Photothermal control device and preparation method thereof

Abstract

The present invention relates to the field of electrochromism, and in particular to a photothermal control device and a method for preparing the same. The method for preparing the photothermal control device comprises: forming a first conductive layer on a first substrate by electron beam thermal evaporation. Forming a photothermal control layer on the side of the first conductive layer facing away from the first substrate by first performing electron beam thermal evaporation and then annealing in a heating device to form a first layer group. Forming a second conductive layer on a second substrate by electron beam thermal evaporation to form a second layer group. An electrolyte layer is formed between the first layer group and the second layer group. The photothermal control device obtained by the above-mentioned preparation method can simultaneously control visible light, near-infrared light, medium-wave and long-wave infrared radiation.

Description

Technical Field

[0001] The present invention belongs to the field of electrochromism, and in particular relates to a photothermal control device and a preparation method thereof. Background Art

[0002] Sunlight mainly consists of visible light and near-infrared light containing a large amount of heat. Photothermal control devices can selectively and reversibly control the amount of visible light and near-infrared thermal radiation entering buildings and indoor spaces when voltage is applied. This can significantly reduce building energy consumption and improve living comfort.

[0003] In order to achieve independent control of near-infrared and visible light, people have developed a large number of electrochromic photothermal control materials. In 2013, the Milliron group pioneered the research on electrochromic photothermal control technology by doping ITO nanocrystals into amorphous niobium oxide (NbOx) to prepare a nanocomposite film, which used visible light selective components and near-infrared light regulation components intentionally integrated in different potential windows to form a two-component composite material. Two-component electrochromic photothermal control nanocomposites usually require precise and complex design and manufacturing to form an interconnected open network at the nanoscale to promote the contact of the electrolyte with the near-infrared and visible light modulation components. Therefore, the use of single-component materials can accelerate the development of electrochromic photothermal control materials. WO3 is the most widely studied single-component electrochromic photothermal control material, which has good environmental protection properties, mature preparation technology and abundant sources of raw materials. However, it is generally necessary to make WO containing oxygen vacancies. 3-x Only nanostructured WO3 can achieve dynamic control in the visible and near-infrared. Large-scale, controllable production of highly stable and uniform nanocomposites and nanostructured films remains a challenge. Currently, the fabrication process for photothermal control devices is complex, and the resulting devices are unable to simultaneously control visible, near-infrared, mid-wave, and long-wave infrared radiation. Summary of the Invention

[0004] In view of this, the present invention aims to provide a photothermal control device and a preparation method thereof. The photothermal control device obtained by the preparation method can simultaneously control visible light, near-infrared light, medium-wave and long-wave infrared radiation.

[0005] To achieve the above object, the technical solution created by the present invention is implemented as follows:

[0006] A method for preparing a photothermal control device, comprising:

[0007] forming a first conductive layer on the first substrate by electron beam thermal evaporation;

[0008] forming a photothermal regulation layer on a side of the first conductive layer facing away from the first substrate by first performing electron beam thermal evaporation and then annealing in a heating device to form a first layer group;

[0009] forming a second conductive layer on the second substrate by electron beam thermal evaporation to form a second layer group; and

[0010] An electrolyte layer is formed between the first layer group and the second layer group.

[0011] Furthermore, forming a first conductive layer on the first substrate by electron beam thermal evaporation includes:

[0012] Placing the first substrate and the first material in a receiving chamber of an electron beam coating machine, evacuating the receiving chamber to a first set pressure, and heating the receiving chamber during the evacuation process to raise the temperature of the receiving chamber to a first set temperature. At the first set temperature, continuously oxygenating the receiving chamber at a set oxygen filling amount;

[0013] The electron beam is directed onto the first material for a first set time, so that the first material is evaporated and formed on the surface to be coated of the first substrate.

[0014] Furthermore, the first set pressure is 1×10 -3 Pa~5×10 -3 Pa; and / or

[0015] The first set temperature is 280°C to 350°C; and / or

[0016] Set the oxygen filling rate to 10 sccm~30 sccm; and / or

[0017] The first setting time is 2min~5min.

[0018] Furthermore, a photothermal regulation layer is formed on the side of the first conductive layer facing away from the first substrate by first performing electron beam thermal evaporation and then annealing in a heating device to prepare a first layer group, including:

[0019] Using the first conductive layer and the first substrate as substrates, placing the substrate and the second material in a receiving chamber of an electron beam coating machine, and evacuating the receiving chamber to a second set pressure at room temperature;

[0020] The electron beam is directed onto the second material for a second set time, so that the second material evaporates and forms on the substrate.

[0021] Furthermore, a photothermal regulation layer is formed on the side of the first conductive layer facing away from the first substrate by first performing electron beam thermal evaporation and then annealing in a heating device to form a first layer group, further comprising:

[0022] heating the interior of the heating device until it reaches a second set temperature;

[0023] The substrate on which the second material is deposited after electron beam thermal evaporation is placed inside a heating device, heated at a second set temperature and in an air environment for a third set time, taken out, and cooled to room temperature.

[0024] Furthermore, an electrolyte layer is formed between the first layer group and the second layer group, comprising:

[0025] Connecting the first layer group and the second layer group by curing, and leaving a reserved space between the first layer group and the second layer group; and

[0026] An electrolyte solution is prepared, injected into the reserved space, and sealed.

[0027] Furthermore, preparing an electrolyte solution comprises:

[0028] The third material is dissolved in a solvent and stirred by a stirrer; wherein the stirrer stirs at a set stirring speed at a third set temperature for a fourth set time to completely dissolve the third material in the solvent to form an electrolyte solution.

[0029] Furthermore, the third set temperature is 80° C.; and / or

[0030] Set the stirring speed to 400 r / min~1200 r / min; and / or

[0031] The fourth setting time is 0.5h~5h; and / or

[0032] The third material is lithium perchlorate; and / or

[0033] The solvent is polypropylene carbonate solvent.

[0034] A photothermal regulation device is prepared using the preparation method described above, and the photothermal regulation device includes a first substrate, a first conductive layer, a photothermal regulation layer, an electrolyte layer, a second conductive layer, and a second substrate stacked in sequence.

[0035] Furthermore, the first substrate and the second substrate are made of glass; and / or

[0036] The first conductive layer and the second conductive layer are made of indium tin oxide; and / or

[0037] The material of the photothermal regulation layer is tungsten trioxide; and / or

[0038] The material of the electrolyte layer is inorganic ions; and / or

[0039] The first conductive layer and the second conductive layer are polycrystalline structures; and / or

[0040] The photothermal regulation layer is an amorphous / nanocrystalline heterojunction structure; and / or

[0041] The thickness of the first conductive layer and the second conductive layer is 50 nm to 100 nm; and / or

[0042] The thickness of the photothermal regulation layer is greater than or equal to 100 nm.

[0043] Compared with existing technologies, the present invention achieves the following beneficial effects: The method for preparing the photothermal control device described in the present invention is simple, and the resulting photothermal control device not only independently and dynamically modulates visible and near-infrared light with excellent selectivity, exhibiting three photothermal control modes: bright, cold, and dark, under different driving potentials, but also effectively performs dynamic radiative cooling of medium-wave and long-wave infrared radiation, with high emissivity regulation capability, thereby significantly reducing indoor temperature and the surface temperature of hot targets. It can perform combined modulation of visible light, solar radiation, and medium-wave and long-wave infrared radiation, achieving excellent modulation effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The accompanying drawings, which constitute part of the present invention, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0045] Figure 1 A schematic diagram of a photothermal control device according to an embodiment of the present invention;

[0046] Figure 2 A flow chart of a method for preparing a photothermal control device according to an embodiment of the present invention;

[0047] Figure 3 A further flow chart of the method for preparing the photothermal regulation device according to an embodiment of the present invention;

[0048] Figure 4 A schematic diagram comparing the transmittance of the first conductive layer according to an embodiment of the present invention and a conventional conductive layer manufactured on the market using a conventional manufacturing method;

[0049] Figure 5 A further flow chart of the method for preparing the photothermal regulation device according to an embodiment of the present invention;

[0050] Figure 6 TEM image of the photothermal regulation layer described in the embodiment of the present invention;

[0051] Figure 7 A schematic diagram of the charge retention of the photothermal regulation layer according to an embodiment of the present invention during cycling under a set cycle;

[0052] Figure 8 Schematic diagram of the transmittance of the photothermal regulation layer in the visible light region of 380nm~2500nm and the near-infrared light region according to an embodiment of the present invention;

[0053] Figure 9 The transmittance of the photothermal regulation layer described in the embodiment of the present invention in the visible light region of 380nm~2500nm and the near-infrared light region, as well as the emissivity spectrum in the medium-wave and long-wave infrared region of 4μm~25μm;

[0054] Figure 10 Transmittance of the comparative photothermal regulation layer prepared by the preparation method for comparison experiment in the visible light region of 380nm~2500nm and the near-infrared light region, as well as the emissivity spectrum in the medium-wave and long-wave infrared region of 4μm~25μm;

[0055] Figure 11 A further flow chart of the method for preparing the photothermal regulation device according to an embodiment of the present invention;

[0056] Figure 12 This is a graph showing the test results of the dimming and heat regulation capabilities of the photothermal regulation device described in an embodiment of the present invention under different photothermal regulation modes.

[0057] Description of reference numerals:

[0058] Photothermal regulation device 10; first substrate 11; first conductive layer 12; photothermal regulation layer 13; first layer group 14; second substrate 15; second conductive layer 16; second layer group 17; electrolyte layer 18. DETAILED DESCRIPTION

[0059] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present 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 present invention and do not constitute a limitation to the present invention. Similar elements in different embodiments use associated similar element numbers. In the following embodiments, many detailed descriptions are intended to enable the present 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 elements, materials, or methods. In some cases, some operations related to the present invention are not shown or described in the specification. This is to avoid the core part of the present invention being overwhelmed by too much description. For those skilled in the art, it is not necessary to describe these related operations in detail. They can fully understand the related operations based on the description in the specification and the general technical knowledge in the art.

[0060] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments of the present invention 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 orders in the description and the drawings are only for the purpose of clearly describing a certain embodiment and are not intended to be a required order, unless otherwise specified that a certain order must be followed.

[0061] In the description of the present 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" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present 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 present 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 the indicated technical features. Therefore, features defined as "first", "second", etc. may explicitly or implicitly include one or more of the features. In the description of the present invention, unless otherwise specified, "multiple" means two or more.

[0062] In the description of the present invention, it should be noted that, unless otherwise expressly specified or limited, the terms "installed," "connected," and "connected" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to mechanical connections or electrical connections; they can refer to direct connections or indirect connections through an intermediate medium; and they can refer to internal connections between two components. Those skilled in the art can understand the specific meanings of the above terms in the present invention based on specific circumstances.

[0063] The present invention will be described in detail below with reference to the accompanying drawings and in combination with embodiments.

[0064] The present invention provides a method for preparing a photothermal control device. Figure 1 and Figure 2 As shown, the method for preparing the photothermal regulation device 10 includes steps S101 to S104.

[0065] In step S101, a first conductive layer 12 is formed on a first substrate 11 by electron beam thermal evaporation. The first substrate 11 may be made of glass or polyimide. The formed first conductive layer 12 may have a polycrystalline structure and a thickness of 50 nm to 100 nm.

[0066] See also Figure 1 and Figure 3 As shown, in one embodiment, step S101 includes steps S201-S202.

[0067] In step S201, the first substrate 11 and the first material are placed in the receiving chamber of the electron beam coating machine, and the receiving chamber is evacuated to a first set pressure. That is, the receiving chamber is evacuated until the pressure in the receiving chamber reaches the first set pressure. The first set pressure is 1×10 -3 Pa~5×10 -3 Pa. During the vacuuming process, the interior of the receiving chamber is heated to raise the temperature of the receiving chamber to a first set temperature. The first set temperature is 280°C to 350°C. The receiving chamber can be vacuumed, and after the pressure in the receiving chamber reaches 8 Pa, the receiving chamber is heated. At the first set temperature, oxygen is continuously added to the receiving chamber at a set oxygen filling amount. The set oxygen filling amount is 10 sccm to 30 sccm. The first material can be indium tin oxide (ITO). Continuously adding oxygen to the receiving chamber at a set oxygen filling amount can prevent the indium tin oxide from losing oxygen, so that the indium tin oxide can have better resistance and transmittance.

[0068] In one embodiment, before placing the first substrate 11 and the first material in the receiving chamber of the electron beam coating machine, the preparation method may further include: wrapping a high-temperature tape on the outer surface of the first substrate 11 except the surface to be coated of the first substrate 11.

[0069] In step S202, an electron beam is directed onto the first material for a first set time, so that the first material evaporates and is deposited on the surface to be coated of the first substrate 11. The first set time is 2 minutes to 5 minutes.

[0070] In one embodiment, step S202 includes: directing an electron beam onto the first material to form a spot, increasing the electron beam current until it reaches a first set value. The first set value is 7 mA to 15 mA. The size and position of the spot are adjusted to maintain the rate of evaporating the first material at the first set rate. The first set rate is 1 Å / s to 4 Å / s. Setting the oxygen level in this manner matches the rate of evaporating the first material, thereby changing the mobility and carrier concentration of the first conductive layer 12 and improving the transmittance of infrared light.

[0071] In this embodiment, a glass with a thickness of 1 mm is selected as the first substrate 11. The first substrate 11 and indium tin oxide are placed in the receiving chamber of the electron beam coating machine, and the receiving chamber is vacuumed to 3×10 -3 Pa, and the chamber is heated to 310°C. Oxygen is continuously introduced into the chamber at 15 sccm (15 cubic centimeters per minute) at 310°C. An electron beam is directed onto the indium tin oxide to form a spot. The electron beam current is increased to 8 mA and maintained for 4 minutes. The size and position of the spot are adjusted to maintain an indium tin oxide evaporation rate of 3.5 Å / s, causing the indium tin oxide to evaporate and deposit on the surface to be coated on the first substrate 11, thereby forming the first conductive layer 12.

[0072] See also Figure 4 As shown, Figure 4 A schematic diagram comparing the transmittance of the first conductive layer 12 prepared by the preparation method of this embodiment and the conventional conductive layer prepared by the conventional preparation method on the market is shown. Figure 4 The horizontal axis of the coordinate system is wavelength, and the vertical axis is transmittance. It can be seen that by forming the first conductive layer 12 on the first substrate 11 using the preparation method of this embodiment, a broadband transparent conductive layer can be prepared. The first conductive layer 12 can have an average initial transmittance of 84.2% in the visible light region and near-infrared light region of 380nm~2500nm, and the contrast with the initial transmittance of the traditional conductive layer can be as high as 66.5%@2330 nm. And the prepared first conductive layer 12 can maintain good conductivity while significantly improving the near-infrared light transmittance, and its surface resistance is 100Ω / □. At the same time, the average emissivity in the medium-wave infrared of 4μm~8μm can reach 0.77, and the average emissivity in the long-wave infrared of 8μm~25μm can reach 0.52.

[0073] In step S102, a photothermal regulation layer 13 is formed on the side of the first conductive layer 12 facing away from the first substrate 11 by first performing electron beam thermal evaporation followed by annealing in a heating device, thereby forming a first layer group 14. The first layer group 14 includes the first substrate 11, the first conductive layer 12, and the photothermal regulation layer 13. The formed photothermal regulation layer 13 can have an amorphous / nanocrystalline heterojunction structure with a thickness greater than or equal to 100 nm.

[0074] See also Figure 5 As shown, in one embodiment, step S102 includes steps S301-S302.

[0075] In step S301, the first conductive layer 12 and the first substrate 11 are used as substrates, and the substrate and the second material are placed in the receiving chamber of the electron beam coating machine. The receiving chamber is evacuated to a second set pressure at room temperature. That is, the receiving chamber is evacuated at room temperature until the pressure in the receiving chamber reaches the second set pressure. The second set pressure is 1×10 - 3 Pa~5×10 -3 Pa.

[0076] In one embodiment, before placing the substrate and the second material in the accommodating chamber of the electron beam coating machine, the preparation method may further include: wrapping a high-temperature tape on the outer surface of the substrate except for the side of the first conductive layer 12 facing away from the first substrate 11 .

[0077] In step S302, an electron beam is directed onto a second material for a second set time to evaporate the second material and deposit it on the substrate. The second material may be tungsten trioxide (WO3), and the second set time is greater than or equal to 10 minutes.

[0078] In one embodiment, step S302 further includes: directing the electron beam onto the second material to form a spot, increasing the electron beam current until it reaches a second set value. The second set value is 7 mA to 15 mA. The size and position of the spot are adjusted to maintain the deposition rate of the second material at the second set rate. The second set rate is 1 Å / s to 5 Å / s.

[0079] In one embodiment, step S102 further includes steps S303 - S304 .

[0080] In step S303, the interior of the heating device is heated until it reaches a second set temperature. The heating device may be a vacuum tube furnace, which has an air atmosphere rather than a vacuum atmosphere. The interior of the heating device may be heated to the second set temperature, which may be between 310°C and 400°C.

[0081] In step S304, the substrate on which the second material is deposited after electron beam thermal evaporation is placed inside a heating device, and is taken out after being heated for a third set time at a second set temperature and in an air environment, and is cooled to room temperature. The third set time is 15 minutes to 1000 minutes. The interior of the heating device is in an air atmosphere, and the substrate on which the second material is deposited can be placed on a ceramic supporting structure and sent into the interior of the heating device, and taken out after being heated for a third set time in an air environment. After being taken out, it can be cooled in an indoor environment to room temperature. The formed photothermal regulation layer 13 can realize three photothermal regulation modes of bright, cold, and dark in the visible light band and near-infrared light band of 380nm to 2500nm, and has good optical contrast, response time, stability, and memory effect performance, and can perform effective dynamic radiation cooling in the mid- and far-infrared band of 4μm to 25μm.

[0082] In this embodiment, the first conductive layer 12 and the first substrate 11 prepared by the above preparation method are used as substrates. The substrate and tungsten trioxide are placed in the receiving chamber of the electron beam coating machine, and the receiving chamber is vacuumed to 3×10 -3 Pa. An electron beam was directed onto the tungsten trioxide to form a spot. The electron beam current was increased to 8 mA and maintained for 30 minutes. The size and position of the spot were adjusted to maintain the tungsten trioxide evaporation rate at 2 Å / s. This allowed the tungsten trioxide to evaporate and deposit on the substrate, forming a 400 nm thick tungsten trioxide film.

[0083] The interior of the heating device is heated to 400° C. The substrate on which the tungsten trioxide thin film is deposited after electron beam thermal evaporation is placed inside the heating device and heated at 400° C. in an air environment for 30 minutes. The substrate is then removed and cooled to room temperature, thereby forming the photothermal regulation layer 13.

[0084] See also Figure 6 As shown, Figure 6 A TEM (Transmission Electron Microscope) image of the photothermal control layer 13 prepared using the preparation method of this embodiment is shown. By using electron beam thermal evaporation followed by annealing in a heating device to form the photothermal control layer 13, a large number of amorphous / nanocrystalline (cubic phase) heterointerfaces can be obtained, thereby forming an ultra-wideband electrochromic photothermal control layer having an amorphous / nanocrystalline heterojunction structure. The amorphous / nanocrystalline heterojunction structure has a large number of amorphous / nanocrystalline (cubic phase) heterointerfaces.

[0085] See also Figure 7 As shown, Figure 7The schematic diagram shows the charge retention of the photothermal control layer 13 formed by the preparation method of this embodiment under a set cycle. The horizontal axis is the number of cycles, and the vertical axis is the normalized charge retention. The set cycle is to maintain a potential of -0.3 V for 15 seconds and then maintain a potential of +0.6 V for 20 seconds. Figure 7 As can be seen from the figure, after 8000 cycles, the charge retention can still be maintained at 0.7 of the maximum charge retention. This shows that the photothermal regulation layer 13 formed by the preparation method of this embodiment has good durability and high reliability.

[0086] See also Figure 8 As shown, Figure 8 A schematic diagram shows the transmittance of the photothermal regulation layer 13 prepared by the preparation method of this embodiment in the visible light region of 380nm~2500nm and the near-infrared light region. The horizontal axis is the wavelength and the vertical axis is the transmittance. The photothermal regulation layer 13 prepared by the preparation method of this embodiment can exhibit three photothermal regulation modes in the visible light band of 380nm~2500nm and the near-infrared light band 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 both blocked). Among them, when no driving potential is provided, the photothermal regulation mode is a bright mode. When the driving potential is -0.2V~-0.5V, the photothermal regulation mode is a cold mode. When the driving potential is -0.7V~-1V, the photothermal regulation mode is a dark mode. Figure 8 In the embodiment shown, the driving potential of the cold mode is -0.3V, and the driving potential of the dark mode is -0.7V. It can be seen that in the bright mode, the average transmittance of the visible light band and the near-infrared light band is 80%. In the cold mode, the visible light wavelength at 620nm can maintain a transmittance of 72.1%, and the near-infrared band of 780nm~2500nm has an average transmittance of 80% blocked. In the dark mode, the visible light band of 380nm~780nm has an average transmittance of 77.7% blocked, and the near-infrared band of 780nm~2500nm has an average transmittance of 98.8% blocked. And at a wavelength of 2500 nm, the transmittance difference between the bright mode and the dark mode is 70.5%, still with a high optical contrast of 70.5%, and a large optical adjustment range. The photothermal control layer 13 fabricated in this manner can independently and dynamically selectively modulate visible and near-infrared light, exhibiting three photothermal control modes: bright, cold, and dark, under different driving potentials. Furthermore, it can achieve modulation of the visible and near-infrared wavelengths from 380nm to 2500nm, encompassing a wide optical modulation range.

[0087] A comparative experiment was set up to obtain a comparative example of a light-heat regulation layer. The difference between the preparation method of the comparative experiment and the preparation method of this embodiment is that the interior of the heating device is heated until it reaches 300°C.

[0088] See also Figure 9 and Figure 10 As shown, the photothermal regulation layer 13 prepared by the preparation method of this embodiment and the comparative photothermal regulation layer prepared by the preparation method of the comparative experiment were tested and compared, and the results were as follows: Figure 9 and Figure 10 As shown in . Figure 9 The transmittance of the photothermal regulation layer 13 prepared by the preparation method of this embodiment in the visible light region of 380nm~2500nm and the near-infrared light region, as well as the emissivity spectrum in the medium-wave and long-wave infrared region of 4μm~25μm. Figure 10 The transmittance of the comparative photothermal regulation layer prepared by the preparation method of the comparative experiment in the visible light region of 380nm~2500nm and the near-infrared light region, as well as the emissivity spectrum in the medium-wave and long-wave infrared region of 4μm~25μm. Figure 9 and Figure 10 The horizontal axis in the graph is wavelength, the vertical axis on the left is transmittance, and the vertical axis on the right is emissivity. It can be seen that the photothermal control layer 13 prepared using the preparation method of this embodiment can exhibit three photothermal control modes in the visible light band of 380nm to 2500nm and the near-infrared light band under different driving potentials: bright mode (high transmission of both visible light and near-infrared light), cold mode (high transmission of visible light and blocking of near-infrared light), and dark mode (blocking of both visible light and near-infrared light). The photothermal control layer 13 prepared in this manner can independently and dynamically perform excellent selective modulation of visible light and near-infrared light, exhibiting three photothermal control modes: bright, cold, and dark, under different driving potentials. Furthermore, it can achieve regulation in the visible light band of 380nm to 2500nm and the near-infrared light band, with a wide optical regulation range. In contrast, the comparative example photothermal control layer prepared using the preparation method of the comparative experiment failed to achieve high transmission of visible light and blocking of near-infrared light, i.e., it failed to achieve the cold mode among the control modes.

[0089] The photothermal control layer 13 prepared using the preparation method of this embodiment has an average emissivity of 0.97 in bright mode within the mid-wave infrared range of 4μm to 8μm, decreasing to 0.75 in cool mode and 0.38 in dark mode. In the long-wave infrared range of 8μm to 25μm, the maximum emissivity change between bright and dark modes can be reduced from 0.93 to 0.34 (at 8μm), thereby enabling effective dynamic radiative cooling. In contrast, the photothermal control layer prepared using the preparation method of the comparative experiment maintained essentially unchanged emissivity in the mid-wave and long-wave infrared bands across all three photothermal control modes, lacking dynamic radiative cooling capability. This demonstrates that the photothermal control layer 13 prepared using the preparation method of this embodiment can effectively perform dynamic radiative cooling of mid-wave and long-wave infrared radiation, exhibiting a high emissivity regulation capability, thereby significantly reducing indoor temperatures and the surface temperature of hot objects.

[0090] Table 1 below compares the important properties of the current photothermal control layer reported in recent papers and the photothermal control layer 13 prepared using the preparation method of this embodiment. The optical contrast (ΔT) refers to the maximum optical transmittance difference of the photothermal control layer 13 at a specific wavelength, expressed as ΔT = T b -T c . T b is the transmittance in the faded state at a specified wavelength, T c is the transmittance in the colored state at a specified wavelength. The faded state refers to the state in which the photothermal control layer 13 returns from a certain color to a transparent and colorless state after applying an appropriate voltage. The colored state refers to the state in which the photothermal control layer 13 exhibits a certain color after applying an appropriate voltage.

[0091] The response time (coloring time / fading time) refers to the time it takes for the transmittance change to reach 90% of the optical contrast when the photothermal regulation layer 13 switches between the colored state and the faded state.

[0092] Cycling stability (number of cycles / charge retention) is measured by alternating application of a coloring voltage and a fading voltage to the photothermal modulation layer 13 or photothermal modulation device 10 for the duration of the voltage response, observing the change in charge retention over the number of cycles. The coloring voltage is the voltage applied to the photothermal modulation layer 13 to cause it to transition from a faded state to a colored state. The fading voltage is the voltage applied to the photothermal modulation layer 13 to cause it to transition from a colored state to a faded state.

[0093] Table 1

[0094]

[0095] Table 2 below compares the memory effect performance of current photothermal control layers reported in recent papers with that of the photothermal control layer 13 prepared using the preparation method of this embodiment. The memory effect is the duration of a colored state after the applied voltage is removed. A smaller change in transmittance in the colored state after a single application of a potential indicates lower energy consumption, eliminating the need for long-term electrical connections and improving energy efficiency.

[0096] Table 2

[0097]

[0098] As shown in Tables 1 and 2, the photothermal control layer 13 prepared using the preparation method of this embodiment exhibits high optical contrast in the visible and near-infrared regions, demonstrating a wide optical modulation range for the photothermal control layer 13. The coloring and fading times are relatively short, demonstrating the rapid response of the photothermal control layer 13. High charge retention over a high number of cycles demonstrates the cyclic stability of the photothermal control layer 13. The low increase in transmittance after a single application of voltage for coloring and a one-hour standstill from power off demonstrates the excellent memory effect of the photothermal control layer 13, resulting in lower energy consumption.

[0099] The preparation method of this embodiment allows for the convenient and controllable formation of a photothermal control layer 13 capable of independently and dynamically performing excellent selective modulation of visible and near-infrared light. Furthermore, the resulting photothermal control layer 13 possesses a rich amorphous / nanocrystalline heterojunction, generating a built-in electric field that accelerates directional electron transfer and ion migration, ultimately achieving excellent electrochromic modulation performance, including a wide optical adjustment range and amplitude, fast response time, excellent memory effect, and high stability.

[0100] In step S103, a second conductive layer 16 is formed on the second substrate 15 using electron beam thermal evaporation to form a second layer group 17. The second layer group 17 includes the second substrate 15 and the second conductive layer 16. The specific preparation method for forming the second conductive layer 16 on the second substrate 15 is the same as the specific preparation method for forming the first conductive layer 12 on the first substrate 11. The first substrate 11 and the second substrate 15 have the same structure, thickness, and material. The first conductive layer 12 and the second conductive layer 16 have the same structure, thickness, and material.

[0101] In step S104, an electrolyte layer 18 is formed between the first layer group 14 and the second layer group 17. The electrolyte layer 18 is made of an inorganic ion electrolyte, wherein the inorganic ions are lithium ions. The method for preparing the photothermal control device 10 is simple.

[0102] See also Figure 11As shown, in one embodiment, step S104 includes S401-S402.

[0103] In step S401, the first layer group 14 and the second layer group 17 are cured and connected, leaving a reserved space between the first layer group 14 and the second layer group 17. The edges of the first layer group 14 and the second layer group 17 can be bonded together using UV-curable adhesive, so that the first layer group 14, the second layer group 17, and the UV-curable adhesive enclose the reserved space. The first conductive layer 12 of the first layer group 14 and the second conductive layer 16 of the second layer group 17 are located on the inner side.

[0104] In step S402 , an electrolyte solution is prepared and injected into the reserved space and sealed. The electrolyte solution can be injected into the reserved space and sealed with a UV curable adhesive, thereby forming the electrolyte layer 18 .

[0105] In one embodiment, step S402 includes dissolving a third material in a solvent and stirring the solution using a stirrer. The stirrer stirs the solution at a set stirring speed and a set stirring time at a third set temperature to completely dissolve the third material in the solvent, forming an electrolyte solution. The third material is lithium perchlorate (LiClO4). The solvent is polypropylene carbonate (PC). Lithium perchlorate can be weighed and dissolved in a corresponding volume of PC solvent, stirring the solution using a magnetic stirrer. The corresponding volume of PC solvent refers to, for a 1 mol / L electrolyte solution concentration, 1.06392 g of lithium perchlorate powder corresponds to 10 ml of PC solvent, 2.12784 g of lithium perchlorate powder corresponds to 20 ml of PC solvent, and so on. The third set temperature is 80°C. The stirring speed is set between 400 rpm and 1200 rpm. The fourth set time is between 0.5 h and 5 h. In this way, the third material can be completely dissolved in the solvent to form a liquid electrolyte solution.

[0106] In this embodiment, the first layer group 14 and the second layer group 17 are bonded together using UV-curable adhesive, with a reserved space between them. 1.06392 g of lithium perchlorate is dissolved in 10 ml of polypropylene carbonate solvent and placed in a blender. The blender is stirred at 80°C and 800 rpm for 1 hour to form an electrolyte solution. The electrolyte solution is then injected into the reserved space, filling it completely. The space is then sealed with UV-curable adhesive. After complete curing, the photothermal control device 10 is obtained.

[0107] In this embodiment, the specific preparation steps are as follows:

[0108] Step 1: Select glass with a thickness of 1 mm as the first substrate 11 and the second substrate 15 .

[0109] Step 2: Place the first substrate 11 and indium tin oxide in the accommodating chamber of the electron beam coating machine, and evacuate the accommodating chamber to 3×10 -3 Pa, and the chamber is heated to 310°C. Oxygen is continuously added to the chamber at 15 sccm (15 cubic centimeters per minute) at 310°C. An electron beam is directed onto the indium tin oxide to form a spot. The electron beam current is increased to 8 mA and maintained for 4 minutes. The size and position of the spot are adjusted to maintain an indium tin oxide evaporation rate of 3.5 Å / s. This causes the indium tin oxide to evaporate and deposit on the surface to be coated on the first substrate 11, thereby forming a first conductive layer 12 with a thickness of 80 nm.

[0110] Step 3: Using the first conductive layer 12 and the first substrate 11 prepared in step 2 as substrates, place the substrate and tungsten trioxide in the chamber of the electron beam coating machine, and evacuate the chamber to 3×10 -3 Pa. An electron beam is directed onto tungsten trioxide to form a spot, and the beam current of the electron beam is increased until it reaches 8 mA and continued for 30 minutes. The size and position of the spot are adjusted to maintain the rate of tungsten trioxide evaporation at 2Å / s, so that the tungsten trioxide evaporates and deposits on the substrate, thereby forming a tungsten trioxide film with a thickness of 400 nm. The interior of the heating device is heated until it is heated to 400°C. The substrate on which tungsten trioxide is deposited after electron beam thermal evaporation is placed inside the heating device, and after heating for 30 minutes in an air environment, it is taken out and cooled to room temperature, thereby forming a photothermal regulation layer 13 with a thickness of approximately 350 nm, thereby obtaining a first layer group 14. The first layer group 14 includes a first substrate 11, a first conductive layer 12, and a photothermal regulation layer 13.

[0111] Step 4: Using the same conditions and steps as step 2, a second conductive layer 16 with a thickness of 80 nm is formed on the surface to be coated of the second substrate 15 to obtain a second layer group 17. The second layer group 17 includes the second substrate 15 and the second conductive layer 16.

[0112] Step 5: Dissolve 1.06392 g of lithium perchlorate in 10 ml of polypropylene carbonate solvent and place the solution in a stirrer. Stir the mixture at 80°C and 800 rpm for 1 hour to form an electrolyte solution. The stirrer may be a magnetic stirrer.

[0113] Step 6: The first layer group 14 obtained in step 3 and the second layer group 17 obtained in step 4 are cured and connected using UV curable adhesive, leaving a space between the first layer group 14 and the second layer group 17. The first conductive layer 12 of the first layer group 14 and the second conductive layer 16 of the second layer group 17 are located on the inner side.

[0114] Step 7: inject the electrolyte solution prepared in step 5 into the reserved space, fill the reserved space, and seal it with ultraviolet curing glue. After it is completely cured, the photothermal control device 10 is obtained.

[0115] See again Figure 1 As shown, an embodiment of the present invention further provides a photothermal control device 10, which is prepared using the preparation method described in the above embodiment. The photothermal control device 10 includes a first substrate 11, a first conductive layer 12, a photothermal control layer 13, an electrolyte layer 18, a second conductive layer 16, and a second substrate 15, which are stacked in sequence. The first substrate 11 and the second substrate 15 are made of glass. The first conductive layer 12 and the second conductive layer 16 are made of indium tin oxide. The photothermal control layer 13 is made of tungsten trioxide. The electrolyte layer 18 is made of inorganic ions. The first conductive layer 12 and the second conductive layer 16 are polycrystalline. The photothermal control layer 13 is an amorphous / nanocrystalline heterojunction structure. The thickness of the first conductive layer 12 and the second conductive layer 16 is 50 nm to 100 nm. The thickness of the photothermal control layer 13 is greater than or equal to 100 nm.

[0116] See also Figure 12 As shown, Figure 12 The figure shows the test results of the light and heat regulation capabilities of the light and heat regulation device 10 prepared by the preparation method of this embodiment in different light and heat regulation modes. Figure 12 On the left is the transmittance spectrum of the photothermal control device 10 prepared by the preparation method of this embodiment in the visible light region of 380nm~2500nm and the near-infrared light region, wherein the horizontal axis is the wavelength and the vertical axis is the transmittance. It can be seen that the photothermal control device 10 prepared by the preparation method of this embodiment can exhibit three photothermal control modes in the visible light band of 380nm~2500nm and the near-infrared light band under different driving potentials, namely bright mode (visible light and near-infrared light are 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). Among them, when no driving potential is provided, the photothermal control mode is a bright mode. When the driving potential is -3V~-5V, the photothermal control mode is a cold mode. When the driving potential is -6V~-8V, the photothermal control mode is a dark mode. Figure 12In the illustrated embodiment, the driving potential for the cold mode is -4.5V, and the driving potential for the dark mode is -7V. As can be seen, the prepared photothermal control device 10 is capable of independently and dynamically performing excellent selective modulation of visible light and near-infrared light. Under different driving potentials, it can exhibit three photothermal control modes: bright, cold, and dark. Furthermore, it can achieve modulation in the visible light band from 380nm to 2500nm and the near-infrared band, with a wide optical adjustment range.

[0117] from Figure 12 The infrared thermal imaging image on the right also shows that the temperature can be effectively reduced by 10.8°C in cold mode and 13.8°C in dark mode, indicating that the photothermal control device 10 can achieve dynamic light and heat regulation. The photothermal control device 10 prepared using the preparation method of this embodiment can simultaneously control visible light, near-infrared light, medium-wave and long-wave infrared radiation, with excellent control effects.

[0118] The preparation method of the photothermal control device 10 provided in the embodiments of the present invention is simple and controllable. During the preparation process, not only the transmittance of the photothermal control layer 13 but also the transmittance of the conductive layer is taken into account. This allows the optical contrast to be increased while also expanding the wavelength range to 380nm-2500nm. The photothermal control device 10 prepared using this preparation method has excellent control performance and a simple structure. It integrates electrochromism, solar thermal radiation control, and dynamic radiative cooling functions. It can not only independently and dynamically perform excellent selective modulation of visible and near-infrared light, but also exhibit three photothermal control modes of bright, cold, and dark under different driving potentials. It can also effectively perform dynamic radiative cooling of medium-wave and long-wave infrared radiation, with a high emissivity adjustment capability, which can significantly reduce the indoor temperature and the surface temperature of hot target objects. It achieves combined modulation of visible light, solar radiation, medium-wave, and long-wave infrared radiation, with good modulation effect.

[0119] It should be understood that the various forms of the processes 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 disclosed in the present disclosure can be achieved. This is not limited herein.

[0120] The above specific embodiments do not limit the scope of protection of the present invention. Those skilled in the art will appreciate that various modifications, combinations, sub-combinations, and substitutions may be made based on design requirements and other factors. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention are intended to be included within the scope of protection of the present invention.

Claims

1. A method for preparing a photothermal control device, characterized in that: include: forming a first conductive layer on the first substrate by electron beam thermal evaporation; forming a photothermal regulation layer on a side of the first conductive layer facing away from the first substrate by first performing electron beam thermal evaporation and then annealing in a heating device to form a first layer group; forming a second conductive layer on the second substrate by electron beam thermal evaporation to form a second layer group; and An electrolyte layer is formed between the first layer group and the second layer group.

2. The method for preparing a photothermal control device according to claim 1, wherein: The method of forming a first conductive layer on a first substrate by using electron beam thermal evaporation includes: Placing the first substrate and the first material in a receiving chamber of an electron beam coating machine, evacuating the receiving chamber to a first set pressure, heating the receiving chamber during the evacuation process to raise the temperature of the receiving chamber to a first set temperature, and continuously oxygenating the receiving chamber at a set oxygen volume at the first set temperature; The electron beam is directed onto the first material for a first set time, so that the first material evaporates and forms a film on the surface of the first substrate to be coated.

3. The method for preparing a photothermal control device according to claim 2, wherein: The first set pressure is 1×10 -3 Pa~5×10 -3 Pa; and / or The first set temperature is 280°C to 350°C; and / or The setting oxygen filling amount is 10 sccm to 30 sccm; and / or The first set time is 2 minutes to 5 minutes.

4. The method for preparing a photothermal control device according to claim 1, wherein: The method of first performing electron beam thermal evaporation and then annealing in a heating device to form a photothermal regulation layer on a side of the first conductive layer facing away from the first substrate to prepare a first layer group includes: Using the first conductive layer and the first substrate as substrates, placing the substrate and the second material in a receiving chamber of an electron beam coating machine, and evacuating the receiving chamber to a second set pressure at room temperature; The electron beam is directed onto the second material for a second set time, so that the second material evaporates and forms on the substrate.

5. The method for preparing a photothermal control device according to claim 4, wherein: The method of first performing electron beam thermal evaporation and then annealing in a heating device to form a photothermal regulation layer on a side of the first conductive layer facing away from the first substrate to form a first layer group further includes: heating the interior of the heating device until it reaches a second set temperature; The substrate on which the second material is deposited after electron beam thermal evaporation is placed inside the heating device, heated at the second set temperature and air environment for a third set time, taken out, and cooled to room temperature.

6. The method for preparing a photothermal control device according to claim 1, wherein: The forming of an electrolyte layer between the first layer group and the second layer group comprises: Connecting the first layer group and the second layer group by curing, and leaving a reserved space between the first layer group and the second layer group; and An electrolyte solution is prepared, injected into the reserved space, and sealed.

7. The method for preparing a photothermal control device according to claim 6, wherein: The preparation of the electrolyte solution comprises: The third material is dissolved in a solvent and stirred by a stirrer; wherein the stirrer stirs at a set stirring speed at a third set temperature for a fourth set time to completely dissolve the third material in the solvent to form the electrolyte solution.

8. The method for preparing a photothermal control device according to claim 7, characterized in that: The third set temperature is 80° C.; and / or The stirring speed is set to 400 r / min to 1200 r / min; and / or The fourth set time is 0.5h~5h; and / or The third material is lithium perchlorate; and / or The solvent is polypropylene carbonate solvent.

9. A photothermal control device, characterized in that: The photothermal regulation device is prepared by the preparation method according to any one of claims 1 to 8, and includes a first substrate, a first conductive layer, a photothermal regulation layer, an electrolyte layer, a second conductive layer and a second substrate stacked in sequence.

10. The photothermal control device according to claim 9, characterized in that: The first substrate and the second substrate are made of glass; and / or The material of the first conductive layer and the second conductive layer is indium tin oxide; and / or The material of the photothermal regulation layer is tungsten trioxide; and / or The material of the electrolyte layer is inorganic ions; and / or The first conductive layer and the second conductive layer are polycrystalline structures; and / or The photothermal regulation layer is an amorphous / nanocrystalline heterojunction structure; and / or The thickness of the first conductive layer and the second conductive layer is 50 nm to 100 nm; and / or The thickness of the photothermal regulation layer is greater than or equal to 100 nm.

Images