CN116136630A - Bistable electrochromic device with thermal switch response and preparation method thereof - Google Patents

Abstract

The invention relates to a bistable electrochromic device with thermal switch response and a preparation method thereof. The bistable electrochromic device of thermal switch response includes: a transparent electrode layer, a thermally induced phase change switch layer, an electrochromic layer, an ion conducting layer and a top electrode layer which are sequentially arranged; the thermally-induced phase change switch layer is at least one selected from vanadium dioxide, vanadium trioxide, vanadium pentoxide and samarium nickelate; preferably, the thickness of the thermally induced phase change switching layer is 5nm to 40nm, more preferably 10nm to 30 nm.

Description

Bistable electrochromic device with thermal switch response and preparation method thereof

Technical Field

The invention relates to a bistable electrochromic device with thermal switch response and a preparation method thereof, belonging to the technical field of chemical material synthesis and functional materials.

Background

The energy is an important foundation for maintaining national economic sustainable development and guaranteeing the living standard of people's substances. Today, the problems of energy shortage, environmental pollution and the like are increasingly severe, and scientists are striving to find a method for saving energy and reducing consumption while developing new energy. The building is one of the main sites where human beings perform production and living activities, and in the total energy consumption of human beings, the building energy consumption accounts for a large proportion, while in the building energy consumption, the energy consumption of the lighting and air conditioning system for improving the comfort of the building accounts for more than 75 percent. Both parts of energy consumption are related to door and window glass, so developing building glass with energy-saving effect is an important way for realizing energy saving of building. The current way of controlling energy loss of architectural glass is static, for example Low-E glass with high reflectivity in the infrared band, which can prevent infrared from penetrating through the window; the hollow glass utilizes the low coefficient of thermal conductivity of air to reduce the conduction and heat dissipation between the indoor and outdoor. Scientists in the last century of 80 s put forward the concept of an intelligent window based on electrochromic materials, namely a building window structural material capable of actively regulating and controlling visible and near infrared transmission light intensity, dynamically regulating the intensity of the incident indoor light according to the difference between indoor and outdoor environments, reducing the use of an air conditioner and a lighting system, and combining with Low-E and hollow glass to achieve better energy-saving effect. The performance of electrochromic materials determines the intensity of the light adjusting capability of the intelligent window, and electrochromic materials are widely paid attention to. Electrochromic refers to the phenomenon that the optical properties of a material, such as transmittance, and reflectivity change reversibly under low voltage driving, and the appearance of the material shows reversible changes between blue and transparent states. Electrochromic is a hot spot studied nowadays and has a wide application range. The electrochromic device and the technology are mainly applied to the fields of energy-saving building glass, other movable body windows, anti-dazzle rearview mirrors of automobiles, display screens, electronic paper, camouflage and the like.

Conventional electrochromic devices are composed of five layers of thin films, including two transparent conductive layers, an ion storage layer, an electrochromic layer, and an ion conducting layer. Wherein, the ion storage layer assists the electrochromic layer to apply low voltage on the first and second conductive layers to realize electrochromic reaction. Ion conductive layers are provided with lithium ions and a diffusion film layer, which is responsible for ensuring ion conductivity under the action of an electric field, and the structure and the preparation process of the ion conductive layers are one of the most important technologies for ensuring electrochromic performance of devices. Electrochromic devices can be classified into three types according to the state of an ion conducting layer, respectively: liquid electrochromic devices, gel electrochromic devices, and all-solid electrochromic devices, wherein the gel electrochromic devices are quasi-solid electrochromic devices. Packaging, leakage and the like of the liquid electrochromic device; compared with the problems of slow response time, poor ionic conductivity and the like of an all-solid-state electrochromic device, the quasi-solid-state electrochromic device has better stability, simple preparation process and higher response time than the all-solid-state electrochromic device. Moreover, conventional electrochromic devices tend to have some bistable electrochromic properties, but such devices can only be driven by an electric field.

Disclosure of Invention

Aiming at the problem that the bistable electrochromic device in the prior art is often controlled by an electric field only and is difficult to meet the application requirements of increasing complexity, the invention aims to provide the bistable electrochromic device with thermal switch response and a preparation method thereof. The bistable property means that after the device is colored under the applied voltage, the voltage is removed, the color of the device can be still maintained, and the low transmittance can be still maintained for a long time until the device is restored to the original state after the corresponding reverse voltage is applied.

In one aspect, the present invention provides a thermally-responsive bistable electrochromic device comprising: a transparent electrode layer, a thermally induced phase change switch layer, an electrochromic layer, an ion conducting layer and a top electrode layer which are sequentially arranged; the thermally-induced phase change switch layer is at least one selected from vanadium dioxide, vanadium trioxide, vanadium pentoxide and samarium nickelate; the method comprises the steps of carrying out a first treatment on the surface of the Preferably, the thickness of the thermally induced phase change switching layer is 5nm to 40nm, more preferably 10nm to 30nm, and most preferably 15nm to 25nm. Wherein the transparent electrode layer and the thermally-induced phase change switch layer exist as a composite electrode.

In the present disclosure, a thermal phase change material (semiconductor state before phase change, capable of effectively isolating electrons, and making a device have better electronic insulation property) with specific composition and thickness is introduced as a thermal switch for controlling an electrochromic device. Thus, the prepared bistable electrochromic device has the following four states according to temperature and voltage: (1) at room temperature, electrically non-drivable; (2) heating, electrochromic; (3) cooling, and presenting bistable property; (4) And heating and applying reverse voltage to restore the device to the original state. If the thermally induced phase change switch layer is too thick, the resistance is higher, so that the resistance of the composite electrode of the thermally induced color change layer and the transparent conductive electrode is too high, the response speed of the electrochromic process of the subsequent device is slow, and the driving voltage is too high. On the other hand, if the thermally-induced phase change switching layer is too thin, it is difficult to completely cover the rough electrode surface, and a relatively clear thermal control effect is not achieved.

Preferably, the electrochromic layer is a wide bandgap semiconductor oxide, preferably selected from WO ₃ 、MoO、TiO ₂ At least one of ZnO.

Preferably, the electrochromic layer has a thickness of 400 to 2000nm, preferably 500 to 800nm.

Preferably, the transparent electrode layer is at least one of a transparent conductive oxide, a transparent silicon electrode and a transparent noble metal nanowire electrode; preferably, the transparent conductive oxide is selected from at least one of FTO, ITO, ATO.

Preferably, the sheet resistance of the transparent electrode layer is 5-50 ohm/cm ² The average visible light transmittance is more than 75 percent。

Preferably, the top electrode layer is at least one of a transparent conductive oxide, a transparent silicon electrode and a transparent noble metal nanowire electrode; preferably, the transparent conductive oxide is selected from at least one of FTO, ITO, ATO.

Preferably, the sheet resistance of the top electrode layer is 5-50 ohm/cm ² The average visible light transmittance is more than 75%.

Preferably, the ion conducting layer is a photocurable resin dispersion liquid with a cation content of 1-10 wt% (mass concentration); the cation includes Li ⁺ 、Na ⁺ 、Al ³⁺ At least one of them.

Preferably, the bistable electrochromic device of the thermal switch response cannot cause device discoloration when voltage is applied at room temperature; when the temperature is heated to be above the phase transition temperature, the voltage applying device is colored; when the temperature is reduced below the phase transition temperature, the bistable state performance is presented; and when the temperature is heated to be above the phase transition temperature again, the device returns to the initial state after the reverse voltage is applied.

In another aspect, the present invention provides a method of preparing a thermally-responsive bistable electrochromic device comprising:

(1) Depositing a thermally-induced phase change switch layer and an electrochromic layer on the surface of the transparent electrode layer by magnetron sputtering;

(2) Printing a photo-curing resin dispersion liquid with the cation content of 1-10% (mass concentration) on the surface of the electrochromic layer through a screen;

(3) And after preparing the top electrode by magnetron sputtering deposition, ultraviolet light is adopted for curing, so that the bistable electrochromic device with the thermal switch response is obtained.

The beneficial effects are that:

the invention provides a bistable electrochromic device with thermal switch response and a preparation method thereof. The contact state between interfaces of all layers is regulated by regulating the thickness and the preparation process of all functional layers in the device, so that the bistable electrochromic device which can be widely popularized and has use value is obtained.

In the invention, after the bistable electrochromic device responded by the thermal switch is colored under the applied voltage, the voltage is removed, the color of the device can still be kept, and the low transmittance can still be kept unchanged for a long time until the device is restored to the initial state after the corresponding reverse voltage is applied. On the contrary, when the device is in a transmission state, the state can be kept until the applied voltage becomes a coloring state, more change modes are presented, and more application scenes can be met.

Drawings

FIG. 1 is a schematic diagram of a bistable electrochromic device having a thermal switch response;

FIG. 2 is a graph of spectral performance of the thermally-switched-response bistable electrochromic device of example 1 in four states;

fig. 3 is a graph showing bistable performance of a bistable electrochromic device having a thermal switch response in example 1.

Detailed Description

The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.

The currently disclosed bistable electrochromic device is designed to regulate the migration rate of lithium ions by structural design so that it can remain confined in the electrochromic layer after the voltage is removed. All-solid-state electrochromic devices, which typically have bistable properties, require some degree of Li confinement ⁺ And therefore the fading speed is slow or a large voltage needs to be applied to completely fade.

In the present disclosure, the basic structure of a bistable electrochromic device includes: a transparent electrode layer, a thermally-induced phase change switching layer, an electrochromic layer, an ion conducting layer, and a top electrode layer. The invention breaks through the limitation that the conventional electrochromic device is only driven by electricity, and can realize thermoelectric double control. The device prepared had four states: room temperature, electric non-driving; heating, electrochromic; cooling, and having bistable property; and heating and applying reverse voltage to restore the device to the original state.

The bistable electrochromic device prepared by using heat as a switch is provided in the patent, namely, the bistable electrochromic device is driven by an electric field, and the thermal field can be driven, so that the use scene of the device is richer. By inserting a layer of thermal phase change material between the electrode and the electrochromic layer, the device cannot be discolored when voltage is applied when the device is prepared at room temperature; when the temperature is heated to be above the phase transition temperature, the voltage applying device is colored; when the temperature is reduced below the phase transition temperature, the device presents bistable property; and when the temperature is heated to be above the phase transition temperature again, the device returns to the initial state after the reverse voltage is applied. The all-solid-state electrochromic device with multiple states can meet the requirements of more and more complex application scenes.

In an alternative embodiment, the thermally-induced phase change switching layer may be at least one of vanadium dioxide, vanadium trioxide, vanadium pentoxide, or samarium nickelate. The thickness of the thermally induced phase change switching layer may be 10 to 30nm, preferably 15 to 25nm. Within this preferred thickness range, the bistable electrochromic device maintains a 3 hour transmittance decay of 15% or less, preferably < 10%, at a wavelength of 670 nm.

In an alternative embodiment, the electrochromic layer comprises WO ₃ 、MoO、TiO ₂ At least one of wide band gap semiconductor oxides such as ZnO. The electrochromic layer may have a thickness of 400 to 2000nm, preferably 500 to 800nm. Bistable displays are a class of erasable smart color-changing devices with ultra-low power consumption and ultra-long standby time. Compared with the traditional LED display, the LED display has the advantages of high contrast, high transparent display, high cycle durability and the like without an external power supply for a long time. Because the low power consumption, the frequent display and the small switching times can effectively reduce the energy consumption of the electronic shelf labels, the electronic labels, the intelligent windows and other practical applications.

The following illustrates exemplary fabrication of a thermally-switch-responsive bistable electrochromic device.

And (3) preparing the thermally-induced phase change switch layer. The magnetron sputtering is adopted, a transparent electrode layer (transparent conductive glass) is used as a substrate, vanadium trioxide or samarium nickelate is used as a target, the total pressure is controlled to be 0.5-2.0Pa, and the oxygen partial pressure is controlled to be 0-50%. The distance between the target and the substrate is 10-20cm. The initial substrate temperature was room temperature. The power of the direct current power supply applied to the target material is 100-400W or the power densityThe degree is 2-8.0W/cm ² The surface is deposited using a direct current power supply. Final deposition of V of 10nm to 30nm ₂ O ₃ 、V ₂ O ₅ 、VO ₂ Or SmNiO ₃ A film.

And preparing an electrochromic layer on the surface of the thermochromic phase-change switch layer. By a magnetron sputtering method, metal tungsten, zinc, molybdenum or titanium is used as a target, sputtering gas is argon and oxygen, the total pressure is 0.5-2.0Pa, and the oxygen partial pressure is 0-50%. The distance between the target and the substrate is 10-20cm. The initial substrate temperature was room temperature. The power of the direct current power supply applied to the target material is 30-150W or the power density is 0.6-3.0W/cm ² The surface is deposited using a direct current power supply. Finally, the electrochromic layer film with the thickness of 500nm-800nm is obtained by deposition.

The resin precursor is prepared according to the prior art, and the slurry is filled between the electrochromic layer and the top electrode by means of vacuum filling or coating. The ion conducting layer is obtained by curing resin slurry conducting cations, and the composition of the resin slurry conducting cations comprises: a solvent, a resin, a stabilizer, an ultraviolet absorber, an organic precursor and an ion source solution, wherein the organic precursor comprises an acid ester compound, and the resin comprises a photo-curing resin or/and a thermosetting resin; the mass ratio of the solvent to the resin to the stabilizer to the ultraviolet absorbent to the organic precursor to the ion source solution is (1-5): 0.5-5): 0.1-2): 0.01-0.2): 0.5-5): 1. The organic precursor is one of ethoxylated trimethylolpropane triacrylate and trimethylolpropane triacrylate. The solvent is at least one of isopropanol, propylene glycol methyl ether acetate, dimethyl nylon acid, dimethylformamide and dimethyl sulfoxide; the thermosetting resin is at least one of polyethylene oxide, epoxy resin, polypropylene resin and phenolic resin, and the photo-curing resin is ultraviolet light curing resin. The stabilizer is a transition metal organic compound, preferably ferrocene and derivatives thereof; the ultraviolet absorber is selected from at least one of BYK1130, BYK 292, UV-234 and UV 5411. The solute in the ion source solution is perchlorate, preferably at least one of lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, zinc perchlorate and aluminum perchlorate; the solvent of the ion source solution is at least one selected from propylene carbonate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and the like; preferably, the mass ratio of the perchlorate to the solvent is 1 (0.5-20).

And preparing the ion conducting layer by adopting a curing treatment mode such as ultraviolet radiation curing or thermal curing and the like to obtain the complete and quick-response bistable electrochromic device. The curing treatment mode is photo-curing treatment or heat-curing treatment; the light curing treatment is that an ultraviolet lamp with the weight of 50-300W is irradiated for 30 seconds-30 minutes; the heat curing treatment is carried out at a temperature of 50-100 ℃ for 10 minutes-2 hours. Preferably, the thickness of the ion conductive layer is 3 to 100 μm.

The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below. The dc magnetron sputtering system apparatus used in the magnetron sputtering deposition of the present invention may include a deposition chamber, a sample introduction chamber, a plurality of targets, a substrate plate, a dc current, and a series of mechanical pumps and vacuum pumps, wherein the targets are at a certain angle to the substrate plate, and a dc power supply is connected to the targets, unless otherwise specified. And ultrasonically cleaning the substrate, respectively ultrasonically cleaning the substrate for 20min by using acetone, absolute ethyl alcohol and deionized water, and drying by using compressed air. Covering a certain part of conductive substrate with high temperature adhesive tape as electrode, fixing on substrate tray, placing into sample chamber, opening mechanical pump to below 5Pa, opening baffle valve, and feeding into vacuum degree (background vacuum degree) of 10 ^-4 Pa and below.

Example 1

Firstly, two ITO transparent conductive glass substrates are used, the substrates are respectively ultrasonically cleaned by acetone, ethanol and deionized water for 20min, then are fixed on a substrate tray by a high-temperature adhesive tape, are put into a sample injection chamber, are mechanically pumped to below 5Pa, are opened to be sent into a vacuum degree (background vacuum degree) to reach 10 ^-4 A sputtering chamber having a pressure of Pa or less. And respectively preparing the electrochromic layer and the thermochromic layer by continuous deposition on the surfaces of the electrochromic layer and the thermochromic layer through a magnetron sputtering method. In V form ₂ O ₃ The method comprises the steps of using a direct current power supply to deposit VO with the power of 20nm on the surface of a target material, wherein the total pressure is 1.0Pa, the oxygen partial pressure is 1.5%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of the direct current power supply applied to the target material is 150W ₂ A film. The method comprises the steps of taking tungsten as a target, taking argon and oxygen as sputtering gas, enabling the total pressure to be 2.0Pa, enabling the oxygen partial pressure to be 6%, enabling the distance between the target and a substrate to be 15cm, enabling the initial substrate temperature to be room temperature, and enabling the direct current power supply applied to the target to be 70W or enabling the power density to be 1.54W/cm ² The deposition time is 45min, and the electrochromic layer film with the thickness of about 550nm is obtained. According to the prior art, a mixture of organic solvent (PMA), stabilizer (ETPTA), curing resin (Mehtou 35), counter electrode (ferrocene) and ion source (PC solution of lithium perchlorate, 1 mol/L) was prepared by vacuum drip or screen printing in a ratio of 2:1:1:0.1:1, filling the resin slurry between the tungsten oxide film and the vanadium oxide film by vacuum filling. The completed device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. Wherein the light curing is to uniformly irradiate the device under a 100W ultraviolet lamp for 1min. After the device is solidified, organic solvent is used to remove the organic matters on the surface of the redundant device. The electrochromic intelligent window device provided by the invention can be obtained, and the structural schematic diagram is shown in figure 1. Since the phase transition temperature of vanadium dioxide is 60 ℃, the phase transition temperature value can be reduced to room temperature by proper doping. Thus, the thermally controlled responsive bistable electrochromic device based on vanadium dioxide thermally induced phase change material in this embodiment is applied to room temperature environment. FIG. 2 shows four voltages of a device, state 1 is a normal state, and the device cannot be driven by electricity to change color; state 2 is a high temperature state, electrically driven such that the deviceColoring; 3, cooling to room temperature, and keeping good color retention of the device; and 4, reheating and applying a reverse voltage to restore the device to the original state. Fig. 3 shows the bistable behavior exhibited in state 3 of the device, since it is seen that the 3-hour transmittance decay is less than 10% at a wavelength of 670 nm.

Example 2

Firstly, two ITO transparent conductive glass substrates are used, the substrates are respectively ultrasonically cleaned by acetone, ethanol and deionized water for 20min, then are fixed on a substrate tray by a high-temperature adhesive tape, are put into a sample injection chamber, are mechanically pumped to below 5Pa, are opened to be sent into a vacuum degree (background vacuum degree) to reach 10 ^-4 A sputtering chamber having a pressure of Pa or less. And respectively preparing the electrochromic layer and the thermochromic layer by continuous deposition on the surfaces of the electrochromic layer and the thermochromic layer through a magnetron sputtering method. In V form ₂ O ₃ The method comprises the steps of using a direct current power supply to deposit VO of 10nm on a surface with 150W of direct current power supply power applied to the target, wherein the total pressure is 1.0Pa, the oxygen partial pressure is 1.5%, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature ₂ A film. The method comprises the steps of taking tungsten as a target, taking argon and oxygen as sputtering gas, enabling the total pressure to be 2.0Pa, enabling the oxygen partial pressure to be 6%, enabling the distance between the target and a substrate to be 15cm, enabling the initial substrate temperature to be room temperature, and enabling the direct current power supply applied to the target to be 70W or enabling the power density to be 1.54W/cm ² The deposition time is 45min, and the electrochromic layer film with the thickness of about 550nm is obtained. According to the prior art, a resin slurry is prepared from an organic solvent (PMA), a stabilizer (ETPTA), a curing resin (Mehtou 35), a counter electrode (ferrocene) and an ion source (PC solution of lithium perchlorate, 1 mol/L) in a ratio of 2:1:1:0.1:1 by vacuum drip irrigation, and is filled between a tungsten oxide film and a vanadium oxide film by vacuum irrigation. The completed device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. Wherein the light curing is to uniformly irradiate the device under a 100W ultraviolet lamp for 1min. After the device is solidified, organic matters on the surface of the redundant device are removed by using an organic solvent, and the electrochromic intelligent window device provided by the invention can be obtained. Tests show that when the vanadium oxide is too thin, the coarse film is difficult to fully coverThe electrode with larger roughness causes poor color retention of the device in state 3, and the attenuation is more than 20% after 3 hours at 670 nm.

Example 3

Firstly, two ITO transparent conductive glass substrates are used, the substrates are respectively ultrasonically cleaned by acetone, ethanol and deionized water for 20min, then are fixed on a substrate tray by a high-temperature adhesive tape, are put into a sample injection chamber, are mechanically pumped to below 5Pa, are opened to be sent into a vacuum degree (background vacuum degree) to reach 10 ^-4 A sputtering chamber having a pressure of Pa or less. And respectively preparing the electrochromic layer and the thermochromic layer by continuous deposition on the surfaces of the electrochromic layer and the thermochromic layer through a magnetron sputtering method. In V form ₂ O ₃ The method comprises the steps of using a direct current power supply to deposit VO (volatile organic compound) of 30nm on a surface with 150W of direct current power supply power applied to a target, wherein the total pressure is 1.0Pa, the oxygen partial pressure is 1.5%, the distance between the target and a substrate is 15cm, the initial substrate temperature is room temperature ₂ A film. The method comprises the steps of taking tungsten as a target, taking argon and oxygen as sputtering gas, enabling the total pressure to be 2.0Pa, enabling the oxygen partial pressure to be 6%, enabling the distance between the target and a substrate to be 15cm, enabling the initial substrate temperature to be room temperature, and enabling the direct current power supply applied to the target to be 70W or enabling the power density to be 1.54W/cm ² The deposition time is 45min, and the electrochromic layer film with the thickness of about 550nm is obtained. According to the prior art, a resin slurry is prepared from an organic solvent (PMA), a stabilizer (ETPTA), a curing resin (Mehtou 35), a counter electrode (ferrocene) and an ion source (PC solution of lithium perchlorate, 1 mol/L) in a ratio of 2:1:1:0.1:1 by vacuum drip irrigation, and is filled between a tungsten oxide film and a vanadium oxide film by vacuum irrigation. The completed device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. Wherein the light curing is to uniformly irradiate the device under a 100W ultraviolet lamp for 1min. After the device is solidified, organic matters on the surface of the redundant device are removed by using an organic solvent, and the electrochromic intelligent window device provided by the invention can be obtained. Tests show that if the thermally induced phase change switch layer is too thick, the resistance is higher, so that the resistance of the composite electrode of the thermally induced color change layer and the transparent conductive electrode is too high, the response speed of the electrochromic process of the subsequent device is slow, and the device is electrically drivenThe pressure is too high. The attenuation is more than 20% after 3h at 670nm, which not only leads to the decrease of the visible light transmittance of the whole device, but also leads to the overhigh voltage during the electrochromic driving of the state 1.

Example 4

Firstly, two ITO transparent conductive glass substrates are used, the substrates are respectively ultrasonically cleaned by acetone, ethanol and deionized water for 20min, then are fixed on a substrate tray by a high-temperature adhesive tape, are put into a sample injection chamber, are mechanically pumped to below 5Pa, are opened to be sent into a vacuum degree (background vacuum degree) to reach 10 ^-4 A sputtering chamber having a pressure of Pa or less. And respectively preparing the electrochromic layer and the thermochromic layer by continuous deposition on the surfaces of the electrochromic layer and the thermochromic layer through a magnetron sputtering method. In V form ₂ O ₃ The method comprises the steps of using a direct current power supply to deposit VO with the power of 20nm on the surface of a target material, wherein the total pressure is 1.0Pa, the oxygen partial pressure is 1.5%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of the direct current power supply applied to the target material is 150W ₂ A film. The method comprises the steps of taking tungsten as a target, taking argon and oxygen as sputtering gas, enabling the total pressure to be 2.0Pa, enabling the oxygen partial pressure to be 6%, enabling the distance between the target and a substrate to be 15cm, enabling the initial substrate temperature to be room temperature, and enabling the direct current power supply applied to the target to be 70W or enabling the power density to be 1.54W/cm ² The deposition time is 45min, and the electrochromic layer film with the thickness of about 500nm is obtained. According to the prior art, a resin slurry is prepared from an organic solvent (PMA), a stabilizer (ETPTA), a curing resin (Mehtou 35), a counter electrode (ferrocene) and an ion source (PC solution of lithium perchlorate, 1 mol/L) in a ratio of 2:1:1:0.1:1 by vacuum drip irrigation, and is filled between a tungsten oxide film and a vanadium oxide film by vacuum irrigation. The completed device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. Wherein the light curing is to uniformly irradiate the device under a 100W ultraviolet lamp for 1min. After the device is solidified, organic matters on the surface of the redundant device are removed by using an organic solvent, and the electrochromic intelligent window device provided by the invention can be obtained. At this time, the device is liable to cause insufficient coloring ability of the device.

Example 5

First, two pieces of ITO are transparentThe conductive glass substrate is characterized in that a substrate is ultrasonically cleaned by acetone, ethanol and deionized water for 20min respectively, then is fixed on a substrate tray by a high-temperature adhesive tape, is put into a sample injection chamber, is mechanically pumped to below 5Pa, is opened to be sent into a vacuum degree (background vacuum degree) to reach 10 ^-4 A sputtering chamber having a pressure of Pa or less. And respectively preparing the electrochromic layer and the thermochromic layer by continuous deposition on the surfaces of the electrochromic layer and the thermochromic layer through a magnetron sputtering method. In V form ₂ O ₃ The method comprises the steps of using a direct current power supply to deposit VO with the power of 20nm on the surface of a target material, wherein the total pressure is 1.0Pa, the oxygen partial pressure is 1.5%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature, the power of the direct current power supply applied to the target material is 150W ₂ A film. The method comprises the steps of taking tungsten as a target, taking argon and oxygen as sputtering gas, enabling the total pressure to be 2.0Pa, enabling the oxygen partial pressure to be 6%, enabling the distance between the target and a substrate to be 15cm, enabling the initial substrate temperature to be room temperature, and enabling the direct current power supply applied to the target to be 70W or enabling the power density to be 1.54W/cm ² The deposition time is 45min, and the electrochromic layer film with the thickness of about 800nm is obtained. According to the prior art, a resin slurry is prepared from an organic solvent (PMA), a stabilizer (ETPTA), a curing resin (Mehtou 35), a counter electrode (ferrocene) and an ion source (PC solution of lithium perchlorate, 1 mol/L) in a ratio of 2:1:1:0.1:1 by vacuum drip irrigation, and is filled between a tungsten oxide film and a vanadium oxide film by vacuum irrigation. The completed device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. Wherein the light curing is to uniformly irradiate the device under a 100W ultraviolet lamp for 1min. After the device is solidified, organic matters on the surface of the redundant device are removed by using an organic solvent, and the electrochromic intelligent window device provided by the invention can be obtained. At this point, the device is susceptible to excessive slow fading in state 4.

Example 6

Firstly, two ITO transparent conductive glass substrates are used, the substrates are respectively ultrasonically cleaned by acetone, ethanol and deionized water for 20min, then are fixed on a substrate tray by a high-temperature adhesive tape, are put into a sample injection chamber, are mechanically pumped to below 5Pa, are opened to be sent into a vacuum degree (background vacuum degree) to reach 10 ^-4 A sputtering chamber having a pressure of Pa or less. And respectively preparing the electrochromic layer and the thermochromic layer by continuous deposition on the surfaces of the electrochromic layer and the thermochromic layer through a magnetron sputtering method. In V form ₂ O ₃ The method comprises the steps of using high-purity argon as sputtering gas, enabling the pressure to be 1.0Pa, enabling the distance between the target and a substrate to be 15cm, enabling the initial substrate temperature to be room temperature, enabling the power of a direct current power supply applied to the target to be 150W, and depositing 20nm of V on the surface by using the direct current power supply ₂ O ₃ A film. The method comprises the steps of taking tungsten as a target, taking argon and oxygen as sputtering gas, enabling the total pressure to be 2.0Pa, enabling the oxygen partial pressure to be 6%, enabling the distance between the target and a substrate to be 15cm, enabling the initial substrate temperature to be room temperature, and enabling the direct current power supply applied to the target to be 70W or enabling the power density to be 1.54W/cm ² The deposition time is 45min, and the electrochromic layer film with the thickness of about 550nm is obtained. According to the prior art, a resin slurry is prepared from an organic solvent (PMA), a stabilizer (ETPTA), a curing resin (Mehtou 35), a counter electrode (ferrocene) and an ion source (PC solution of lithium perchlorate, 1 mol/L) in a ratio of 2:1:1:0.1:1 by vacuum drip irrigation, and is filled between a tungsten oxide film and a vanadium oxide film by vacuum irrigation. The completed device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. Wherein the light curing is to uniformly irradiate the device under a 100W ultraviolet lamp for 1min. After the device is solidified, organic solvent is used to remove the organic matters on the surface of the redundant device. The electrochromic intelligent window device provided by the invention can be obtained, and the structural schematic diagram is shown in figure 1. FIG. 2 shows four voltages of a device, state 1 is a normal state, and the device cannot be driven by electricity to change color; state 2 is a high temperature state, electrically driven to color the device; 3, cooling to room temperature, and keeping good color retention of the device; and 4, reheating and applying a reverse voltage to restore the device to the original state. Fig. 3 shows the bistable behavior exhibited in state 3 of the device, since it is seen that the 3-hour transmittance decay is less than 10% at a wavelength of 670 nm. Since the phase transition temperature of vanadium trioxide is 160k, the thermal switching temperature of the device is reduced to 160k at the moment, and the device can be applied to a low-temperature scene.

Example 7

Firstly, two pieces of ITO are used for penetratingThe transparent conductive glass substrate is prepared by respectively ultrasonic cleaning the substrate with acetone, ethanol and deionized water for 20min, fixing on a substrate tray with high temperature adhesive tape, placing into a sample injection chamber, opening a mechanical pump to below 5Pa, opening a baffle valve, and delivering into vacuum degree (background vacuum degree) to reach 10 ^-4 A sputtering chamber having a pressure of Pa or less. And respectively preparing the electrochromic layer and the thermochromic layer by continuous deposition on the surfaces of the electrochromic layer and the thermochromic layer through a magnetron sputtering method. In V form ₂ O ₃ The method comprises the steps of using a direct current power supply to deposit a surface with the power of 150W applied to the target material, annealing at the temperature of 250 ℃ for 30 seconds in air to obtain V with the thickness of 20nm, wherein the total pressure is 1.0Pa, the oxygen partial pressure is 10%, the distance between the target material and a substrate is 15cm, the initial substrate temperature is room temperature ₂ O ₅ A film. The method comprises the steps of taking tungsten as a target, taking argon and oxygen as sputtering gas, enabling the total pressure to be 2.0Pa, enabling the oxygen partial pressure to be 6%, enabling the distance between the target and a substrate to be 15cm, enabling the initial substrate temperature to be room temperature, and enabling the direct current power supply applied to the target to be 70W or enabling the power density to be 1.54W/cm ² The deposition time is 45min, and the electrochromic layer film with the thickness of about 550nm is obtained. According to the prior art, a resin slurry is prepared from an organic solvent (PMA), a stabilizer (ETPTA), a curing resin (Mehtou 35), a counter electrode (ferrocene) and an ion source (PC solution of lithium perchlorate, 1 mol/L) in a ratio of 2:1:1:0.1:1 by vacuum drip irrigation, and is filled between a tungsten oxide film and a vanadium oxide film by vacuum irrigation. The completed device is formed by uv or thermal curing. The thickness of the resin layer was controlled to 80 μm by the surface tension of the hard template and the resin solution. Wherein the light curing is to uniformly irradiate the device under a 100W ultraviolet lamp for 1min. After the device is solidified, organic matters on the surface of the redundant device are removed by using an organic solvent, and the electrochromic intelligent window device provided by the invention can be obtained, wherein the vanadium pentoxide (the phase transition temperature is about 200 ℃), namely the device prepared in the embodiment can be applied to a high-temperature region.

Example 8

The bistable electrochromic device of thermal switch response in this example 8 is distinguished with reference to example 1 in that: depositing the obtained thermally-induced phase-change switching layer VO ₂ Is 1 in average thickness5nm。

Example 9

The bistable electrochromic device of thermal switch response in this example 9 is distinguished with reference to example 1 in that: depositing the obtained thermally-induced phase-change switching layer VO ₂ Is 25nm.

Example 10

The bistable electrochromic device of thermal switch response in this example 10 is distinguished with reference to example 1 in that: depositing the obtained thermally-induced phase-change switching layer VO ₂ The average thickness of (2) was 5nm.

Example 11

The bistable electrochromic device of thermal switch response in this example 11 is distinguished with reference to example 1 in that: depositing the obtained thermally-induced phase-change switching layer VO ₂ The average thickness of (2) was 40nm.

Example 12

The bistable electrochromic device of thermal switch response in this example 12 is distinguished with reference to example 1 in that: the electrochromic layer WO obtained by deposition ₃ Is 600nm thick.

Example 13

The bistable electrochromic device of thermal switch response in this example 13 is distinguished with reference to example 1 in that: the electrochromic layer WO obtained by deposition ₃ Is 700nm thick.

Table 1 shows the performance parameters of the thermally controlled switch responsive bistable electrochromic devices prepared according to the present invention:

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Claims (7)

1. a bistable electrochromic device of the thermal switch response, comprising: a transparent electrode layer, a thermally induced phase change switch layer, an electrochromic layer, an ion conducting layer and a top electrode layer which are sequentially arranged; the thermally-induced phase change switch layer is at least one selected from vanadium dioxide, vanadium trioxide, vanadium pentoxide and samarium nickelate; preferably, the thickness of the thermally induced phase change switching layer is 5nm to 40nm, more preferably 10nm to 30 nm.

2. A bistable electrochromic device according to claim 1, characterized in that said electrochromic layer is a wide bandgap semiconductor oxide, preferably selected from WO ₃ 、MoO、TiO ₂ At least one of ZnO; the electrochromic layer has a thickness of 400 to 2000 a nm a, preferably 500 to 800 a nm a.

3. The thermally-switched-responsive bistable electrochromic device of claim 1, wherein said transparent electrode layer is at least one of a transparent conductive oxide, a transparent silicon electrode, a transparent noble metal nanowire electrode; preferably, the transparent conductive oxide is selected from at least one of FTO, ITO, ATO; the sheet resistance of the transparent electrode layer is 5-50 omega/cm ² The average visible light transmittance is more than 75%.

4. The thermally-switched-responsive bistable electrochromic device of claim 1, wherein said top electrode layer is at least one of a transparent conductive oxide, a transparent silicon electrode, a transparent noble metal nanowire electrode; preferably, the transparent conductive oxide is selected from at least one of FTO, ITO, ATO; the sheet resistance of the top electrode layer is 5-50 omega/cm ² The average visible light transmittance is more than 75%.

5. The thermally-switch-responsive bistable electrochromic device of claim 1, wherein said ion-conducting layer is a photocurable resin dispersion having a cation content of 1-10 wt%; the cation includes Li ⁺ 、Na ⁺ 、Al ³⁺ At least one of (a)One of the two.

6. The thermally-responsive bistable electrochromic device of claim 1, wherein said thermally-responsive bistable electrochromic device is not capable of causing device discoloration upon application of a voltage at room temperature; when the temperature is heated to be above the phase transition temperature, the voltage applying device is colored; when the temperature is reduced below the phase transition temperature, the bistable state performance is presented; and when the temperature is heated to be above the phase transition temperature again, the device returns to the initial state after the reverse voltage is applied.

7. A method of making a thermally switched responsive bistable electrochromic device according to any one of claims 1 to 6, comprising:

(1) Depositing a thermally-induced phase change switch layer and an electrochromic layer on the surface of the transparent electrode layer by magnetron sputtering;

(2) Printing a light-cured resin dispersion liquid with the cation content of 1-10wt% on the surface of the electrochromic layer through a screen;

(3) And after preparing the top electrode by magnetron sputtering deposition, ultraviolet light is adopted for curing, so that the bistable electrochromic device with the thermal switch response is obtained.

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