A fast-response bistable electrochromic device

Abstract

The present invention relates to a fast-response bistable electrochromic device, which comprises a transparent electrode layer, an electrochromic layer with a relatively low lithium-ion binding energy, an electrochromic layer with a relatively high lithium-ion binding energy, an ion conduction layer and a top electrode layer arranged in sequence; and a first fast ion conductor layer and a second fast ion conductor layer are respectively arranged on the upper and lower surfaces of the electrochromic layer with a relatively high lithium-ion binding energy; preferably, the first fast ion conductor layer and the second fast ion conductor layer are selected from at least one of LLZO, LLTO and LIPON.

Description

Technical Field

[0001] The present invention relates to a fast-responsive bistable electrochromic device and a preparation method thereof, belonging to the technical fields of chemical material synthesis and functional materials. Background Art

[0002] Energy is an important foundation for maintaining the sustainable development of a country's economy and ensuring the material living standards of its people. Nowadays, problems such as energy shortage and environmental pollution are becoming increasingly severe. While scientists are developing new energy sources, they are also striving to find ways to save energy and reduce consumption. Buildings are one of the main places where human production and living activities take place. Among the total energy consumption of human production and living, building energy consumption accounts for a large proportion. Among building energy consumption, the energy consumption of lighting and air-conditioning systems used to improve building comfort accounts for more than 75% of the total building energy consumption. The energy consumption of these two parts is related to window glass. Therefore, developing energy-saving building glass is an important way to achieve building energy conservation. The current way for building glass to control energy loss is static. For example, Low-E glass with a high reflectivity in the infrared band can prevent infrared rays from passing through the window; insulating glass uses the low thermal conductivity of air to reduce the conduction heat dissipation between indoors and outdoors. In the 1980s, based on electrochromic materials, scientists proposed the concept of "smart window" - an architectural window structure material that actively regulates the intensity of visible and near-infrared transmitted light, can dynamically adjust the intensity of light entering the room according to the differences in the indoor and outdoor environments, reduce the use of air-conditioning and lighting systems, and can achieve better energy-saving effects when combined with Low-E and insulating glass. The performance of electrochromic materials determines the ability of "smart windows" to regulate light, and electrochromic materials have thus attracted extensive attention. Electrochromism refers to the phenomenon that the optical properties of materials, such as transmittance and reflectivity, undergo reversible color changes under low-voltage drive, and it appears as a reversible change between blue and transparent states in appearance. As a current research hotspot, electrochromism has a wide range of application fields. Electrochromic devices and technologies are mainly applied in fields such as energy-saving building glass, windows of other moving bodies, automotive anti-glare rearview mirrors, display screens, electronic paper, stealth camouflage, etc.

[0003] Traditional electrochromic devices mainly consist of five thin films, including two transparent conductive layers, an ion storage layer, an electrochromic layer, and an ion conduction layer. Among them, the ion storage layer assists the electrochromic layer to apply a low voltage on the first and second conductive layers to achieve an electrochromic reaction. The ion conduction layer is a thin film layer that provides lithium ions and diffusion, and is responsible for ensuring the ion conductivity under the action of an electric field. Its structure and preparation process are one of the most important technologies to ensure the electrochromic performance of the device. Electrochromic devices can be divided into three types according to the state of the ion conduction layer, namely: liquid electrochromic devices, gel electrochromic devices, and all-solid-state electrochromic devices, among which gel electrochromic devices are also quasi-solid-state electrochromic devices. Compared with the problems of packaging and liquid leakage of liquid electrochromic devices; compared with the problems of slow response time and poor ion conductivity of all-solid-state electrochromic devices, quasi-solid-state electrochromic devices have better stability, simple preparation process, and their response time is higher than that of all-solid-state electrochromic devices.

[0004] Although theoretically electrochromic devices should have good stability, that is, they can still maintain good coloring performance after removing the voltage. However, in practice, the leakage current inside the device allows lithium ions to migrate out, resulting in the device fading. Summary of the Invention

[0005] Aiming at the slow response speed of existing bistable electrochromic devices, the so-called bistable performance means that after the device is colored under an applied voltage, when the voltage is removed, the color of the device can still be maintained, and the low transmittance can still be maintained for a long time until the corresponding reverse voltage is applied and the device returns to its initial state. Usually, all-solid-state electrochromic devices with bistable performance need to restrict the free movement of Li + to a certain extent, so the coloring and fading speed is slow, or a larger voltage needs to be applied to completely fade (the purpose of this patent is to overcome these two problems). To this end, the present invention introduces a lithium ion fast migration layer (the first fast ion conductor layer and the second fast ion conductor layer), thereby improving the response speed of the device. Further setting the composition of the migrating ions, a bistable electrochromic device with a significantly improved response speed is finally obtained.

[0006] On the one hand, the present invention provides a fast-response bistable electrochromic device, which includes a transparent electrode layer, an electrochromic layer with a lower lithium ion binding energy, an electrochromic layer with a higher lithium ion binding energy, an ion conduction layer, and a top electrode layer arranged in sequence; and a first fast ion conductor layer and a second fast ion conductor layer are respectively arranged on the upper and lower surfaces of the electrochromic layer with a higher lithium ion binding energy; preferably, the first fast ion conductor layer and the second fast ion conductor layer are selected from at least one of LLZO, LLTO, and LIPON.

[0007] In the present disclosure, the inventors have found through research that solid electrolytes with a perovskite structure, such as LLTO, LLTO, and LIPON, all have advantages such as kinetic stability, antioxidant properties, and high room-temperature ionic conductivity (for example, Li 0.33 La 0.56 TiO3 (LLTO) lithium-ion conductor, which has a bulk conductivity as high as 10 -3 S cm -1 at room temperature. Monovalent Li ions and trivalent La ions jointly occupy the A site and are both located at the center of the [TiO6] octahedra sharing vertices. The introduction of large-radius trivalent La ions creates a large number of A-site vacancies, so LLTO has a high bulk conductivity). Therefore, solid electrolytes with a perovskite structure, such as LLTO, LLTO, and LIPON, are introduced on both sides of the electrochromic layer with a relatively high lithium-ion binding energy. These materials are fast lithium-ion conducting materials, and lithium ions have a high conduction speed. Therefore, preparing a high-quality fast ion conductor layer by the method proposed in this patent helps the overall migration of lithium ions at the multilayer film interface, rather than occurring first at defects or crystal planes., thereby improving the response speed of the device. Finally, after the obtained fast-response bistable electrochromic device is colored under an applied voltage, when the voltage is removed, the color of the device can still be maintained, and it can still maintain a low transmittance for a long time until the corresponding reverse voltage is applied and the device returns to the initial state. Conversely, when the device is in the transmissive state, it can always maintain this state until a voltage is applied to change it to the colored state.

[0008] Preferably, the thickness of the first fast ion conductor layer and the second fast ion conductor layer is ≤ 10 nm, and preferably 5 - 10 nm.

[0009] Preferably, the electrochromic layer with a relatively high lithium-ion binding energy is a wide-bandgap semiconductor oxide, preferably selected from at least one of WO3, MoO, TiO2, and ZnO.

[0010] Preferably, the thickness of the electrochromic layer with a relatively high lithium-ion binding energy is 500 - 800 nm.

[0011] Preferably, the electrochromic layer with a relatively high lithium-ion binding energy is a strongly electron-correlated material, preferably selected from at least one of VO2, V2O3, and SmNiO3.

[0012] Preferably, the thickness of the electrochromic layer with a relatively high lithium-ion binding energy is 30 - 100 nm.

[0013] 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, and ATO; the sheet resistance of the transparent electrode layer is 5 - 50 Ω / cm 2, the average visible light transmittance is greater than 75%.

[0014] 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, and ATO; the sheet resistance of the top electrode layer is 5-50 Ω / cm 2 , the average visible light transmittance is greater than 75%.

[0015] Preferably, the ion conduction layer is a photocurable resin dispersion liquid with a composite cation (i.e., a conducting cation) content of 1-10 wt% (mass concentration); the composite cation includes a main cation and an auxiliary cation; preferably, the main cation in the middle can be Li + , Na + , Al 3+ at least one of them, and the auxiliary cation is Mg 2+ ;; More preferably, the molar ratio of the main cation to the auxiliary cation is (5-59):1, preferably (9-49):1.

[0016] Preferably, after applying a coloring voltage, the fast-response bistable electrochromic device is colored, and after removing the voltage, the transmittance change rate at 670 nm is less than 1% at 2 hours, less than 5% at 4 hours, and less than 10% at 8 hours.

[0017] Preferably, the coloring response time of the fast-response bistable electrochromic device is less than 10 s when applying a voltage of 0 to -4 V, and the fading response time is less than 5 s when applying a voltage of 2 V to 0 V.

[0018] Preferably, the first fast ion conductor layer and the second fast ion conductor layer are prepared by pulsed laser deposition, vacuum evaporation, or magnetron sputtering deposition; pulsed laser deposition is preferably used; more preferably, the parameters of the pulsed laser deposition include: deposition temperature 50-400 °C, working pressure 5-8 Pa, pulsed laser power 1.0-4.0 J / cm 2 .

[0019] Beneficial effects:

[0020] In the present disclosure, by introducing a fast ion migration channel and adjusting the composition of the migrating ions, a bistable electrochromic device with fast response ability is obtained. The bistable electrochromic device proposed in the present disclosure has the advantages of fast response speed and good bistable performance, and can be applied to future electronic displays, military camouflage and other fields.

[0021] The present invention provides an electrochromic device with fast-responsive bistable performance and a preparation method thereof. By adjusting the thicknesses of the functional layers in the device and the preparation process, and adjusting the contact state between the interfaces of the layers, a bistable electrochromic device that can be widely promoted and has practical value is obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a schematic structural diagram of a fast-responsive bistable electrochromic device;

[0023] Figure 2 is the response speed of the coloring and fading of the fast-responsive bistable electrochromic device in Example 1;

[0024] Figure 3 is the bistable performance of the fast-responsive bistable electrochromic device in Example 1, where the abscissa is time (Time) / second and the ordinate is transmittance (Transmittance) / %. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0025] The present invention will be further described below by the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention and do not limit the present invention.

[0026] In the present disclosure, by designing a lithium ion fast migration layer, a significantly improved response speed is obtained. A fully solid-state structure device is designed, and by adjusting the composition of the migrating ions and optimizing the ion migration path, it can meet the applications in more scenarios.

[0027] In the present invention, after the obtained fast-responsive bistable electrochromic device is colored under an applied voltage, when the voltage is removed, the color of the device can still be maintained, and the low transmittance can still be maintained unchanged for a long time until the corresponding reverse voltage is applied and the device returns to the initial state.

[0028] In an embodiment of the present invention, the basic structure of the fast-responsive bistable electrochromic device includes: a transparent electrode, electrochromic layers with lower and higher lithium ion binding energies, an ion conduction layer, and a top electrode layer, which are orderly arranged. Among them, fast ion conductor layers (referred to as the first fast ion conductor layer and the second fast ion conductor layer respectively) are deposited on the upper and lower surfaces of the electrochromic layer with a higher lithium ion binding energy.

[0029] In an alternative embodiment, the material of the fast ion conductor layer can be at least one of LLZO, LLTO, and LIPON. The thicknesses of the first fast ion conductor layer and the second fast ion conductor layer are 5-10 nm respectively.

[0030] In an alternative embodiment, the ion conduction layer is a photocurable resin dispersion liquid with a composite cation content of 1-10 wt%, and the main cation can be Li + , Na+ , Al 3+ etc., and the auxiliary cation is Mg 2+ . The molar ratio between the auxiliary cation and the main cation can be 1:49 - 1:9. The inventors further designed the composition of the migrating ions, and finally obtained a bistable electrochromic device with significantly improved response speed.

[0031] In an alternative embodiment, the film layer with a relatively high lithium ion binding energy is at least one of strong electron correlation materials such as VO2, V2O3, SmNiO3, etc. The thickness of the film layer with a relatively high lithium ion binding energy can be 30 - 100 nm.

[0032] In an alternative embodiment, the film layer composition with a relatively low lithium ion binding energy is at least one of wide bandgap semiconductor oxides such as WO3, MoO, TiO2, ZnO, etc. The thickness of the film layer with a relatively low lithium ion binding energy can be 500 - 800 nm.

[0033] The preparation process of the fast - response bistable electrochromic device is exemplarily described below.

[0034] Using a transparent conductive glass substrate, an inorganic electrochromic layer and an electron blocking layer are continuously deposited on its surface. By magnetron sputtering method. Using metal tungsten, zinc, molybdenum or titanium as the target. The sputtering gas is argon and oxygen, and the total pressure can be 0.5 - 2.0 Pa, and the oxygen partial pressure is 0 - 50%. The distance between the target and the substrate can be 10 - 20 cm. The initial substrate temperature can be room temperature. The DC power applied to the target can be 30 - 150 W or the power density can be 0.6 - 3.0 W / cm 2 A DC power supply is used on the surface. Finally, an electrochromic layer thin film with a low lithium ion binding energy and a thickness of 500 nm - 800 nm is deposited.

[0035] On the basis of the electrochromic layer thin film with a low lithium ion binding energy, a first fast ion conductor layer is prepared by pulsed laser deposition method. Using LLTO, LLZO or LIPON, etc. as the ceramic target. The working gas can be high - purity oxygen, and the total pressure can be 5 - 8 Pa. The distance between the target and the substrate can be 10 - 20 cm. The initial substrate temperature is room temperature, and the substrate is heated to 50 - 400 °C at a rate of 5 - 30 °C / min (10 °C / min). The pulsed laser energy density applied to the target can be 1.0 - 4.0 J / cm 2 . The deposition time can be 5 - 20 min. The thickness of the first fast ion conductor layer thin film is about 5 - 10 nm.

[0036] Prepare an electrochromic layer with a high lithium ion binding energy on the surface of the first fast ion conductor layer. As an example, using V2O3 as the target, the total pressure is 0.5 - 2.0 Pa, and the oxygen partial pressure is 0 - 50%. The distance between the target and the substrate can be 10 - 20 cm. The initial substrate temperature is room temperature. The DC power supply power applied to the target is 100 - 400 W or the power density is 2 - 8.0 W / cm 2 Use a DC power supply on the surface. The final deposited thickness can be a V2O3 thin film or a VO2 thin film with a thickness of 30 nm - 100 nm.

[0037] Deposit a second fast ion conductor layer on the surface of the electrochromic layer with a high lithium ion binding energy. Use ceramic targets such as LLTO, LLZO, or LIPON. The working gas can be high-purity oxygen, and the total pressure can be 5 - 8 Pa. The distance between the target and the substrate can be 10 - 20 cm. The initial substrate temperature is room temperature, and the substrate is heated to 50 - 400 °C at a rate of 5 - 30 °C / min (10 °C / min). The pulsed laser energy density applied to the target can be 1.0 - 4.0 J / cm 2 The deposition time can be 5 - 20 min. The thickness of the first fast ion conductor layer thin film can be approximately 5 - 10 nm.

[0038] Subsequently, a resin precursor slurry is configured. The ion conduction layer is obtained by curing a resin slurry that conducts cations. The composition of the resin slurry that conducts cations includes: a solvent, a resin, a stabilizer, an ultraviolet absorber, an organic precursor, and an ion source solution. The organic precursor includes an acid ester compound. The resin includes a photocurable resin or / and a thermosetting resin. The mass ratio of the solvent, resin, stabilizer, ultraviolet absorber, organic precursor, and 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 isopropyl alcohol, propylene glycol methyl ether acetate, dimethyl adipate, dimethylformamide, and dimethyl sulfoxide. The thermosetting resin is at least one of polyethylene oxide, epoxy resin, polypropylene resin, and phenolic resin. The photocurable resin is an ultraviolet curable resin. The stabilizer is a transition metal organic compound, preferably ferrocene and its derivatives. The ultraviolet absorber is selected from at least one of BYK1130, BYK 292, UV-234, and UV5411. The solute in the ion source solution is a 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 selected from at least one of propylene carbonate, acetonitrile, dimethyl sulfoxide, and N,N-dimethylformamide, etc. Preferably, the mass ratio of the perchlorate to the solvent is 1:(0.5-20). On this basis, an appropriate proportion of magnesium perchlorate is added as an auxiliary cation salt, and the ratio of magnesium perchlorate to the main cation is preferably 1:49-1:9.

[0039] The resin precursor slurry is filled between the second fast ion conductor layer and the top electrode by means of vacuum filling or coating. The ion conduction layer is prepared by a curing treatment such as ultraviolet irradiation curing or thermal curing to obtain a complete fast-response bistable electrochromic device. The curing treatment method is photocuring treatment or thermal curing treatment. The photocuring treatment is irradiation with an ultraviolet lamp of 50-300W for 30 seconds to 30 minutes. The temperature of the thermal curing treatment is 50-100°C, and the time is 10 minutes to 2 hours. Preferably, the thickness of the ion conduction layer is 3-100μm.

[0040] The beneficial effects of the present invention are as follows:

[0041] 1. A bistable electrochromic device with fast response performance is designed, which can meet the applications in more scenarios;

[0042] 2. The device with fast response can reduce the driving voltage and reduce the damage to the interface caused by high voltage, thereby obtaining a better device cycle life.

[0043] The following are further examples to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention fall within the protection scope of the present invention. The specific process parameters and the like in the following examples are only an example within a suitable range, that is, those skilled in the art can make selections within a suitable range through the description herein, rather than being limited to the specific values in the following examples. Unless otherwise specified, in the following examples and comparative examples, the DC magnetron sputtering system equipment used for magnetron sputtering deposition may include a deposition chamber, a sample introduction chamber, several target heads, a substrate plate, a DC current, and a series of mechanical pumps and vacuum pumps, wherein the target head forms a certain angle with the substrate plate and is separated by a certain distance, and the DC power supply is connected to the target head. The substrate is ultrasonically cleaned, and the substrate is ultrasonically cleaned with acetone, absolute ethanol, and deionized water for 20 minutes each, and then dried with compressed air. A certain part of the conductive substrate is covered with high-temperature tape as an electrode, fixed on the substrate tray, placed in the sample introduction chamber, the mechanical pump is turned on to pump to below 5 Pa, and then the baffle valve is opened to send it into the sputtering chamber with a vacuum degree (background vacuum degree) of 10 -4 Pa or less. The chemical composition of the LLTO ceramic target used is Li 0.33 La 0.56 TiO3.

[0044] Example 1

[0045] First, using a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer are continuously deposited on its surface. By the magnetron sputtering method, using metal tungsten as the target material, the sputtering gases are argon and oxygen, the total pressure is 0.7 Pa, the oxygen partial pressure is 10%, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power supply power applied to the target material is 100 W or the power density is 2.0 W / cm 2 A thin film of an electrochromic layer with a low lithium ion binding energy of 600 nm is deposited on the surface using a DC power supply. Secondly, on the basis of the above thin film, the pulsed laser deposition method is used, with the LLTO ceramic target material, the working gas is high-purity oxygen, the total pressure is 6 Pa, the distance between the target material and the substrate is 15 cm, the initial substrate temperature is room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target material is 2.0 J / cm 2, the deposition time was 10 min, and the film thickness was about 7 nm. Then, using V2O3 as the target, the total pressure was 1.0 Pa, the oxygen partial pressure was 1.5%, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, and the DC power applied to the target was 150 W. A 50-nm VO2 film was deposited on the surface using a DC power supply. Using an LLTO ceramic target, high-purity oxygen as the working gas, the total pressure was 6 Pa, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, the substrate was heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target was 2.0 J / cm 2 , the deposition time was 12 min, and the film thickness was about 10 nm. Subsequently, a resin precursor was prepared according to the prior art, with lithium perchlorate as the main cation salt, and an appropriate proportion of magnesium perchlorate was added as an auxiliary cation salt. The total concentration of Li + and Mg 2+ was 5 wt%, and the ratio of magnesium perchlorate to the main cation was 1:20. Finally, the above slurry was filled between two electrodes by means of vacuum filling or coating. Finally, an ion conduction layer was prepared by ultraviolet irradiation curing technology to obtain a complete device. Figure 1 is the structure of the device. Figure 2 is the response speed of the device. The fading time was about 3.1 s, and the coloring time was about 6.2 s. Figure 3 is the bistable performance of the device. After maintaining for 4 h, the transmittance change rate was less than 3%.

[0046] Example 2

[0047] First, using a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer were continuously deposited on its surface. By magnetron sputtering, using metals such as tungsten, zinc, molybdenum or titanium as the target, the sputtering gases were argon and oxygen, the total pressure was 0.7 Pa, the oxygen partial pressure was 10%, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, and the DC power applied to the target was 100 W or the power density was 2.0 W / cm 2A thin film of an electrochromic layer with a low lithium ion binding energy of 600 nm is deposited on the surface using a DC power supply. Secondly, based on the above thin film, the pulsed laser deposition method is used. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, the pulsed laser energy density applied to the target is 2.0 J / cm2, the deposition time is 6 min, and the film thickness is about 5 nm. Then, using V2O3 as the target, a total pressure of 1.0 Pa, an oxygen partial pressure of 1.5%, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the DC power supply power applied to the target is 150 W, and a 50-nm VO2 thin film is deposited on the surface using a DC power supply. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target is 2.0 J / cm 2 , the deposition time is 12 min, and the film thickness is about 10 nm. Subsequently, the resin precursor is configured according to the prior art, with lithium perchlorate as the main cationic salt, and an appropriate proportion of magnesium perchlorate is added as the auxiliary cationic salt. The total concentration of Li + and Mg 2+ is 5 wt%, and the ratio of magnesium perchlorate to the main cation is 1:20. Finally, the above slurry is filled between the two electrodes by means of vacuum filling or coating. Finally, an ion conduction layer is prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device is about 10 s, and the fading time is about 5 s.

[0048] Example 3

[0049] First, on a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer are continuously deposited on its surface. By magnetron sputtering, using a metal tungsten, zinc, molybdenum or titanium target, the sputtering gas is argon and oxygen, the total pressure is 0.7 Pa, the oxygen partial pressure is 10%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power supply power applied to the target is 100 W or the power density is 2.0 W / cm 2The electrochromic layer thin film with a low lithium ion binding energy of 600 nm is deposited on the surface using a DC power supply. Secondly, based on the above thin film, the pulsed laser deposition method is used with an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, heating the substrate to 300 °C at a rate of 10 °C / min, a pulsed laser energy density applied to the target of 2.0 J / cm2, a deposition time of 12 min, and a thin film thickness of approximately 10 nm. Then, using V2O3 as the target, a total pressure of 1.0 Pa, an oxygen partial pressure of 1.5%, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, and a DC power supply power of 150 W applied to the target, a 50-nm VO2 thin film is deposited on the surface. Using an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, heating the substrate to 300 °C at a rate of 10 °C / min, a pulsed laser energy density applied to the target of 2.0 J / cm 2 , a deposition time of 12 min, and a thin film thickness of approximately 10 nm. Subsequently, a resin precursor is configured according to the prior art, lithium perchlorate is used as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as an auxiliary cation salt. The total concentration of Li + and Mg 2+ is 5 wt%, and the ratio of magnesium perchlorate to the main cation is 1:20. Finally, the above slurry is filled between the two electrodes by means of vacuum filling or coating. Finally, an ion conduction layer is prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device is approximately 10 s, and the fading time is approximately 8 s.

[0050] Example 4

[0051] First, on a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer are continuously deposited on its surface. By the magnetron sputtering method, using a metal tungsten, zinc, molybdenum, or titanium target, the sputtering gas is argon and oxygen, the total pressure is 0.7 Pa, the oxygen partial pressure is 10%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power supply power applied to the target is 100 W or the power density is 2.0 W / cm 2A thin film of an electrochromic layer with a low lithium ion binding energy of 600 nm is deposited on the surface using a DC power supply. Secondly, on the basis of the above thin film, pulsed laser deposition is used. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, the pulsed laser energy density applied to the target is 2.0 J / cm2, the deposition time is 10 min, and the thin film thickness is about 7 nm. Then, using V2O3 as the target, a total pressure of 1.0 Pa, an oxygen partial pressure of 1.5%, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, and a DC power supply power of 150 W applied to the target, a 50-nm VO2 thin film is deposited on the surface using a DC power supply. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target is 2.0 J / cm 2 , the deposition time is 10 min, and the thin film thickness is about 7 nm. Subsequently, a resin precursor is configured according to the prior art, with lithium perchlorate as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as an auxiliary cation salt on this basis. The total concentration of Li + and Mg 2+ is 5 wt%, and the ratio of magnesium perchlorate to the main cation is 1:20. Finally, the above slurry is filled between the two electrodes by means of vacuum filling or coating. Finally, an ion conduction layer is prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device is about 8 s, and the fading time is about 6 s.

[0052] Example 5

[0053] First, on a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer are continuously deposited on its surface. By magnetron sputtering, using a metal tungsten, zinc, molybdenum or titanium target, argon and oxygen as the sputtering gases, a total pressure of 0.7 Pa, an oxygen partial pressure of 10%, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, and a DC power supply power of 100 W or a power density of 2.0 W / cm 2 A thin film of an electrochromic layer with a low lithium ion binding energy of 600 nm is deposited on the surface using a DC power supply. Secondly, on the basis of the above thin film, pulsed laser deposition is used. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target is 2.0 J / cm 2, the deposition time was 10 min and the film thickness was approximately 7 nm. Then, using V2O3 as the target, the total pressure was 1.0 Pa, the oxygen partial pressure was 1.5%, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, and the DC power applied to the target was 150 W. A 50-nm VO2 film was deposited on the surface using a DC power supply. Using an LLTO ceramic target, the working gas was high-purity oxygen, the total pressure was 6 Pa, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, the substrate was heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target was 2.0 J / cm 2 , the deposition time was 6 min and the film thickness was approximately 5 nm. Subsequently, the resin precursor was prepared according to the prior art, with lithium perchlorate as the main cationic salt, and an appropriate proportion of magnesium perchlorate was added as the auxiliary cationic salt. The total concentration of Li + and Mg 2+ was 5%, and the ratio of magnesium perchlorate to the main cation was 1:20. Finally, the above slurry was filled between the two electrodes by means such as vacuum filling or coating. Finally, an ion conduction layer was prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device was approximately 8 s, and the fading time was approximately 5 s.

[0054] Example 6

[0055] First, using a transparent conductive glass substrate, an inorganic electrochromic layer and an electron blocking layer were continuously deposited on its surface. By magnetron sputtering, using a metal tungsten, zinc, molybdenum or titanium target, the sputtering gases were argon and oxygen, the total pressure was 0.7 Pa, the oxygen partial pressure was 10%, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, and the DC power applied to the target was 100 W or the power density was 2.0 W / cm 2A thin film of an electrochromic layer with a low lithium ion binding energy of 600 nm is deposited on the surface using a DC power supply. Secondly, on the basis of the above thin film, pulsed laser deposition is used with an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, the pulsed laser energy density applied to the target is 2.0 J / cm2, the deposition time is 10 min, and the thin film thickness is about 7 nm. Then, using V2O3 as the target, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power supply power applied to the target is 150 W. A 50-nm VO2 thin film is deposited on the surface using a DC power supply. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, the pulsed laser energy density applied to the target is 2.0 J / cm 2 , the deposition time is 12 min, and the thin film thickness is about 10 nm. Subsequently, a resin precursor is configured according to the prior art, with lithium perchlorate as the main cationic salt, and an appropriate proportion of magnesium perchlorate is added as an auxiliary cationic salt on this basis. The total concentration of Li + and Mg 2+ is 5%, and the ratio of magnesium perchlorate to the main cation is 1:49. Finally, the above slurry is filled between the two electrodes by means of vacuum filling or coating. Finally, an ion conduction layer is prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device is about 7 s, and the fading time is about 4 s.

[0056] Example 7

[0057] First, on a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer are continuously deposited on its surface. By magnetron sputtering, using a metal tungsten, zinc, molybdenum or titanium target, the sputtering gas is argon and oxygen, the total pressure is 0.7 Pa, the oxygen partial pressure is 10%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power supply power applied to the target is 100 W or the power density is 2.0 W / cm 2 A thin film of an electrochromic layer with a low lithium ion binding energy of 600 nm is deposited on the surface using a DC power supply. Secondly, on the basis of the above thin film, pulsed laser deposition is used with an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, the pulsed laser energy density applied to the target is 2.0 J / cm 2, the deposition time is 10 min, and the film thickness is about 7 nm. Then, using V2O3 as the target, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power applied to the target is 150 W. A 50-nm VO2 film is deposited on the surface using a DC power supply. Using an LLTO ceramic target, the working gas is high-purity oxygen, the total pressure is 6 Pa, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target is 2.0 J / cm 2 , the deposition time is 12 min, and the film thickness is about 10 nm. Subsequently, a resin precursor is configured according to the prior art, with lithium perchlorate as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as an auxiliary cation salt. The total concentration of Li + and Mg 2+ is 5%, and the ratio of magnesium perchlorate to the main cation is 1:9. Finally, the above slurry is filled between two electrodes by means of vacuum filling or coating. Finally, an ion conduction layer is prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device is about 11 s, and the fading time is about 4 s.

[0058] Example 8

[0059] First, using a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer are continuously deposited on its surface. By magnetron sputtering, using metal tungsten, zinc, molybdenum or titanium as the target, the sputtering gas is argon and oxygen, the total pressure is 0.7 Pa, the oxygen partial pressure is 10%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power applied to the target is 100 W or the power density is 2.0 W / cm 2 A 800-nm electrochromic layer film with a low lithium ion binding energy is deposited on the surface using a DC power supply. Secondly, on the basis of the above film, pulsed laser deposition is used. Using an LLTO ceramic target, the working gas is high-purity oxygen, the total pressure is 6 Pa, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target is 2.0 J / cm 2, the deposition time was 10 min and the film thickness was about 7 nm. Then, using V2O3 as the target, the total pressure was 1.0 Pa, the oxygen partial pressure was 1.5%, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, and the DC power applied to the target was 150 W. A 50-nm VO2 film was deposited on the surface using a DC power supply. Using an LLTO ceramic target, high-purity oxygen as the working gas, the total pressure was 6 Pa, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, the substrate was heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target was 2.0 J / cm 2 , the deposition time was 12 min and the film thickness was about 10 nm. Subsequently, a resin precursor was prepared according to the prior art, with lithium perchlorate as the main cationic salt, and an appropriate proportion of magnesium perchlorate was added as an auxiliary cationic salt. The total concentration of Li + and Mg 2+ was 5%, and the ratio of magnesium perchlorate to the main cation was 1:9. Finally, the above slurry was filled between two electrodes by means of vacuum filling or coating. Finally, an ion conduction layer was prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device was about 11 s and the fading time was about 8 s.

[0060] Example 9

[0061] First, on a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer were continuously deposited on its surface. By magnetron sputtering, using metal tungsten, zinc, molybdenum or titanium as the target, the sputtering gases were argon and oxygen, the total pressure was 0.7 Pa, the oxygen partial pressure was 10%, the distance between the target and the substrate was 15 cm, the initial substrate temperature was room temperature, and the DC power applied to the target was 100 W or the power density was 2.0 W / cm 2A thin film of an electrochromic layer with a low lithium ion binding energy of 500 nm is deposited on the surface using a DC power supply. Secondly, based on the above thin film, the pulsed laser deposition method is used with an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, the pulsed laser energy density applied to the target is 2.0 J / cm2, the deposition time is 10 min, and the thin film thickness is about 7 nm. Then, using V2O3 as the target, the total pressure is 1.0 Pa, the oxygen partial pressure is 1.5%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power supply power applied to the target is 150 W. A 50-nm VO2 thin film is deposited on the surface using a DC power supply. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target is 2.0 J / cm 2 , the deposition time is 12 min, and the thin film thickness is about 10 nm. Subsequently, a resin precursor is configured according to the prior art, lithium perchlorate is used as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as an auxiliary cation salt on this basis. The total concentration of Li + and Mg 2+ is 5%, and the ratio of magnesium perchlorate to the main cation is 1:9. Finally, the above slurry is filled between the two electrodes by means such as vacuum filling or coating. Finally, an ion conduction layer is prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device is about 12 s, and the fading time is about 6 s.

[0062] Example 10

[0063] First, on a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer are continuously deposited on its surface. By the magnetron sputtering method, using a metal tungsten, zinc, molybdenum or titanium target, the sputtering gas is argon and oxygen, the total pressure is 0.7 Pa, the oxygen partial pressure is 10%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, and the DC power supply power applied to the target is 100 W or the power density is 2.0 W / cm 2A thin film of an electrochromic layer with a low lithium ion binding energy of 600 nm is deposited on the surface using a DC power supply. Secondly, on the basis of the above thin film, the pulsed laser deposition method is used. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, the pulsed laser energy density applied to the target is 2.0 J / cm2, the deposition time is 10 min, and the thin film thickness is about 7 nm. Then, using V2O3 as the target, a total pressure of 1.0 Pa, an oxygen partial pressure of 1.5%, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, a DC power supply power of 150 W is applied to the target, and a 30-nm VO2 thin film is deposited on the surface using a DC power supply. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, and the pulsed laser energy density applied to the target is 2.0 J / cm 2 , the deposition time is 12 min, and the thin film thickness is about 10 nm. Subsequently, the resin precursor is configured according to the prior art, lithium perchlorate is used as the main cationic salt, and an appropriate proportion of magnesium perchlorate is added as the auxiliary cationic salt on this basis. The total concentration of Li + and Mg 2+ is 5%, and the ratio of magnesium perchlorate to the main cation is 1:9. Finally, the above slurry is filled between the two electrodes by means such as vacuum filling or coating. Finally, an ion conduction layer is prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device is about 11 s, and the fading time is about 8 s. Due to the too thin VO2 layer, the bistable performance decreases, that is, the coloring performance decreases by more than 10% after the device is open-circuited for 4 h.

[0064] Example 11

[0065] First, on a transparent conductive glass substrate, an inorganic electrochromic layer and a fast ion conductor layer are continuously deposited on its surface. By the magnetron sputtering method, using a metal tungsten, zinc, molybdenum or titanium target, argon and oxygen as the sputtering gases, a total pressure of 0.7 Pa, an oxygen partial pressure of 10%, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, a DC power supply power of 100 W or a power density of 2.0 W / cm 2A thin film of an electrochromic layer with a low lithium ion binding energy of 600 nm is deposited on the surface using a DC power supply. Secondly, on the basis of the above-mentioned thin film, the pulsed laser deposition method is used. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, the pulsed laser energy density applied to the target is 2.0 J / cm2, the deposition time is 10 min, and the thickness of the thin film is about 7 nm. Then, using V2O3 as the target, a total pressure of 1.0 Pa, an oxygen partial pressure of 1.5%, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the DC power supply power applied to the target is 150 W, and a 100-nm VO2 thin film is deposited on the surface using a DC power supply. With an LLTO ceramic target, high-purity oxygen as the working gas, a total pressure of 6 Pa, a distance between the target and the substrate of 15 cm, an initial substrate temperature of room temperature, the substrate is heated to 300 °C at a rate of 10 °C / min, the pulsed laser energy density applied to the target is 2.0 J / cm 2 , the deposition time is 12 min, and the thickness of the thin film is about 10 nm. Subsequently, the resin precursor is configured according to the existing technology, with lithium perchlorate as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as the auxiliary cation salt on this basis. The total concentration of Li + and Mg 2+ is 6%, and the ratio of magnesium perchlorate to the main cation is 1:9. Finally, the above-mentioned slurry is filled between the two electrodes by means of vacuum filling or coating. Finally, an ion conduction layer is prepared by ultraviolet irradiation curing technology to obtain a complete device. The coloring time of the device is about 20 s, and the fading time is about 8 s. Since the VO2 layer is too thick, a higher voltage needs to be applied to fully color the device.

[0066] Example 12

[0067] This Example 12 refers to Example 7, the difference is that: lithium perchlorate is used as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as the auxiliary cation salt on this basis, and the ratio of magnesium perchlorate to the main cation is 0:10.

[0068] Example 13

[0069] This Example 13 refers to Example 7, the difference is that: lithium perchlorate is used as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as the auxiliary cation salt on this basis, and the ratio of magnesium perchlorate to the main cation is 1:59.

[0070] Example 14

[0071] Example 14 refers to Example 1, with the difference that: the first fast ion conductor layer and the second fast ion conductor layer are LLZO (chemical composition Li7La3Zr2O 12 ) / 7nm and LLZO / 10nm respectively.

[0072] Example 15

[0073] Example 15 refers to Example 1, with the difference that: the first fast ion conductor layer and the second fast ion conductor layer are LiPON / 7nm and LiPON / 10nm respectively.

[0074] Example 16

[0075] Example 16 refers to Example 7, with the difference that: lithium perchlorate is used as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as the auxiliary cation salt on this basis. The ratio of magnesium perchlorate to the main cation is 1:29.

[0076] Example 17

[0077] Example 17 refers to Example 7, with the difference that: lithium perchlorate is used as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as the auxiliary cation salt on this basis. The ratio of magnesium perchlorate to the main cation is 1:39.

[0078] Example 18

[0079] Example 18 refers to Example 7, with the difference that: lithium perchlorate is used as the main cation salt, and an appropriate proportion of magnesium perchlorate is added as the auxiliary cation salt on this basis. The ratio of magnesium perchlorate to the main cation is 1:5.

[0080] Comparative Example 1

[0081] Comparative Example 1 refers to Example 1, with the difference that: the first fast ion conductor layer and the second fast ion conductor layer are not deposited.

[0082] Comparative Example 2

[0083] Comparative Example 2 refers to Example 1, with the difference that: the thickness of the first fast ion conductor layer is 15nm, and the second fast ion conductor layer is 15nm.

[0084] Comparative Example 3

[0085] Comparative Example 3 refers to Example 1, with the difference that: only the second fast ion conductor layer is deposited.

[0086] Comparative Example 4

[0087] Comparative Example 4 refers to Example 1, with the difference that: only the first fast ion conductor layer is deposited.

[0088] Table 1 shows the composition and performance parameters of the fast-response bistable electrochromic device prepared by the present invention:

[0089]

[0090]

[0091]

[0092] . Among them, the meaning of the ion ratio is "the molar ratio of the co-cation to the main oxygen ion".

Claims

1. A fast-response bistable electrochromic device, characterized in that, It includes a transparent electrode layer, an electrochromic layer with a lower lithium-ion binding energy, an electrochromic layer with a higher lithium-ion binding energy, an ion conduction layer, and a top electrode layer arranged in sequence; and a first fast ion conductor layer and a second fast ion conductor layer are respectively provided on the upper and lower surfaces of the electrochromic layer with a higher lithium-ion binding energy; the first fast ion conductor layer and the second fast ion conductor layer are selected from at least one of LLZO, LLTO, and LIPON.

2. The fast response bistable electrochromic device according to claim 1, characterized in that The thickness of the first fast ion conductor layer and the second fast ion conductor layer ≤ 10 nm.

3. The fast-response bistable electrochromic device according to claim 2, wherein The thickness of the first fast ion conductor layer and the second fast ion conductor layer is 5 - 10 nm.

4. The fast-response bistable electrochromic device according to claim 1, wherein The electrochromic layer with a higher lithium-ion binding energy is a wide-bandgap semiconductor oxide, selected from at least one of WO3, MoO, TiO2, and ZnO; the thickness of the electrochromic layer with a higher lithium-ion binding energy is 500 - 800 nm.

5. The fast response bistable electrochromic device according to claim 1, wherein The electrochromic layer with a higher lithium-ion binding energy is a strong electron correlation material, selected from at least one of VO2, V2O3, and SmNiO3; the thickness of the electrochromic layer with a higher lithium-ion binding energy is 30 - 100 nm.

6. The fast-response bistable electrochromic device according to claim 1, wherein The transparent electrode layer is at least one of a transparent conductive oxide, a transparent silicon electrode, and a transparent noble metal nanowire electrode; the transparent conductive oxide is selected from at least one of FTO, ITO, and ATO; the sheet resistance of the transparent electrode layer is 5 to 50 Ω / cm 2 , and the average visible light transmittance is greater than 75%.

7. The fast-response bistable electrochromic device according to claim 1, wherein The top electrode layer is at least one of a transparent conductive oxide, a transparent silicon electrode, and a transparent noble metal nanowire electrode; the transparent conductive oxide is selected from at least one of FTO, ITO, and ATO; the sheet resistance of the top electrode layer is 5 to 50 Ω / cm 2 , and the average visible light transmittance is greater than 75%.

8. The fast-response bistable electrochromic device according to claim 1, characterized in that, The ion conduction layer is a photocurable resin dispersion liquid with a composite cation content of 1 to 10 wt%; the composite cation includes a main cation and an auxiliary cation; the main cation is Li + , Na + , Al 3+ or at least one of them, and the auxiliary cation is Mg 2+ ; the molar ratio of the main cation to the auxiliary cation is (5 to 59):

1.

9. The fast response bistable electrochromic device according to claim 8, wherein The molar ratio of the main cation to the auxiliary cation is (9 - 49):

1.

10. The fast-response bistable electrochromic device according to claim 1, wherein When the fast-response bistable electrochromic device is colored after applying a coloring voltage, the transmittance change rate at 670 nm is less than 1% at 2 hours, less than 5% at 4 hours, and less than 10% at 8 hours after removing the voltage.

11. The fast response bistable electrochromic device according to claim 1, wherein When the fast-response bistable electrochromic device is applying a voltage of 0 to -4V, the coloring response time is less than 10 s, and when applying a voltage of 2V to 0V, the fading response time is less than 5 s.

12. The fast-response bistable electrochromic device according to any one of claims 1-11, characterized in that, The first fast ion conductor layer and the second fast ion conductor layer are prepared by pulsed laser deposition, vacuum evaporation, or magnetron sputtering deposition.

13. The fast response bistable electrochromic device according to claim 12, characterized in that, Pulsed laser deposition is used; The parameters of the pulsed laser deposition include: deposition temperature of 50 to 400 °C, working gas pressure of 5 to 8 Pa, and pulsed laser power of 1.0 to 4.0 J / cm 2 .

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