior of the electron beam coating device is evacuated. When the pressure inside the electron beam coating device reaches 8 Pa, the internal temperature of the electron beam coating device begins to increase until the temperature of the first substrate 11 reaches 200° C. During this process, the evacuation is continued until the pressure inside the electron beam coating device reaches 2.8×10 -3 Pa. An electron beam is projected onto the cerium-doped indium oxide, and the electron beam is adjusted so that the rate of evaporation of the cerium-doped indium oxide is maintained at 0.2 nm / s, and the evaporation is continued for 25 min, so that the cerium-doped indium oxide is deposited on one side of the first substrate 11 to form a first transparent conductive layer 12, and the thickness of the formed first transparent conductive layer 12 is 300 nm. During the deposition process of the first transparent conductive layer 12, the real-time deposition thickness of the first transparent conductive layer 12 can be determined by continuous detection using a quartz crystal microbalance.

[0028] In step S102, the second material is first deposited on the side of the first transparent conductive layer 12 away from the first substrate 11, and then subjected to air thermal oxidation to form the electrochromic layer 13. The second material is tungsten trioxide (WO3). The electrochromic layer 13 described below is the second crystalline electrochromic layer 13, and its thickness is 100nm~1000nm.

[0029] In one embodiment, the second material is first 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 deposited with the first transparent conductive layer 12 in an electron beam coating device, and evacuating the interior of the electron beam coating device until the pressure inside the device reaches a second set pressure. The interior of the electron beam coating device is evacuated until the pressure inside the device reaches the second set pressure. The second set pressure is 2.5×10 -3 Pa~2.8×10 -3 Pa. At room temperature, the second material is deposited on the side of the first transparent conductive layer 12 away from the first substrate 11 by electron beam evaporation to form a first crystalline electrochromic layer 13 .

[0030] In one embodiment, the second material is deposited on the side of the first transparent conductive layer 12 away from the first substrate 11 by electron beam evaporation to form a first crystalline electrochromic layer 13, including: striking the electron beam on the second material, adjusting the electron beam so that the rate of evaporating the second material is maintained at a second set rate, and continuing the evaporation for a second set time. The electron beam is struck on the second material to form a light spot on the second material, and adjusting the electron beam may refer to adjusting the size and position of the light spot so that the rate of evaporating the second material is maintained at the second set rate. Among them, the second set rate is 0.1nm / s~0.5nm / s. The second set time is greater than or equal to 30min. The thickness of the first crystalline electrochromic layer 13 deposited on the side of the first transparent conductive layer 12 away from the first substrate 11 can be 110nm~1010nm. When the electrochromic material used is WO3, amorphous WO can be obtained after deposition. 3-x The electrochromic layer 13, that is, the first crystalline state is amorphous.

[0031] In one embodiment, air thermal oxidation is then performed to form the electrochromic layer 13, including: at a second set temperature, the first transparent conductive layer 12 and the first substrate 11 deposited with the first crystalline electrochromic layer 13 are heated in an air atmosphere for a third set time to perform air thermal oxidation. A vacuum tube furnace can be selected to increase the temperature inside the vacuum tube furnace to the second set temperature, and then the first transparent conductive layer 12 and the first substrate 11 deposited with the first crystalline electrochromic layer 13 are placed inside the vacuum tube furnace, which can be placed in a high temperature resistant ceramic crucible and then placed at the center of the vacuum tube furnace. Among them, the second set temperature is 400°C~450°C. The third set time is 30min~1000min. After air thermal oxidation, it is taken out and cooled to room temperature to form the second crystalline electrochromic layer 13. The thickness of the second crystalline electrochromic layer 13 after cooling can be changed to 100nm~1000nm. When the electrochromic material used is WO3, after the air thermal oxidation step, the amorphous WO 3-x The electrochromic layer 13 becomes high-purity monoclinic WO 3-x The nanocrystalline electrochromic layer 13, that is, the second crystalline state is a high-purity monoclinic nanocrystal. 3-x The average grain size of nanocrystals is 7nm~10nm.

[0032] In this embodiment, tungsten trioxide powder and the first substrate 11 deposited with the first transparent conductive layer 12 are placed inside the electron beam coating device, and the inside of the electron beam coating device is evacuated to 2.8×10 -3 Pa, and at room temperature, an electron beam is directed onto tungsten trioxide, and the electron beam is adjusted so that the rate of evaporation of tungsten trioxide is maintained at 0.2nm / s, and the evaporation is continued for 30min to form amorphous WO 3-x The temperature inside the vacuum tube furnace is raised until the temperature inside the center 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 electrochromic layer 13 is deposited are placed at the center of the vacuum tube furnace and heated in an air atmosphere for 30 minutes to perform air thermal oxidation. After air thermal oxidation, the substrate is taken out and cooled to room temperature to form a second crystalline electrochromic layer 13. 3-x The electrochromic layer 13 becomes high-purity monoclinic WO 3-x The nanocrystalline electrochromic layer 13 is formed to have a thickness of 400 nm.

[0033] See also Figure 3 As shown, Figure 3FIG. 1 shows a TEM (Transmission Electron Microscope) image of the electrochromic layer 13 prepared by the preparation method of this embodiment. Figure 3 As shown in the left figure (a), the high-purity monoclinic WO 3-x The average grain size of nanocrystals is 10nm. Figure 3 As shown in the right figure (b), high-purity monoclinic WO can be prepared by the preparation method of this embodiment. 3-x The nanocrystalline electrochromic layer 13 has only a monoclinic crystal phase and a lattice constant of 0.42 nm, wherein the lattice constant refers to the distance between two adjacent lattice points in a crystal.

[0034] See also Figure 4 As shown, Figure 4 The schematic diagram shows the average response time of coloring and the average response time of fading of the electrochromic layer 13 prepared by the preparation method of this embodiment under visible light (wavelength range of 380nm~780nm) and near infrared light (wavelength range of 780nm~2500nm). Fading refers to the process in which the electrochromic layer 13 recovers from a certain color to transparent and colorless after applying an appropriate voltage. Coloring refers to the process in which the electrochromic layer 13 presents a certain color after applying an appropriate voltage. Among them, the response time is the time required for the change in transmittance to reach 90%. Figure 4 The horizontal axis is time and the vertical axis is transmittance. Figure 4 The process from 0s to 35s is the coloring process, and the transmittance gradually decreases with the change of time. The process from 35s to 70s is the fading process, and the transmittance gradually increases with the change of time. It can be seen that at a wavelength of 680nm, the average response time of coloring is 24.1s, and the average response time of fading is 16.3s. At a wavelength of 1000nm, the average response time of coloring is 15.9s, and the average response time of fading is 18.5s. The average response time of coloring and the average response time of fading are relatively short. In the related art, the average response time of coloring and the average response time of fading of some electrochromic layers are long, and the average response time of fading is particularly long. For example, amorphous WO prepared by a solution colloid method 3-x The average response time of coloring is 22s, the average response time of fading is 75s, and the average response time of triclinic WO 3-x The average response time of the nanocrystals to fade in the near-infrared region can even reach 105s. It can be seen that the electrochromic layer 13 prepared by the preparation method of this embodiment has a shorter average response time for coloring and a shorter average response time for fading than the electrochromic layer in the related art.

[0035] See also Figure 5 As shown, Figure 5 A schematic diagram showing the coloration efficiency (CE) value of the electrochromic layer 13 prepared by the preparation method of this embodiment is shown. 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. Among them, the higher the coloration efficiency, the stronger the light modulation ability. Figure 5 The horizontal axis is the amount of charge injected per unit area (ΔQ), and the vertical axis is the change in optical density at a fixed wavelength (ΔOD). The coloring efficiency is expressed by the formula: It can be seen that at a wavelength of 680nm, the coloring efficiency value is 110.8cm 2 / C. At a wavelength of 1000nm, the coloring efficiency value is 284.2cm 2 Therefore, the electrochromic layer 13 prepared by the preparation method of this embodiment has a strong light modulation capability in both visible light and near infrared light bands.

[0036] The first substrate 11, the first transparent conductive layer 12 and the electrochromic layer 13 prepared by the above preparation method constitute a layer group 17. A comparative experiment is set up to obtain a layer group of a comparative example. The difference between the preparation method of the comparative experiment and the preparation method of this embodiment is that the electrochromic layer of the layer group of the comparative example is not subjected to air thermal oxidation.

[0037] See also Figure 6 As shown, Figure 6 A schematic diagram showing the transmittance comparison between the layer group 17 prepared by the preparation method of this embodiment and the layer group of the comparative example under different potential control is shown. Figure 7 The horizontal axis is wavelength, and the vertical axis is transmittance. Among them, the left figure (a) is the layer group 17 prepared by the preparation method of this embodiment, and the right figure (b) is the comparative layer group. It can be seen that the layer group 17 prepared by the preparation method of this embodiment can exhibit three photothermal regulation modes in the visible light band and near-infrared light band of 380nm~2500nm under different driving potentials, namely bright mode (visible light and near-infrared light are both highly transmitted), cold mode (visible light is highly transmitted and near-infrared light is blocked), and dark mode (visible light and near-infrared light are blocked). Figure 6In the embodiment shown, the driving potential of the bright mode is 0.8V. The driving potential of the cold mode is -0.3V and -0.4V, and the driving potential of the dark mode is -0.8V. It has an optical contrast of 76.3% at a wavelength of 680nm in the visible light band, and an optical contrast of 95% at a wavelength of 1300nm in the near-infrared light band, that is, the difference in transmittance between the bright mode and the dark mode is as high as 95%, surpassing the current maximum infrared optical contrast, so the optical contrast of visible light and near-infrared light is high. Among them, 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 show three light and heat control modes of bright, cold and dark under different driving potentials. And it can realize the partition adjustment of the visible light band and the near-infrared light band of 380nm~2500nm, with good partition modulation ability, large optical adjustment range, and high optical contrast.

[0038] However, the comparative layer group prepared by the preparation method of the comparative experiment cannot achieve high visible light transmission while blocking near infrared light, that is, it cannot achieve the cold mode in the regulation mode. In addition, the optical contrast of the comparative layer group is relatively lower.

[0039] It can be seen that compared with the comparative layer group, the layer group prepared by the preparation method of this embodiment achieves a significant improvement in the optical contrast in the near-infrared light band, and achieves an improvement in the partitioned modulation capability in the visible light and near-infrared light bands.

[0040] In step S103, the first material is deposited on one side of the second substrate 14 to form a second transparent conductive layer 15. The specific preparation method for forming the second transparent conductive layer 15 on one side of the second substrate 14 is the same as the specific preparation method for forming the first transparent conductive layer 12 on the first substrate 11. The first substrate 11 and the second substrate 14 have the same structure, thickness, and material. The first transparent conductive layer 12 and the second transparent conductive layer 15 have the same structure, thickness, and material.

[0041] In step S104, an 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 ions are lithium ions. The thickness of the electrolyte layer 16 can be 1 mm to 2 mm.

[0042] See also Figure 7 As shown, in one embodiment, step S104 includes steps S1041 to S1042.

[0043] In step S1041, a reserved space is left between the electrochromic layer 13 and the second transparent conductive layer 15, and the two are cured and connected. The edge between the electrochromic layer 13 and the second transparent conductive layer 15 can be bonded by ultraviolet curing glue. The reserved space can be formed by enclosing the electrochromic layer 13, the second transparent conductive layer 15 and the ultraviolet curing glue.

[0044] In step S1042, an electrolyte solution is prepared, injected into the reserved space and sealed to form an electrolyte layer 16. The electrolyte solution can be injected into the reserved space through a glue injection hole connecting the reserved space with the outside by a pipette gun, and the glue injection hole can be sealed with ultraviolet curing glue.

[0045] In one embodiment, preparing an electrolyte solution includes: dissolving a third material in a solvent, and stirring at a third set temperature and a set stirring speed for a fourth set time, so that the third material is completely dissolved in the solvent to form an electrolyte solution. The stirring can be performed by a magnetic stirrer. Among them, the third material can be lithium perchlorate (LiClO4), and the solvent can be a polypropylene carbonate (PC, Propylene Carbonate) solvent. The configuration concentration of the electrolyte solution is 0.9mol / L~1mol / L. Lithium perchlorate can be weighed and dissolved in a corresponding volume of polypropylene carbonate solvent, wherein the corresponding volume of polypropylene carbonate solvent refers to when the configuration concentration of the electrolyte solution is 1mol / L, 1.06392g of lithium perchlorate powder corresponds to 10ml of polypropylene carbonate solvent; 2.12784g of lithium perchlorate powder corresponds to 20ml of polypropylene carbonate solvent, and so on. A magnetic stirrer is placed in the solvent, placed on a magnetic stirrer, and stirred by the magnetic stirrer. Among them, the third set temperature is 80℃~100℃. The stirring speed is set to 600 r / min to 800 r / min. The fourth setting time is 2 h to 3 h, so that the third material is completely dissolved in the solvent to form a liquid electrolyte solution.

[0046] 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 bonded by ultraviolet curing glue. 1.06392g of lithium perchlorate is dissolved in 10 ml of polypropylene carbonate solvent, a magnetic stirrer is placed in the solvent, and the solution is placed on a magnetic stirrer, and stirred at a temperature of 80°C and a stirring speed of 800r / min for 2h to form an electrolyte solution. The electrolyte solution is injected into the reserved space, the reserved space is filled, and the ultraviolet curing glue is used to seal it, and the electrochromic device 10 is obtained after complete curing.

[0047] See also Figure 8 As shown, Figure 8The figure shows the test results of the dimming and heat regulation capabilities of the electrochromic device 10 prepared by the preparation method of this embodiment in different light and heat regulation modes. Figure 8 The upper figure (a) in the figure is a diagram of the dimming capability of the electrochromic device 10 under different light-heat control modes. As can be seen from the figure, the electrochromic device 10 can present a certain color after applying an appropriate voltage (such as -6V). It can also restore from a certain color to transparent and colorless after applying an appropriate voltage (such as 6V). Figure 8 The lower figure (b) in the figure is a diagram of the heat regulation capability of the electrochromic device 10 in different light-heat regulation modes. As can be seen from the figure, the temperature can be effectively reduced by 16°C in the cold mode and by 18.5°C in the dark mode. Figure 8 It can be known that the electrochromic device 10 can realize three light-heat control modes, namely, bright mode, cold mode and dark mode, under different driving potentials, and can achieve the effect of dynamic light and heat regulation.

[0048] The present invention provides a method for preparing an electrochromic device 10 provided in an embodiment of the invention. The first transparent conductive layer 12 prepared by the method can effectively improve the optical transmittance of infrared light and expand the range of light modulation to 2500nm. The electrochromic layer 13 prepared by the method uses electron beam thermal evaporation to deposit the second material on the side of the first transparent conductive layer 12 away from the first substrate 11 to form a first crystalline electrochromic layer 13, so that the prepared electrochromic layer 13 is more uniform and firm. Then, the first transparent conductive layer 12 and the first substrate 11 deposited with the first crystalline electrochromic layer 13 are subjected to air thermal oxidation, so that the size, microstructure and crystal system of the first crystalline electrochromic layer 13 can be adjusted, so that the first crystalline electrochromic layer 13 is changed into the second crystalline electrochromic layer 13, and the air thermal oxidation method is adopted to make the method for preparing the second crystalline electrochromic layer 13 simpler. The first substrate 11, the first transparent conductive layer 12 and the electrochromic layer 13 prepared by the preparation method form a layer group 17. The obtained layer group 17 has an optical contrast of 76.3% at a wavelength of 680nm in the visible light band and an optical contrast of 95% at a wavelength of 1300nm in the near-infrared light band, which exceeds the current maximum infrared optical contrast. At the same time, the prepared electrochromic device 10 can realize three independent photothermal control modes of "bright", "cold" and "dark" under different potential control, and 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.

[0049] See again Figure 1As shown, the present invention also provides an electrochromic device 10, which is prepared according to the preparation method of the electrochromic device 10 as described above. The electrochromic device 10 includes 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 stacked in sequence.

[0050] It should be understood that the various forms of processes shown above can be used to reorder, add or delete steps. For example, the steps described in the disclosure of the present invention can be performed in parallel, sequentially or in different orders, as long as the desired results of the technical solution disclosed in the present invention can be achieved, and this document does not limit this.

[0051] The above specific implementations do not constitute a limitation on the protection scope of the present invention. It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and substitutions can be made according to design requirements and other factors. Any modification, equivalent substitution and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing an electrochromic device, characterized in that: include: Depositing a first material on one side of the first substrate to form a first transparent conductive layer; Firstly, a second material is deposited on the side of the first transparent conductive layer facing away from the first substrate, and then subjected to air thermal oxidation to form an electrochromic layer; Depositing the first material on one side of the 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 an electrochromic device according to claim 1, characterized in that: The step of depositing the first material on one side of the first substrate to form a first transparent conductive layer includes: The first material and the first substrate are placed in an electron beam coating device, the interior of the electron beam coating device is evacuated until the pressure inside the device reaches a first set pressure, and the internal temperature of the electron beam coating device is increased until the temperature of the first substrate reaches a first set temperature; the first material is deposited on one side of the first substrate by electron beam evaporation to form the first transparent conductive layer; wherein the first set pressure is 2.5×10 -3 Pa~2.8×10 -3 Pa; the first set temperature is 180℃~200℃.

3. The method for preparing an electrochromic device according to claim 2, characterized in that: The step of forming the first transparent conductive layer by electron beam evaporating the first material on one side of the first substrate includes: An electron beam is directed onto the first material, and the electron beam is adjusted so that the rate of evaporating the first material is maintained at a first set rate, and the evaporation is continued 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.

4. The method for preparing an electrochromic device according to claim 1, characterized in that: The step of first depositing the second material on a side of the first transparent conductive layer facing away from the first substrate comprises: The second material and the first substrate on which the first transparent conductive layer is deposited are placed in an electron beam coating device, the interior of the electron beam coating device is evacuated until the pressure inside the device reaches a second set pressure, and the second material is deposited on the side of the first transparent conductive layer away from the first substrate by electron beam evaporation at room temperature to form a first crystalline electrochromic layer; wherein the second set pressure is 2.5×10 -3 Pa~2.8×10 -3 Pa.

5. The method for preparing an electrochromic device according to claim 4, characterized in that: The step of depositing the second material on a side of the first transparent conductive layer away from the first substrate by electron beam evaporation to form a first crystalline electrochromic layer comprises: The electron beam is directed onto 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 is continued for a second set time; wherein the second set rate is 0.1nm / s~0.5nm / s; and the second set time is greater than or equal to 30min.

6. The method for preparing an electrochromic device according to claim 4, characterized in that: The method further performs air thermal oxidation to form an electrochromic layer, comprising: 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 the air thermal oxidation, they are taken out and cooled to room temperature to form a second crystalline electrochromic layer; wherein the second set temperature is 400°C~450°C; and the third set time is 30min~1000min.

7. The method for preparing an electrochromic device according to claim 1, characterized in that: The electrolyte layer is formed between the electrochromic layer and the second transparent conductive layer, comprising: A reserved space is left between the electrochromic layer and the second transparent conductive layer, and the two are connected by curing; An electrolyte solution is prepared, and the electrolyte solution is injected into the reserved space and sealed to form the electrolyte layer.

8. The method for preparing an electrochromic device according to claim 7, characterized in that: The preparation of the electrolyte solution comprises: The third material is dissolved in a solvent, and stirred at a third set temperature and a set stirring speed for a fourth set time, so that the third material is completely dissolved in the solvent to form the electrolyte solution.

9. The method for preparing an 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.

10. An electrochromic device, characterized in that: The electrochromic device is prepared by the preparation method of the electrochromic device according to any one of claims 1 to 9.

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