Dual-band silver-based electrochromic device for dynamically regulating and controlling sun and mid-infrared radiation and application of dual-band silver-based electrochromic device

Abstract

The invention relates to a dual-band silver-based electrochromic device for dynamically regulating and controlling sun and mid-infrared radiation and application thereof.The device comprises two transparent conductive electrodes, silver-based gel electrolyte and a transparent packaging material, the two transparent conductive electrodes serve as a working electrode and a counter electrode respectively, the transparent conductive electrodes are indium tin oxide-quartz glass electrodes, and the silver-based gel electrolyte is arranged between the two transparent conductive electrodes. The working electrode is made of single-sided indium tin oxide-quartz glass, the counter electrode is made of double-sided indium tin oxide-quartz glass, the working electrode and the counter electrode are arranged in parallel and in a staggered manner and are bonded and fixed through a transparent packaging material, and then a silver-based gel electrolyte is injected between the two transparent conductive electrodes, so that the silver-based gel electrolyte is formed. And an electrode-electrolyte-electrode three-layer structure is formed. Compared with the prior art, the device has excellent sunlight and mid-infrared dual-band radiation modulation capability, is controllable in composition and structure and easy to expand, and has great application prospects in the aspect of all-season dynamic thermal management of transparent enclosure structures such as buildings and automobiles.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromic devices, and relates to a dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation and applications thereof. Background Art

[0002] Transparent enclosures (building windows, curtain walls, car skylights, etc.), as the interface between indoor and outdoor environments, are the main source of energy loss, accounting for 60% of the total energy loss, and play a key role in improving energy conservation. Traditional windows, as static components, cannot effectively respond to climate changes that vary with time and space to meet cooling and heating needs. At present, some windows based on electrochromic technology that intelligently adjust the transmission of sunlight (0.3-2.5μm) have been developed. They dynamically adjust the amount of solar radiation entering the room by reversibly switching between transparent and opaque states, which to a certain extent solves the problem of the "static" optical properties of traditional windows.

[0003] On the basis of dynamically regulating solar heating, if the energy efficiency of transparent enclosures is to be further improved, the modulation range needs to be extended to the mid-infrared (2.5-20μm) spectrum to dynamically control the radiative heat exchange between indoors, windows and outdoors. When cooling is required, the high emissivity of the mid-infrared band (especially the atmospheric window, 8-13μm) can dissipate indoor heat to outer space through spontaneous infrared radiation without any energy consumption, which helps to achieve "net zero energy consumption". When heating is required, the mid-infrared band should be adjusted to low emissivity to minimize the loss of indoor heat to the outside world.

[0004] In summary, transparent enclosures in different seasons should have the following characteristics: in hot seasons, transparent enclosures should have the characteristics of high solar reflection and high and medium infrared emission. High solar reflection can effectively block solar heat from entering the room, and high and medium infrared emission can effectively dissipate indoor heat to the outside, which is conducive to achieving cooling effect; in cold seasons, transparent enclosures should have the characteristics of high solar transmittance and low medium infrared emission. High solar transmittance can effectively use solar heat for indoor heating, and low medium infrared emission can minimize the loss of indoor heat to the outside, which is conducive to achieving heating effect. Therefore, it is necessary to further explore and develop dual-band electrochromic devices that can coordinately regulate solar radiation and medium infrared radiation, optimize indoor and outdoor energy exchange, and meet the cooling and heating needs of different seasons and regions. Summary of the invention

[0005] The purpose of the present invention is to provide a dual-band silver-based electrochromic device and its application for dynamically regulating solar and mid-infrared radiation. By applying / removing voltage to control the deposition / dissolution of silver nanoparticles and combining the plane flipping of glass, it can bidirectionally and reversibly adjust the switching of sunlight between high reflection and high transmission and the switching of mid-infrared between high emission and low emission, adapt to the cooling and heating needs of different time and space, and improve the energy efficiency of windows.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] On the one hand, the present invention provides a dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation, comprising two transparent conductive electrodes serving as a working electrode and a counter electrode, respectively, and a silver-based gel electrolyte and a transparent packaging material, wherein the transparent conductive electrode is an indium tin oxide (ITO)-quartz glass electrode, wherein the working electrode is a single-sided indium tin oxide-quartz glass, and the counter electrode is a double-sided indium tin oxide-quartz glass, the working electrode and the counter electrode are placed in parallel and staggered, and are bonded and fixed by a transparent packaging material, and then the silver-based gel electrolyte is injected between the two transparent conductive electrodes to form a three-layer structure of electrode-electrolyte-electrode.

[0008] Furthermore, the thickness of the quartz glass used in the transparent conductive electrode is 1.0-1.2 mm, and the thickness of the indium tin oxide on each side is 135-200 nm. It should be pointed out here that single-sided indium tin oxide-quartz glass refers to one side of the quartz glass coated with an indium tin oxide film, while double-sided indium tin oxide-quartz glass refers to both sides of the quartz glass coated with indium tin oxide films. The indium tin oxide film with a thickness of 135-200 nm has the characteristics of high and medium infrared reflection, corresponding to the characteristics of low mid-infrared emission. The indium tin oxide film with a thickness of 135 nm can achieve a mid-infrared emissivity of less than 20%, and the mid-infrared emissivity of the indium tin oxide film with a thickness of 200 nm can be as low as 10%, which is close to the theoretical limit. The surface of quartz glass has the characteristics of high and medium infrared emissivity, generally close to 90%.

[0009] Furthermore, the indium tin oxide surface of the transparent conductive electrode is also treated with oxygen plasma cleaning and thiol monolayer self-assembly modification.

[0010] Furthermore, in order to improve the deposition quality of silver nanoparticles, the oxygen plasma cleaning process is specifically as follows:

[0011] The transparent conductive electrode was ultrasonically cleaned in acetone, isopropanol, ethanol and deionized water for 12-15 minutes, and then dried at 60°C for 3-4 hours in a nitrogen atmosphere; the dried electrode surface was then cleaned with oxygen plasma for 12-15 minutes to remove residual organic impurities and hydroxylate the surface;

[0012] The self-assembly modification process is specifically as follows:

[0013] The transparent conductive electrode after oxygen plasma cleaning was immersed in a mixed solution of 3-mercaptopropyltrimethoxysilane: toluene with a volume ratio of 1:40 for 12-15 hours; then, the immersed transparent conductive electrode was ultrasonically treated in ethanol for 12-15 minutes, and then the electrode was dried at 60°C in a nitrogen atmosphere for 3-4 hours. The trimethoxysilane group can be anchored on the hydroxyl group on the surface of indium tin oxide, while the terminal thiol group strongly interacts with the deposited silver nanoparticles, ensuring the stability and high reflectivity of the silver film.

[0014] Furthermore, the two transparent conductive electrodes are placed in parallel, and the side with indium tin oxide is located inside the electrode and faces the silver-based gel electrolyte (i.e., single-sided indium tin oxide-quartz glass), while double-sided indium tin oxide-quartz glass has no special requirements due to its symmetrical structure;

[0015] Two transparent conductive electrodes are arranged in a staggered manner, and both sides of the staggered electrodes are exposed by 0.5-1 cm for applying voltage.

[0016] Furthermore, the transparent encapsulation material bonding and fixing process is as follows:

[0017] A transparent packaging material with a thickness of 0.5 mm is used to bond two parallel and offset transparent conductive electrodes, and a liquid injection gap with a width of 0.1 mm is left at the corner of the bonding quadrilateral to facilitate the subsequent injection of the silver-based gel electrolyte.

[0018] Furthermore, the transparent packaging material is VHB closed-cell acrylic foam.

[0019] Furthermore, after injecting the silver-based gel electrolyte, the reserved injection gap was filled with UV-curable glue and the 2 The package is cured under ultraviolet light for 1 hour to form a complete dual-band silver-based electrochromic device, ensuring the long-term stability and sealing of the device.

[0020] Furthermore, the silver-based gel electrolyte is prepared by the following process:

[0021] Dissolve silver nitrate, copper chloride, and tetrabutylammonium bromide in dimethyl sulfoxide;

[0022] Subsequently, polyvinyl butyral accounting for 10% of the total mass of the system was added to dimethyl sulfoxide, and the mixture was mixed with magnetic stirring at 800 rpm at room temperature of 25° C. for 12-15 hours to gel the electrolyte to obtain a silver-based gel electrolyte.

[0023] Furthermore, the molar ratio of bromine element:silver element:copper element is 25:5:1, and the mass of dimethyl sulfoxide solvent is 15 times the sum of the masses of silver nitrate, copper chloride and tetrabutylammonium bromide.

[0024] Furthermore, the polyvinyl butyral accounts for 10% of the total mass of the system.

[0025] In the second aspect, the present invention provides an application of a dual-band silver-based electrochromic device that dynamically regulates solar and mid-infrared radiation. The electrochromic device can be directly used to replace transparent enclosure structures such as vertical windows and skylights of buildings and cars (that is, it can be directly used as a transparent enclosure structure). By applying or removing a -2.5V pulse voltage in combination with a mechanical plane flip, it can be controlled to dynamically and reversibly switch between radiation cooling and solar heating modes to meet the thermal management needs of hot and cold seasons.

[0026] Specifically, in hot seasons, a -2.5V pulse voltage is applied to deposit silver ions onto the surface of the indium tin oxide electrode, putting the device in a state of high solar reflectivity, blocking solar heat from entering the room. In this state, the quartz glass of the device faces the outside world, and it has a high mid-infrared emissivity, which can dissipate indoor heat to outer space through spontaneous infrared radiation, activating the radiation cooling mode. In cold seasons, the device will flip its plane, the applied voltage will be removed, and the silver nanoparticles will dissolve to transform the device into a high solar transmittance state, making full use of solar energy for indoor heating. At this time, the indium tin oxide film facing the outside of the device has the characteristics of low mid-infrared emissivity, which can reduce the loss of indoor heat to the external environment and activate the solar heating mode.

[0027] In summary, by combining silver-based electrochromic and planar mechanical flipping technologies, the device achieves dual-band dynamic regulation of high solar reflectivity / high solar transmittance and high-mid infrared emissivity / low mid-infrared emissivity, enabling it to dynamically switch between radiation cooling and solar heating modes.

[0028] Through the above scheme, the present invention can achieve bidirectional reversible regulation of solar radiation and mid-infrared radiation (dual-band) of transparent enclosure structures (windows), so that it can dynamically switch between radiation cooling and solar heating modes, provide efficient and suitable energy regulation methods for transparent enclosure structures in different seasons and regions, and improve the energy-saving performance of buildings and cars as well as indoor thermal comfort.

[0029] Different from CN202411658707.1 and others, this application has obvious improvements or advantages in the following aspects:

[0030] 1. In terms of structural form, the present application adopts an asymmetric structure of "single-sided indium tin oxide-quartz glass / electrolyte / double-sided indium tin oxide-quartz glass", while CN202411658707.1 adopts a symmetrical structure of "single-sided indium tin oxide-PET / electrolyte / single-sided indium tin oxide-PET";

[0031] 2. In terms of radiation regulation, the device described in this application can realize bidirectional dynamic regulation of sunlight and mid-infrared dual-band radiation, while CN202411658707.1 can only realize radiation regulation of sunlight, and mid-infrared radiation cannot be adjusted;

[0032] 3. In terms of application methods, the device described in this application is limited to "the thickness of the quartz glass is 1.0-1.2mm, and the thickness of the indium tin oxide on each side is 135-200nm". The device itself has sufficient mechanical strength and can be used as a transparent enclosure structure alone; while CN202411658707.1 is limited to "PET thickness 0.125mm, indium tin oxide thickness 55nm", and the device is suitable for use in bonding to transparent enclosure structures.

[0033] 4. In terms of energy efficiency, the device described in CN202411658707.1 has the characteristics of high solar reflectivity and high and medium infrared emissivity in radiation cooling mode, and high solar transmittance and high and medium infrared emissivity in solar heating mode, which makes it unsuitable for the mid-infrared radiation characteristics of transparent enclosures in cold seasons to a certain extent: the mid-infrared emissivity of transparent enclosures in cold seasons should be as low as possible to reduce the loss of indoor heat to the outside. The device described in this application has the characteristics of high solar reflectivity and high and medium infrared emissivity in radiation cooling mode, and high solar transmittance and low mid-infrared emissivity in solar heating mode, which perfectly meets the radiation characteristics requirements of transparent enclosures in hot and cold seasons, and has a stronger all-season energy-saving effect.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] (1) The present invention provides a dual-band silver-based electrochromic device that dynamically regulates solar and mid-infrared radiation. Through the effective combination of voltage application / removal and planar mechanical flipping, dual-band bidirectional reversible regulation of solar radiation and mid-infrared radiation is achieved, so that the device can dynamically switch between a radiation cooling mode with high solar reflectivity and high and medium infrared emissivity and a solar heating mode with high solar transmittance and low mid-infrared emissivity.

[0036] (2) The thickness of the indium tin oxide film of the present invention is carefully designed to meet the characteristics of low mid-infrared emission: the indium tin oxide film with a thickness of 135-200nm has the characteristics of high and medium infrared reflection, corresponding to the characteristics of low mid-infrared emission; the indium tin oxide film with a thickness of 135nm can achieve a mid-infrared emissivity of less than 20%, and the mid-infrared emissivity of the indium tin oxide film with a thickness of 200nm can be as low as 10%, which is close to the theoretical limit.

[0037] (3) Through plasma cleaning of the indium tin oxide electrode surface and self-assembly modification of the thiol monolayer, the binding force of silver nanoparticles on the electrode surface is enhanced, significantly improving the solar reflectivity of the device in the radiation cooling state. Combined with the high emissivity of the quartz glass surface in the mid-infrared band, the energy lost to the outdoors is greater than the solar heat entering the room, and the temperature can be reduced to below the ambient temperature, achieving a "net zero energy consumption" state.

[0038] (4) The device has excellent dual-band solar and mid-infrared radiation modulation capabilities, a simple preparation process, controllable composition and structure, and is easy to customize in size and expand to large-scale production. It has great application prospects in the all-season dynamic thermal management of transparent enclosures such as modern buildings and automobile windows. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 Schematic diagram of the preparation process of the electrochromic device;

[0040] Figure 2 Schematic diagram of the structure and state of the electrochromic device in the radiation cooling mode and the solar heating mode;

[0041] Figure 3 The photos of the electrochromic device in two modes: radiation cooling and solar heating;

[0042] Figure 4 The apparent temperatures of the quartz glass surface and the indium tin oxide surface facing the outside world under the two modes of radiation cooling and solar heating observed by the infrared thermal imager;

[0043] Figure 5 This is a cross-sectional photograph of an indium tin oxide-quartz glass transparent electrode observed using a scanning electron microscope. DETAILED DESCRIPTION

[0044] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0045] In the following examples, unless otherwise specified, raw materials or processing techniques are conventional commercially available raw materials or conventional processing techniques in the art.

[0046] Example 1

[0047] A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation, the preparation method is as follows:

[0048] a) Use commercial single-sided indium tin oxide-quartz glass and double-sided indium tin oxide-quartz glass electrodes (purchased from South China Xiangcheng Technology Co., Ltd., resistance ≤ 6Ω), the thickness of the quartz glass is 1.1mm, and the thickness of the indium tin oxide film is about 190nm (see Figure 5 ).

[0049] b) Plasma cleaning of the indium tin oxide electrode surface: The transparent conductive electrode was ultrasonically cleaned in acetone, isopropanol, ethanol and deionized water for 15 minutes, and then dried at 60°C for 4 hours in a nitrogen atmosphere; the dried electrode surface was cleaned with oxygen plasma for 15 minutes to remove residual organic impurities and hydroxylate the surface.

[0050] c) Self-assembly modification of the thiol monolayer on the surface of the indium tin oxide electrode: the transparent conductive electrode after oxygen plasma cleaning was immersed in a mixed solution of 3-mercaptopropyltrimethoxysilane: toluene (volume ratio of 1:40) for 15 hours; then, the immersed electrode was ultrasonically treated in ethanol for 15 minutes to remove the remaining unbound monomers on the electrode surface; and then the electrode was dried at 60°C in a nitrogen atmosphere for 4 hours.

[0051] d) Preparation of a silver-based gel electrolyte: 170 mg of silver nitrate, 26 mg of copper chloride, and 1612 mg of tetrabutylammonium bromide were dissolved in 25 ml of dimethyl sulfoxide solvent in sequence, and then polyvinyl butyral in an amount of 10% by mass of the total system was added to the dimethyl sulfoxide, and the mixture was mixed with magnetic stirring at 800 rpm at room temperature of 25° C. for 12 h to gel the electrolyte to obtain a silver-based gel electrolyte.

[0052] e) Device assembly: Place the single-sided indium tin oxide-quartz glass working electrode and the double-sided indium tin oxide-quartz glass counter electrode in parallel and offset, with the indium tin oxide conductive layer facing inward. The offset is exposed by 0.5 cm, and the two electrodes are bonded with 3MVHB double-sided transparent adhesive with a thickness of 0.5 mm, leaving a gap of 0.1 mm for injection. Then inject the prepared silver-based gel electrolyte between the two transparent conductive electrodes until the internal gap of the electrodes is filled, constructing a three-layer structure of electrode-electrolyte-electrode.

[0053] f) Device packaging: Use UV curing glue (brand: MECHANIC) to fill the reserved injection gap and 2 The package is cured under ultraviolet light for 1 hour to form a complete dual-band silver-based electrochromic device.

[0054] The optical properties of the device in the range of sunlight wavelength (0.3-2.5μm) were characterized using an ultraviolet-visible near-infrared spectrometer (brand: Shimadzu, model: UV-3600i Plus); the optical properties of the device in the range of mid-infrared wavelength (2.5-20μm) were characterized using a Fourier transform infrared spectrometer (brand: Thermo Fisher Scientific, model Nicolet iS50). The test results show that the device has a sunlight transmittance of 61.16% and a mid-infrared emissivity of 11.6% in the solar heating state (no voltage applied, indium tin oxide film facing the test); a waveform generator (brand: Agilent, model 33210A) was used to apply a pulse voltage of -2.5V, a dense and bright silver nanofilm was deposited at the negative electrode, and the device was flipped (quartz glass surface facing the test), which was in the radiation cooling state, and the device had a sunlight reflectivity of 87.91% and a mid-infrared emissivity of 88.37%.

[0055] Example 2

[0056] A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation, the preparation method is as follows:

[0057] a) Use commercial single-sided indium tin oxide-quartz glass and double-sided indium tin oxide-quartz glass electrodes (purchased from South China Xiangcheng Technology Co., Ltd., resistance ≤ 6Ω), the thickness of the quartz glass is 1.1 mm, and the thickness of the indium tin oxide film is about 190 nm.

[0058] b) Plasma cleaning of the indium tin oxide electrode surface: The transparent conductive electrode was ultrasonically cleaned in acetone, isopropanol, ethanol and deionized water for 12 minutes, and then dried at 60°C for 3 hours in a nitrogen atmosphere; the dried electrode surface was cleaned with oxygen plasma for 12 minutes to remove residual organic impurities and hydroxylate the surface.

[0059] c) Self-assembly modification of the surface of the indium tin oxide electrode with a thiol monolayer: the transparent conductive electrode after oxygen plasma cleaning was immersed in a mixed solution of 3-mercaptopropyltrimethoxysilane: toluene (volume ratio of 1:40) for 12 hours; then, the immersed electrode was ultrasonically treated in ethanol for 12 minutes to remove the remaining unbound monomers on the electrode surface; and then the electrode was dried at 60°C in a nitrogen atmosphere for 3 hours.

[0060] d) Preparation of a silver-based gel electrolyte: 170 mg of silver nitrate, 26 mg of copper chloride, and 1612 mg of tetrabutylammonium bromide were dissolved in 25 ml of dimethyl sulfoxide solvent in sequence, and then polyvinyl butyral in an amount of 10% by mass of the total system was added to the dimethyl sulfoxide, and the mixture was mixed with magnetic stirring at 800 rpm at room temperature of 25° C. for 12 h to gel the electrolyte to obtain a silver-based gel electrolyte.

[0061] e) Device assembly: Place the single-sided indium tin oxide-quartz glass working electrode and the double-sided indium tin oxide-quartz glass counter electrode in parallel and offset, with the indium tin oxide conductive layer facing inward. Exposed 1 cm, use 0.5 mm thick 3M VHB double-sided transparent adhesive to bond the two electrodes, leaving a 0.1 mm wide injection gap. Then inject the prepared silver-based gel electrolyte between the two transparent conductive electrodes until the internal gap of the electrodes is filled, constructing a three-layer structure of electrode-electrolyte-electrode.

[0062] f) Device packaging: Use UV curing glue (brand: MECHANIC) to fill the reserved injection gap and 2 The package is cured under ultraviolet light for 1 hour to form a complete dual-band silver-based electrochromic device.

[0063] The optical properties of the device in the range of sunlight wavelength (0.3-2.5μm) were characterized using an ultraviolet-visible near-infrared spectrometer (brand: Shimadzu, model: UV-3600i Plus); the optical properties of the device in the range of mid-infrared wavelength (2.5-20μm) were characterized using a Fourier transform infrared spectrometer (brand: Thermo Fisher Scientific, model Nicolet iS50). The test results show that the device has a sunlight transmittance of 60.61% and a mid-infrared emissivity of 11.9% in the solar heating state (no voltage applied, indium tin oxide film facing the test); a waveform generator (brand: Agilent, model 33210A) was used to apply a pulse voltage of -2.5V, a dense and bright silver nanofilm was deposited at the negative electrode, and the device was flipped (quartz glass surface facing the test), which was in the radiation cooling state, and the device had a sunlight reflectivity of 85.57% and a mid-infrared emissivity of 89.51%.

[0064] Comparative Example 1

[0065] A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation, the preparation method is as follows:

[0066] a) Two commercial single-sided indium tin oxide-quartz glass electrodes (purchased from South China Xiangcheng Technology Co., Ltd., resistance ≤ 6Ω) were used, the thickness of the quartz glass was 1.1 mm, and the thickness of the indium tin oxide film was about 190 nm.

[0067] b) Plasma cleaning of the indium tin oxide electrode surface: The transparent conductive electrode was ultrasonically cleaned in acetone, isopropanol, ethanol and deionized water for 12 minutes, and then dried at 60°C for 3 hours in a nitrogen atmosphere; the dried electrode surface was cleaned with oxygen plasma for 12 minutes to remove residual organic impurities and hydroxylate the surface.

[0068] c) Self-assembly modification of the surface of the indium tin oxide electrode with a thiol monolayer: the transparent conductive electrode after oxygen plasma cleaning was immersed in a mixed solution of 3-mercaptopropyltrimethoxysilane: toluene (volume ratio of 1:40) for 12 hours; then, the immersed electrode was ultrasonically treated in ethanol for 12 minutes to remove the remaining unbound monomers on the electrode surface; and then the electrode was dried at 60°C in a nitrogen atmosphere for 3 hours.

[0069] d) Preparation of a silver-based gel electrolyte: 170 mg of silver nitrate, 26 mg of copper chloride, and 1612 mg of tetrabutylammonium bromide were dissolved in 25 ml of dimethyl sulfoxide solvent in sequence, and then polyvinyl butyral in an amount of 10% by mass of the total system was added to the dimethyl sulfoxide, and the mixture was mixed with magnetic stirring at 800 rpm at room temperature of 25° C. for 12 h to gel the electrolyte to obtain a silver-based gel electrolyte.

[0070] e) Device assembly: Place two single-sided indium tin oxide-quartz glass electrodes in parallel and offset, with the indium tin oxide conductive layer facing inward. Exposed 1 cm from the offset, use 0.5 mm thick 3M VHB double-sided transparent adhesive to bond the two electrodes, leaving a 0.1 mm wide gap for injection. Then inject the prepared silver-based gel electrolyte between the two transparent conductive electrodes until the internal gap of the electrodes is filled, constructing a three-layer structure of electrode-electrolyte-electrode.

[0071] f) Device packaging: Use UV curing glue (brand: MECHANIC) to fill the reserved injection gap and 2 The package is cured under ultraviolet light for 1 hour to form a complete dual-band silver-based electrochromic device.

[0072] The optical properties of the device in the range of sunlight wavelength (0.3-2.5μm) were characterized using an ultraviolet-visible near-infrared spectrometer (brand: Shimadzu, model: UV-3600i Plus); the optical properties of the device in the range of mid-infrared wavelength (2.5-20μm) were characterized using a Fourier transform infrared spectrometer (brand: Thermo Fisher Scientific, model Nicolet iS50). The test results show that the device has a sunlight transmittance of 63.31% and a mid-infrared emissivity of 89.45% in the solar heating state (no voltage applied, indium tin oxide film facing the test); a waveform generator (brand: Agilent, model 33210A) was used to apply a pulse voltage of -2.5V, a dense and bright silver nanofilm was deposited at the negative electrode, and the device was flipped (quartz glass surface facing the test), which was in the radiation cooling state, and the device had a sunlight reflectivity of 85.9% and a mid-infrared emissivity of 89.23%.

[0073] The device structure and the actual working status are shown in the figure below. Figures 1 to 3 As shown, Figure 1 The preparation process of the dual-band silver-based electrochromic device is presented in the form of a flow chart, including the schematic diagram of plasma cleaning and thiol monolayer self-assembly modification. Figure 2 Schematic diagram of the structure and state of the device in radiation cooling and solar heating modes: in radiation cooling mode, a pulse voltage of -2.5V is applied to the device and the quartz glass surface is facing the outside world. The device as a whole exhibits a state of high reflection of sunlight and high emission of mid-infrared. In solar heating mode, the voltage is removed to restore the device to a high transmittance state, and the device is flipped so that the indium tin oxide film faces the outside world. The device as a whole exhibits a state of high transmittance of sunlight and low emission of mid-infrared. Figure 3 These are photos of the two modes of radiation cooling and solar heating of the actual device prepared in Example 1: applying a pulse voltage of -2.5V puts the device in radiation cooling mode, with high sunlight reflectivity, and the reflection of the panda ornament in front of the device can be clearly seen; removing the applied voltage, the device returns to solar heating mode, with high sunlight transmittance, and the ornament behind the device can be clearly seen.

[0074] Figure 4 Two physical devices prepared in Example 1 that are completely identical are placed on a heating platform at 50°C. The device on the left has the quartz glass side facing upward (corresponding to the radiation cooling mode), and the device on the right has the indium tin oxide side facing upward (corresponding to the solar heating mode). Significant differences are observed using an infrared thermal imaging instrument: the higher apparent temperature of the quartz glass represents its high emissivity in the mid-infrared spectrum, and the lower apparent temperature of the indium tin oxide film represents its low emissivity in the mid-infrared spectrum.

[0075] Figure 5 This is a cross-sectional view of an indium tin oxide-quartz glass electrode observed using a scanning electron microscope. The indium tin oxide film and the quartz glass substrate can be clearly seen. The thickness of the indium tin oxide film is about 190 nm.

[0076] A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation prepared by this method can achieve bidirectional and reversible regulation of solar radiation and mid-infrared radiation (dual-band) of transparent envelope structures (windows), enabling dynamic switching between radiation cooling and solar heating modes, providing an efficient and suitable energy regulation method for transparent envelope structures in different seasons and regions, and improving the energy-saving performance of buildings and automobiles.

[0077] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation, comprising two transparent conductive electrodes as a working electrode and a counter electrode, respectively, a silver-based gel electrolyte and a transparent packaging material, characterized in that: The transparent conductive electrode is an indium tin oxide-quartz glass electrode, wherein the working electrode is a single-sided indium tin oxide-quartz glass, and the counter electrode is a double-sided indium tin oxide-quartz glass. The working electrode and the counter electrode are placed in parallel and offset, and are bonded and fixed by a transparent packaging material. Then, a silver-based gel electrolyte is injected between the two transparent conductive electrodes to form a three-layer structure of electrode-electrolyte-electrode.

2. A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation according to claim 1, characterized in that: The thickness of the quartz glass used in the transparent conductive electrode is 1.0-1.2 mm, and the thickness of the indium tin oxide on each side is 135-200 nm.

3. A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation according to claim 1, characterized in that: The indium tin oxide surface of the transparent conductive electrode is also subjected to oxygen plasma cleaning and thiol monolayer self-assembly modification treatment.

4. A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation according to claim 3, characterized in that: The oxygen plasma cleaning process is specifically as follows: The transparent conductive electrode was ultrasonically cleaned in acetone, isopropanol, ethanol and deionized water for 12-15 minutes, and then dried at 60°C in a nitrogen atmosphere for 3-4 hours; then the dried electrode surface was cleaned with oxygen plasma for 12-15 minutes; The self-assembly modification process is specifically as follows: The transparent conductive electrode after oxygen plasma cleaning was immersed in a mixed solution of 3-mercaptopropyltrimethoxysilane: toluene with a volume ratio of 1:40 for 12-15 hours; then, the immersed transparent conductive electrode was ultrasonically treated in ethanol for 12-15 minutes, and then the electrode was dried at 60°C in a nitrogen atmosphere for 3-4 hours.

5. The dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation according to claim 1, characterized in that: The two transparent conductive electrodes are placed in parallel, and the side with indium tin oxide is located inside the electrode and faces the silver-based gel electrolyte; Two transparent conductive electrodes are arranged in a staggered manner, and both sides of the staggered electrodes are exposed by 0.5-1 cm for applying voltage.

6. A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation according to claim 5, characterized in that: The bonding and fixing process of the transparent packaging material is as follows: A transparent packaging material with a thickness of 0.5 mm is used to bond two parallel and offset transparent conductive electrodes, and a liquid injection gap with a width of 0.1 mm is left at the corner of the bonding quadrilateral.

7. A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation according to claim 6, characterized in that: The transparent packaging material is VHB closed-cell acrylic foam.

8. A dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation according to claim 6, characterized in that: After the silver-based gel electrolyte is injected through the injection gap, the injection gap is encapsulated using ultraviolet curing glue.

9. The dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation according to claim 1, characterized in that: The silver-based gel electrolyte is prepared by the following process: Dissolve silver nitrate, copper chloride, and tetrabutylammonium bromide in dimethyl sulfoxide; Subsequently, polyvinyl butyral was added to dimethyl sulfoxide, and the mixture was mixed with magnetic stirring at 800 rpm at room temperature of 25° C. for 12-15 h to gel the electrolyte to obtain a silver-based gel electrolyte.

10. Application of a dual-band silver-based electrochromic device for dynamically regulating solar and mid-infrared radiation as claimed in any one of claims 1 to 9, characterized in that: By applying or removing a -2.5V pulse voltage combined with mechanical plane flipping, it can be controlled to dynamically reversibly switch between radiative cooling and solar heating modes to adapt to the thermal management needs of hot and cold seasons.

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