Photo-thermal regulation and control device and preparation method thereof

Abstract

The invention relates to the field of electrochromism, in particular to a photo-thermal regulation and control device and a preparation method thereof, and the preparation method of the photo-thermal regulation and control device comprises the following steps: forming a first conductive layer on a first substrate by adopting an electron beam thermal evaporation method; forming a photo-thermal regulation and control layer on one side, deviating from the first substrate, of the first conductive layer by adopting a method of firstly carrying out electron beam thermal evaporation and then carrying out annealing in heating equipment so as to prepare and form a first layer group; and forming a second conductive layer on the second substrate by adopting an electron beam thermal evaporation method to prepare and form a second layer group. An electrolyte layer is formed between the first layer group and the second layer group. The photo-thermal regulation and control device obtained through the preparation method can regulate and control visible light, near-infrared light, medium-wave and long-wave infrared radiation at the same time.

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 regulation materials. In 2013, the Milliron group pioneered the research of electrochromic photothermal regulation technology by preparing nanocomposite films by doping ITO nanocrystals into amorphous niobium oxide (NbOx). It 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 regulation nanocomposites usually require precise and complex design and manufacturing to form an interconnected open network at the nanoscale to promote the contact between the electrolyte and the near-infrared and visible light modulation components. Therefore, the use of single-component materials can accelerate the development of electrochromic photothermal regulation materials. WO3 is the most widely studied single-component electrochromic photothermal regulation material, which has good environmental protection properties, mature preparation process and abundant raw material sources. However, it is generally necessary to make WO containing oxygen vacancies. 3-x Or nanostructured WO3 can achieve dynamic regulation in visible light and near-infrared light. It is still a challenge to prepare nanocomposites and nanostructured films with high stability and uniformity in a large area and in a controllable manner. At present, the preparation process of photothermal regulation devices is complicated, and the prepared photothermal regulation devices cannot simultaneously regulate visible light, near-infrared light, medium-wave and long-wave infrared radiation. Summary of the invention

[0004] In view of this, the present invention aims to provide a photothermal regulation device and a preparation method thereof. The photothermal regulation device obtained by the preparation method can simultaneously regulate 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: A method for preparing a photothermal control device, comprising: 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 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; 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.

[0006] Furthermore, forming a first conductive layer on the first substrate by 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, and 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 filling amount at the first set temperature; The electron beam is projected 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.

[0007] Furthermore, 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 Set the oxygen filling rate to 10 sccm~30 sccm; and / or The first setting time is 2min~5min.

[0008] Furthermore, a photothermal regulation layer is formed on a side of the first conductive layer 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: 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.

[0009] Furthermore, a method of first performing electron beam thermal evaporation and then annealing in a heating device is used to form a photothermal regulation layer on a side of the first conductive layer away from the first substrate to prepare a first layer group, and 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 a heating device, and after being heated for a third set time at a second set temperature and in an air environment, taken out and cooled to room temperature.

[0010] Further, an electrolyte layer is formed between the first layer group and the second layer group, comprising: 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.

[0011] Further, preparing the electrolyte solution comprises: The third material is dissolved in the solvent and stirred by a stirrer; wherein the stirrer stirs 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.

[0012] Further, the third set temperature is 80° C.; and / or Set the stirring speed to 400 r / min~1200 r / min; and / or The fourth setting time is 0.5h~5h; and / or The third material is lithium perchlorate; and / or The solvent is polypropylene carbonate solvent.

[0013] A photothermal regulation device is prepared by the preparation method as 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 which are stacked in sequence.

[0014] Furthermore, the first substrate and the second substrate are made of glass; and / or The materials of the first conductive layer and the second conductive layer are indium tin oxide; and / or The material of the light-heat 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 50nm-100nm; and / or The thickness of the photothermal regulation layer is greater than or equal to 100 nm.

[0015] Compared with the prior art, the invention can achieve the following beneficial effects: the invention creates a method for preparing the photothermal control device, the preparation method is simple, and the prepared photothermal control device can not only independently and dynamically perform excellent selective modulation on visible and near-infrared light, but also display three photothermal control modes of bright, cold and dark under different driving potentials, and can also effectively perform dynamic radiation cooling on medium-wave and long-wave infrared radiation, and has a high emissivity adjustment capability, thereby significantly reducing the indoor temperature and the surface temperature of the hot target object. It can perform combined modulation on visible light, solar radiation, medium-wave and long-wave infrared radiation, and has a good 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 a photothermal control device according to an embodiment of the present invention; Figure 2 A flow chart of a method for preparing a photothermal control device according to an embodiment of the present invention; Figure 3 A further flow chart of the method for preparing the photothermal regulation device described in the embodiment of the present invention; Figure 4 A schematic diagram showing a comparison of transmittances of the first conductive layer described in an embodiment of the present invention and a conventional conductive layer prepared by a conventional preparation method on the market; Figure 5 A further flow chart of the method for preparing the photothermal regulation device described in the embodiment of the present invention; Figure 6 TEM image of the photothermal regulation layer described in the embodiment of the present invention; Figure 7 A schematic diagram of the charge retention of the photothermal regulation layer according to an embodiment of the present invention when cycling under a set cycle; Figure 8 A 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; Fig. 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, and the emissivity spectrum in the medium-wave and long-wave infrared region of 4μm~25μm; Fig.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, and the emissivity spectrum in the medium-wave and long-wave infrared region of 4μm~25μm; Fig.11 A further flow chart of the method for preparing the photothermal regulation device described in the embodiment of the present invention; Fig.12 This is a graph showing the test results of the dimming and heat regulation capabilities of the photothermal regulation device described in the embodiment of the present invention under different photothermal regulation modes.

[0017] Description of reference numerals: 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

[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] 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.

[0024] 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 be a polycrystalline structure, and its thickness may be 50 nm to 100 nm.

[0025] See also Figure 1 and Figure 3 As shown, in one embodiment, step S101 includes steps S201-S202.

[0026] 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. And during the vacuuming process, the containing chamber is heated to raise the temperature of the containing chamber to the first set temperature. The first set temperature is 280°C~350°C. The containing chamber can be vacuumed, and after the pressure in the containing chamber reaches 8Pa, the containing chamber is heated. At the first set temperature, oxygen is continuously added to the containing chamber at a set oxygen filling amount. The oxygen filling amount is set to 10sccm~30sccm. Among them, the first material can be indium tin oxide (ITO, Indium Tin Oxide). Continuously adding oxygen to the containing chamber at a set oxygen filling amount can prevent indium tin oxide from losing oxygen, so that indium tin oxide can have better resistance and transmittance.

[0027] In one embodiment, before placing the first substrate 11 and the first 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 first substrate 11 except the surface to be coated of the first substrate 11 .

[0028] In step S202, an electron beam is directed onto the first material for a first set time, so that the first material is evaporated and deposited on the surface to be coated of the first substrate 11. The first set time is 2 minutes to 5 minutes.

[0029] In one embodiment, step S202 includes: applying an electron beam to the first material to form a light spot, and increasing the beam current of the electron beam until it reaches a first set value. The first set value is 7mA to 15mA. The size and position of the light spot are adjusted to maintain the rate of evaporating the first material at a first set rate. The first set rate is 1 Å / s to 4Å / s. Setting the oxygen filling amount in this way can match the rate of evaporating the first material, so that the mobility and carrier concentration of the first conductive layer 12 change, thereby improving the transmittance of infrared light.

[0030] 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 a receiving chamber of an electron beam coating machine, and the receiving chamber is evacuated to a vacuum of 3×10 -3Pa, and heat the containing cavity to raise the temperature of the containing cavity to 310°C, and continue to oxygenate the containing cavity at a temperature of 310°C at a rate of 15 sccm (i.e., 15 cubic centimeters per minute). An electron beam is directed onto indium tin oxide to form a light spot, and the beam current of the electron beam is increased until it reaches 8 mA, which lasts for 4 minutes. The size and position of the light spot are adjusted to maintain the rate of evaporating indium tin oxide at 3.5Å / s, so that indium tin oxide is evaporated and deposited on the surface to be coated of the first substrate 11, thereby forming a first conductive layer 12.

[0031] See also Figure 4 As shown, Figure 4 A schematic diagram showing a comparison of transmittances of the first conductive layer 12 prepared by the preparation method of this embodiment and a conventional conductive layer prepared by conventional preparation methods 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 of 380nm~2500nm and the near-infrared light region, 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.

[0032] In step S102, a photothermal regulation layer 13 is formed on the side of the first conductive layer 12 away from the first substrate 11 by first performing electron beam thermal evaporation and then annealing in a heating device to prepare 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. The formed photothermal regulation layer 13 may be an amorphous / nanocrystalline heterojunction structure, and its thickness is greater than or equal to 100 nm.

[0033] See also Figure 5 As shown, in one embodiment, step S102 includes steps S301-S302.

[0034] 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, and 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.

[0035] 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 .

[0036] 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.

[0037] In one embodiment, step S302 further includes: striking the electron beam on the second material to form a light spot, increasing the beam current of the electron beam until it reaches a second set value. The second set value is 7mA to 15mA. The size and position of the light spot are adjusted to maintain the rate of evaporating the second material at the second set rate. The second set rate is 1Å / s to 5Å / s.

[0038] In one embodiment, step S102 also includes steps S303-S304.

[0039] 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, and the interior of the vacuum tube furnace is an air atmosphere, not a vacuum atmosphere. The interior of the heating device may be heated to a second set temperature, and the second set temperature is 310°C to 400°C.

[0040] In step S304, the substrate on which the second material is deposited after electron beam thermal evaporation is placed inside the heating device, and is taken out after being heated for a third set time under a second set temperature and air environment, and cooled to room temperature. Among them, the third set time is 15min~1000min. 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 bearing structure, and sent into the interior of the heating device, and taken out after being heated for a third set time under an air environment. After being taken out, it can be cooled in an indoor environment to cool it 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~2500nm, and its optical contrast, response time, stability and memory effect performance are good, and effective dynamic radiation cooling can be performed in the mid-to-far infrared band of 4μm~25μm.

[0041] 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 evacuated to 3×10 -3Pa. The electron beam was hit on the tungsten trioxide to form a spot, and the beam current of the electron beam was increased until it reached 8 mA, which lasted for 30 minutes. The size and position of the spot were adjusted to maintain the rate of evaporation of tungsten trioxide at 2Å / s, so that the tungsten trioxide was evaporated and deposited on the substrate, thereby forming a tungsten trioxide film with a thickness of 400 nm.

[0042] The inside of the heating device is heated to 400° C. The substrate on which the tungsten trioxide film is deposited after electron beam thermal evaporation is placed inside the heating device, and is heated at 400° C. in an air environment for 30 minutes, then taken out and cooled to room temperature, thereby forming a photothermal regulation layer 13 .

[0043] See also Figure 6 As shown, Figure 6 The TEM (Transmission Electron Microscope) image of the photothermal control layer 13 prepared by the preparation method of this embodiment is shown. The photothermal control layer 13 is prepared by first performing electron beam thermal evaporation and then annealing in a heating device, and a large number of amorphous / nanocrystalline (cubic phase) heterogeneous interfaces can be obtained, so that an ultra-wideband electrochromic photothermal control layer with an amorphous / nanocrystalline heterojunction structure can be prepared. Among them, the amorphous / nanocrystalline heterojunction structure has a large number of amorphous / nanocrystalline (cubic phase) heterogeneous interfaces.

[0044] See also Figure 7 As shown, Figure 7 The schematic diagram shows the charge retention of the photothermal regulation 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 It can be seen that after 8000 cycles, the charge retention can still be maintained at 0.7 of the maximum charge retention. It can be seen that the photothermal regulation layer 13 formed by the preparation method of this embodiment has good durability and high reliability.

[0045] See also Figure 8 As shown, Figure 8A schematic diagram of 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 is shown. 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 adopts -0.3V, and the driving potential of the dark mode adopts -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 regulation layer 13 prepared in this way can independently and dynamically perform excellent selective modulation on visible light and near-infrared light, and can display three photothermal regulation modes of bright, cold and dark under different driving potentials. It can also achieve regulation of the visible light band of 380nm~2500nm and the near-infrared light band, with a wide optical regulation range.

[0046] 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 inside of the heating device is heated until it is heated to 300°C.

[0047] See also Fig. 9 and Fig.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 obtained were as follows: Fig. 9 and Fig.10 as shown in . Fig. 9The 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, and the emissivity spectrum of the medium-wave and long-wave infrared in the range of 4μm~25μm. Fig.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 of the medium-wave and long-wave infrared in the range of 4μm~25μm. Fig. 9 and Fig.10 The horizontal axis in the figure 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 regulation layer 13 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 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). The photothermal regulation layer 13 prepared in this way can independently and dynamically perform excellent selective modulation of visible light and near-infrared light, and can exhibit three photothermal regulation modes of bright, cold and dark under different driving potentials. And it can achieve the regulation of the visible light band and near-infrared light band of 380nm~2500nm, and the optical regulation range is large. However, the comparative photothermal regulation layer prepared by the preparation method of the comparative experiment cannot achieve high visible light transmission and near-infrared light blocking, that is, it cannot achieve the cold mode in the regulation mode.

[0048] The photothermal regulation layer 13 prepared by the preparation method of this embodiment has an average emissivity of 0.97 in the bright mode within the mid-wave infrared range of 4μm~8μm, which is reduced to 0.75 in the cold mode and 0.38 in the dark mode. In the long-wave infrared range of 8μm~25μm, the maximum change in emissivity between the bright mode and the dark mode can be reduced from 0.93 to 0.34 (at 8μm), thereby achieving effective dynamic radiation cooling. However, in the comparative photothermal regulation layer prepared by the preparation method of the comparative experiment, the emissivity in the mid-wave and long-wave infrared bands remains basically unchanged under the three photothermal regulation modes, and does not have the ability of dynamic radiation cooling. It can be seen that the photothermal regulation layer 13 prepared by the preparation method of this embodiment can effectively perform dynamic radiation cooling on mid-wave and long-wave infrared radiation, and has a high emissivity adjustment ability, thereby significantly reducing the indoor temperature and the surface temperature of the hot target object.

[0049] Table 1 below is a comparison of the important properties of the current photothermal regulation layer reported in recent papers and the photothermal regulation layer 13 prepared by the preparation method of this embodiment. Among them, the optical contrast (ΔT) refers to the maximum optical transmittance difference of the photothermal regulation layer 13 at a specific wavelength, which is expressed by the formula ΔT = Tb -T c . T b is the transmittance in the faded state at a specified wavelength, T c is the transmittance of the colored state at a specified wavelength. The faded state refers to the state in which the photothermal regulation layer 13 recovers from a certain color to transparent and colorless after applying an appropriate voltage. The colored state refers to the state in which the photothermal regulation layer 13 presents a certain color after applying an appropriate voltage.

[0050] The response time (coloring time / fading time) refers to the time taken for the transmittance change to reach 90% of the optical contrast when the light-heat regulating layer 13 switches between the colored state and the faded state.

[0051] Cyclic stability (number of cycles / charge retention) refers to the change in charge retention with the number of cycles by alternately applying a coloring voltage and a fading voltage to the photothermal regulation layer 13 or the photothermal regulation device 10 continuously with its response time as the voltage duration, and observing the change in charge retention with the number of cycles. The coloring voltage refers to the voltage applied to the photothermal regulation layer 13 to change it from a fading state to a colored state. The fading voltage refers to the voltage applied to the photothermal regulation layer 13 to change it from a colored state to a faded state.

[0052] Table 1

[0053] Table 2 below is a comparison of the memory effect performance of the current photothermal regulation layer reported in a recent paper and the photothermal regulation layer 13 prepared by the preparation method of this embodiment. Among them, the memory effect is the time that the color state can be maintained after the external voltage is stopped. After applying a potential once, the smaller the change in transmittance in the colored state, the smaller the energy consumption, and there is no need to maintain the electrical connection state for a long time, which is energy-saving.

[0054] Table 2

[0055] According to Table 1 and Table 2, the optical contrast in the visible light region and the optical contrast in the near-infrared light region of the photothermal regulation layer 13 prepared by the preparation method of this embodiment are large, which reflects the large optical adjustment range of the photothermal regulation layer 13. The coloring time and fading time are relatively short, which reflects the fast response time of the photothermal regulation layer 13. In the case of a large number of cycles, the charge retention is high, which reflects the cyclic stability of the photothermal regulation layer 13. The increase in transmittance after applying a voltage once and coloring until the power is turned off and standing for 1h (1 hour) is low, which reflects the excellent memory effect of the photothermal regulation layer 13 and lower energy consumption.

[0056] Thus, the preparation method of this embodiment can be used to conveniently and controllably prepare the photothermal control layer 13, and the photothermal control layer 13 can independently and dynamically perform excellent selective modulation of visible light and near-infrared light. In addition, the formed photothermal control layer 13 has a rich amorphous / nanocrystalline heterogeneous interface, and the built-in electric field generated by it can accelerate the directional transfer of electrons and ion migration, and finally achieve excellent electrochromic modulation performance, including a large optical adjustment range and amplitude, fast response time, excellent memory effect and high stability.

[0057] In step S103, a second conductive layer 16 is formed on the second substrate 15 by electron beam thermal evaporation to prepare 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.

[0058] In step S104, an electrolyte layer 18 is formed between the first layer group 14 and the second layer group 17. The material of the electrolyte layer 18 is an inorganic ion electrolyte, and the inorganic ions are lithium ions. The method for preparing the light-heat regulation device 10 is simple.

[0059] See also Fig.11 As shown, in one embodiment, step S104 includes S401-S402.

[0060] In step S401, the first layer group 14 and the second layer group 17 are cured and connected, and a reserved space is formed 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 by ultraviolet curing adhesive, so that the first layer group 14, the second layer group 17 and the ultraviolet curing 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.

[0061] In step S402, an electrolyte solution is prepared, and the electrolyte solution is injected into the reserved space and sealed. The electrolyte solution can be injected into the reserved space and sealed with a UV curing adhesive, so that the electrolyte layer 18 can be formed.

[0062] In one embodiment, step S402 includes: dissolving the third material in a solvent and stirring it by a stirrer. The stirrer stirs at a set stirring speed for a fourth set time at a third set temperature so that the third material is completely dissolved in the solvent to form an electrolyte solution. The third material is lithium perchlorate (LiClO4). The solvent is a polypropylene carbonate (PC) solvent. Lithium perchlorate can be weighed and dissolved in a corresponding volume of polypropylene carbonate solvent and stirred by a magnetic stirrer. The corresponding volume of polypropylene carbonate solvent refers to when the configuration concentration of the electrolyte solution is 1 mol / 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. The third set temperature is 80°C. The stirring speed is set to 400 r / min~1200 r / min. The fourth set time is 0.5h~5h. In this way, the third material can be completely dissolved in the solvent to form a liquid electrolyte solution.

[0063] In this embodiment, the first layer group 14 and the second layer group 17 are cured and connected with ultraviolet curing glue, and a reserved space is provided between the first layer group 14 and the second layer group 17. 1.06392 g of lithium perchlorate is dissolved in 10 ml of polypropylene carbonate solvent and placed on a stirrer, which is stirred at 80° C. and 800 r / min for 1 hour to form an electrolyte solution. The electrolyte solution is injected into the reserved space, filling the reserved space, and sealed with ultraviolet curing glue. After complete curing, the photothermal control device 10 is obtained.

[0064] In this embodiment, the specific preparation steps are as follows: Step 1: Select glass with a thickness of 1 mm as the first substrate 11 and the second substrate 15 .

[0065] Step 2: Place the first substrate 11 and indium tin oxide in the containing chamber of the electron beam coating machine, and evacuate the containing chamber to 3×10 -3 Pa, and heat the containing cavity to raise the temperature of the containing cavity to 310°C, and continue to oxygenate the containing cavity at a temperature of 310°C at a rate of 15 sccm (i.e., 15 cubic centimeters per minute). An electron beam is directed onto indium tin oxide to form a light spot, and the beam current of the electron beam is increased until it reaches 8 mA, which lasts for 4 minutes. The size and position of the light spot are adjusted to maintain the rate of evaporating indium tin oxide at 3.5Å / s, so that indium tin oxide is evaporated and deposited on the surface to be coated of the first substrate 11, thereby forming a first conductive layer 12 with a thickness of 80nm.

[0066] 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 receiving chamber of the electron beam coating machine, and evacuate the receiving chamber to 3×10 -3 Pa. An electron beam is hit on tungsten trioxide to form a light spot, and the beam current of the electron beam is increased until it reaches 8 mA, which lasts for 30 minutes. The size and position of the light spot are adjusted to maintain the rate of evaporation of tungsten trioxide 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 inside 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 is taken out after heating for 30 minutes in an air environment, and cooled to room temperature, thereby forming a photothermal regulation layer 13 with a thickness of about 350nm, and 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.

[0067] 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.

[0068] Step 5: 1.06392 g of lithium perchlorate is dissolved in 10 ml of polypropylene carbonate solvent and placed on a stirrer, and the stirrer is stirred at a temperature of 80° C. and a stirring speed of 800 r / min for 1 hour to form an electrolyte solution. The stirrer may be a magnetic stirrer.

[0069] Step 6: The first layer group 14 obtained in step 3 and the second layer group 17 obtained in step 4 are connected by curing with UV curing adhesive, and a reserved space is provided 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 inside.

[0070] Step seven: inject the electrolyte solution prepared in step five into the reserved space, fill the reserved space, and seal it with ultraviolet curing glue, and obtain the photothermal regulation device 10 after complete curing.

[0071] See again Figure 1As shown, the present invention also provides a photothermal regulation device 10, which is prepared by the preparation method described in the above embodiment. The photothermal regulation device 10 includes a first substrate 11, a first conductive layer 12, a photothermal regulation layer 13, an electrolyte layer 18, a second conductive layer 16, and a second substrate 15 stacked in sequence. Among them, the material of the first substrate 11 and the second substrate 15 is glass. The material of the first conductive layer 12 and the second conductive layer 16 is indium tin oxide. The material of the photothermal regulation layer 13 is tungsten trioxide. The material of the electrolyte layer 18 is inorganic ions. The first conductive layer 12 and the second conductive layer 16 are polycrystalline structures. The photothermal regulation layer 13 is an amorphous / nanocrystalline heterojunction structure. The thickness of the first conductive layer 12 and the second conductive layer 16 is 50nm~100nm. The thickness of the photothermal regulation layer 13 is greater than or equal to 100nm.

[0072] See also Fig.12 As shown, Fig.12 The figure shows the test results of the dimming and heat regulation capabilities of the photothermal regulation device 10 prepared by the preparation method of this embodiment in different photothermal regulation modes. Fig.12 On the left is the transmittance spectrum of the photothermal regulation 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 regulation device 10 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 -3V~-5V, the photothermal regulation mode is a cold mode. When the driving potential is -6V~-8V, the photothermal regulation mode is a dark mode. Fig.12 In the embodiment shown, the driving potential of the cold mode is -4.5V, and the driving potential of the dark mode is -7V. It can be seen that the prepared photothermal regulation device 10 can independently and dynamically perform excellent selective modulation of visible light and near-infrared light, and can display three photothermal regulation modes of bright, cold, and dark under different driving potentials. And it can achieve regulation of the visible light band of 380nm~2500nm and the near-infrared light band, and the optical regulation range is large.

[0073] from Fig.12It can also be seen from the infrared thermal imaging image shown on the right that the temperature can be effectively reduced by 10.8°C in cold mode and by 13.8°C in dark mode. It can be seen that the photothermal control device 10 can achieve the effect of dynamic light and heat regulation. The photothermal control device 10 prepared by the preparation method of this embodiment can simultaneously regulate visible light, near infrared light, medium wave and long wave infrared radiation, and has a good regulation effect.

[0074] The preparation method of the photothermal control device 10 provided by the embodiment of the invention is simple and controllable. In the preparation process, not only the photothermal control layer 13 but also the transmittance of the conductive layer are considered, so that the optical contrast can be expanded while the wavelength range can be expanded to 380nm~2500nm. The photothermal control device 10 prepared by the preparation method has excellent control performance and simple structure. It integrates electrochromic, solar thermal radiation control and dynamic radiation cooling functions, and can not only independently and dynamically perform excellent selective modulation of visible and near-infrared light, but also display three photothermal control modes of bright, cold and dark under different driving potentials. It can also effectively perform dynamic radiation cooling on medium-wave and long-wave infrared radiation, and has a high emissivity adjustment ability, so that the indoor temperature and the surface temperature of the hot target object can be greatly reduced. The combined modulation of visible light, solar radiation, medium-wave and long-wave infrared radiation is realized, and the modulation effect is good.

[0075] 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.

[0076] 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 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 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; 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, characterized in that: The method of forming a first conductive layer on a first substrate by using electron beam thermal evaporation comprises: 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, and continuously oxygenating the receiving chamber at a set oxygen filling amount 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, characterized in that: 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 oxygen filling amount is set to 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, characterized in that: 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 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, characterized in that: 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 away from the first substrate to prepare a first layer group also 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, and after being heated for a third set time at the second set temperature and in an air environment, taken out and cooled to room temperature.

6. The method for preparing a photothermal control device according to claim 1, characterized in that: 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, and the electrolyte solution is injected into the reserved space and sealed.

7. The method for preparing a photothermal control device according to claim 6, characterized in that: 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 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.

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 a 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 which are 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 50nm-100nm; and / or The thickness of the photothermal regulation layer is greater than or equal to 100 nm.

Images