Ultra-wideband regulation and control all-solid-state electrochromic device and preparation method thereof

Abstract

The invention relates to an ultra-wideband regulation and control all-solid-state electrochromic device and a preparation method thereof. The ultra-wideband regulation and control all-solid-state electrochromic device structurally comprises a glass substrate, a first transparent electrode, an ion storage layer, an ion conduction layer / electrolyte layer, an electrochromic layer and a second transparent electrode which are sequentially stacked, or a glass substrate, a first transparent electrode, an electrochromic layer, an ion conduction layer / electrolyte layer, an ion storage layer and a second transparent electrode; wherein the material of the electrochromic layer comprises at least one of WO3-x, MoO3-x and TiO2-x, the surface layer of one side, in contact with the electrolyte layer, of the electrochromic layer is rich in oxygen vacancies, x is greater than 0.2 and less than or equal to 1, and x is greater than or equal to 0 and less than or equal to 0.2 of parts outside the surface layer.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromic functional materials and devices, and specifically relates to an ultra-wideband controlled all-solid-state electrochromic device and a preparation method thereof. Background Art

[0002] Statistics show that buildings account for over 40% of total energy consumption. Current approaches to reducing building energy consumption include active and passive energy conservation. Active energy conservation improves energy efficiency and thereby reduces energy consumption by comprehensively optimizing HVAC systems. Passive energy conservation is achieved by enhancing the insulation between the building and the external heat exchange medium. For example, improving the insulation of building walls, roofs, doors, and windows reduces heat loss and dissipation, thereby reducing building energy consumption. Furthermore, due to lighting and design requirements, the proportion of glazing in doors and windows in a building structure has gradually increased. However, window glass has the poorest insulation performance in building structures. Statistical simulations show that heat exchange through windows accounts for 70% and 60% of a building's total heat exchange in summer and winter, respectively. Clearly, windows consume the majority of a building's energy. Therefore, reducing energy loss through windows and doors is key to improving building energy efficiency.

[0003] Window heat exchange involves heat conduction, convection, and radiation. Radiative heat exchange involves solar radiation in the visible (380–780 nm) and near-infrared (780–2500 nm) ranges, as well as spontaneous room-temperature radiation in the mid-infrared "atmospheric window" (8–14 μm). However, conventional windows generally have difficulty dynamically regulating visible and near-infrared solar radiation, and their ability to regulate room-temperature radiation is weak, resulting in significant energy losses in buildings. On the one hand, the transmittance of visible and near-infrared light is difficult to independently control, and the high natural light transmittance required for indoor lighting sacrifices some of the solar radiation regulation capability. On the other hand, window glass, primarily composed of silica, exhibits strong absorption (i.e., a highly emissive state) in wavelengths above 4 μm. Consequently, in summer, the outdoor ambient and window surface temperatures are higher than those in the room, causing the windows to continuously radiate heat into the room. In winter, the outdoor and window surface temperatures are lower, causing the windows to continuously radiate heat into the room, significantly increasing air conditioning energy consumption for both summer cooling and winter heating.

[0004] Electrochromism refers to the phenomenon that the optical properties of a material (reflectivity, transmittance, absorptivity, etc.) undergo stable and reversible changes under the action of an external electric field, which manifests itself in appearance as reversible changes in color and transparency. Electrochromic devices are generally composed of a transparent electrode, an electrochromic layer, an ion conduction layer (also called an electrolyte layer), an ion storage layer, and a transparent electrode. Among them, WO3 is the most widely used inorganic electrochromic material. The ion conduction layer provides an ion transmission channel between the electrochromic layer and the ion storage layer. It needs to be compatible with the film materials on both sides and have good electronic insulation and ionic conductivity. The electrochromic smart window prepared using electrochromic materials has a series of advantages such as continuous and precise adjustment of optical properties, strong resistance to environmental interference, good adaptability, low power consumption, and fast coloring / fading response speed. Therefore, compared with other stimulation methods, smart windows based on electrochromism have obvious advantages.

[0005] However, currently, wide-band transparent substrates are generally based on single crystal materials, which are often difficult to prepare over a large area. Therefore, the preparation of large-scale wide-band control devices is either costly or technically complex. Moreover, research on wide-band controllable electrochromic devices mainly revolves around the controllable deposition of metal ions, and the high emissivity and low reflection of the mid-infrared after metal deposition are used to construct devices with controllable emissivity. However, this type of device often uses liquid electrolytes, which have problems such as easy leakage, poor stability and unsafety, and also faces problems such as poor uniformity and low coloring rate during the amplification process. At the same time, all-solid-state electrochromic devices are often difficult to adjust over a wide band or have weak control capabilities. Generally, all-solid-state electrochromic devices can only control visible and near-infrared light (0.38-2.5μm) covered by sunlight, and are difficult to control mid- and far-infrared (8-13μm). The effective management of mid-infrared radiation heat is of great significance to further improve energy efficiency. Summary of the Invention

[0006] In response to the above technical problems, the object of the present invention is to provide an ultra-wideband controllable all-solid-state electrochromic device and a preparation method thereof.

[0007] In a first aspect, the present invention provides an ultra-wideband regulated all-solid-state electrochromic device, the structure of which comprises: a glass substrate, a first transparent electrode, an ion storage layer, an ion conduction layer / electrolyte layer, an electrochromic layer, and a second transparent electrode stacked in sequence, or a glass substrate, a first transparent electrode, an electrochromic layer, an ion conduction layer / electrolyte layer, an ion storage layer, and a second transparent electrode; in: The material of the electrochromic layer includes WO 3-x 、MoO 3-x and TiO 2-xAt least one of the above, the surface layer of the electrochromic layer in contact with the electrolyte layer is rich in oxygen vacancies, the surface layer is 0.2<x≤1, and the part outside the surface layer is 0≤x≤0.2.

[0008] Preferably, the material of the first transparent electrode includes at least one of transparent conductive oxide, MXENE, and metal nanowires; Preferably, the sheet resistance of the first transparent electrode is 10 to 400 Ω / cm 2 , the sunlight transmittance in the 0.38~2.5μm band is ≥75%, and the mid-infrared reflectivity in the 2.5~25um band is ≥75%.

[0009] Preferably, the material of the ion conducting layer / electrolyte layer includes LiTaO3, LiNbO3, Li 0.35 La 0.57 At least one of TiO3, Li2Ti2O5; Preferably, the infrared transmittance of the ion conducting layer / electrolyte layer in the 8-13 μm band is ≥80%.

[0010] Preferably, the material of the ion storage layer includes NiO x 、V2O5、CoO x At least one of; Preferably, the infrared transmittance of the ion storage layer in the 8-13 μm band is ≥80%.

[0011] Preferably, the material of the second transparent electrode includes at least one of transparent conductive oxide, MXENE, and metal nanowires; Preferably, the second transparent electrode has a solar transmittance of ≥75% in the 0.38-2.5 μm band and a mid-infrared transmittance of ≥75% in the 2.5-25 μm band.

[0012] Preferably, the ultra-wideband controlled all-solid-state electrochromic device has a stable cycle number of ≥20,000 times, a mid-to-far infrared emissivity adjustment rate of ≥0.3 in the 8-13 μm band, a solar band adjustment capability of ≥0.5, a visible infrared control capability selectivity ratio of ≥0.7, and a device effective area of ​​≥100 cm 2 .

[0013] In a second aspect, the present invention provides a method for preparing the above-mentioned ultra-wide-band controlled all-solid-state electrochromic device, the preparation method comprising: preparing an electrochromic layer on the surface of the ion conduction layer or the first transparent electrode by magnetron sputtering and annealing process; the annealing process is heat treatment under an inert atmosphere, and the heat treatment pressure is 2-200 torr.

[0014] Preferably, the process parameters of the magnetron sputtering include: the sputtering gas is argon and oxygen, the total pressure is 0.5-2.0 Pa, and the oxygen partial pressure is 0-50%; Preferably, the vertical distance between the target and the substrate is 10-20 cm; the initial substrate temperature is room temperature; the DC power applied to the target is 30-200 W or the power density is 0.6-3.0 W / cm 2 .

[0015] Preferably, the heat treatment process is: heating to 300-400°C for 10-40s and then keeping warm for 50-200s, then heating to 350-500°C for 5-20s and then keeping warm for 100-1000s, and naturally cooling to room temperature.

[0016] Beneficial effects (1) The present invention achieves wide-band control from visible light to mid- and far-infrared light by designing a simple all-solid-state electrochromic structure, which can achieve excellent energy-saving effects in major regions around the world; (2) It is usually difficult to prepare a wide-band transparent substrate with a large area, which limits the area of ​​the device. The present invention avoids the use of a wide-band transparent substrate through structural design; (3) In this patent, by optimizing the optical design of the thickness of each film layer, the device not only has excellent control performance in the solar band, but also has excellent control performance in the mid-infrared band (8-13μm). BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a schematic diagram of the exemplary structure of the ultra-wideband controllable all-solid-state electrochromic device provided by the present invention. DETAILED DESCRIPTION

[0018] The present invention is further described below through the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, rather than to limit the present invention.

[0019] First, if Figure 1 As shown, the present invention provides an ultra-wideband regulated all-solid-state electrochromic device. The structure of the ultra-wideband regulated all-solid-state electrochromic device may include: a glass substrate, a first transparent electrode, an ion storage layer, an ion conduction layer / electrolyte layer, an electrochromic layer, and a second transparent electrode stacked in sequence; or a glass substrate, a first transparent electrode, an electrochromic layer, an ion conduction layer / electrolyte layer, an ion storage layer, and a second transparent electrode.

[0020] In some embodiments, the thickness of the glass substrate may be 0.1-5 mm, preferably 0.5-3 mm.

[0021] In some embodiments, the material of the first transparent electrode may include at least one of transparent conductive oxide, MXENE, and metal nanowires; preferably, the sheet resistance of the first transparent electrode may be 10 to 400 Ω / cm 2 , with a solar transmittance of ≥75% in the 0.38-2.5μm band and a mid-infrared reflectance of ≥75% in the 2.5-25μm band. The first electrode used in the present invention has strong solar transmittance and strong infrared reflectance. If the solar transmittance is insufficient, the solar regulation ability will be weak; if the infrared reflectance is insufficient, the infrared regulation ability of the device will also be affected. In addition, if the square resistance is too large, it will make it difficult to drive the device to change color; if the square resistance is too small, there is a risk of device breakdown.

[0022] In some embodiments, the thickness of the first transparent electrode may be 100-600 nm.

[0023] In some embodiments, the material of the electrochromic layer may include WO 3-x 、MoO 3-x and TiO 2-x At least one of the following, 0≤x≤1; and a thickness of 200 to 600 nm. A thickness that is too large will have limited effect on device performance; a thickness that is too small will result in insufficient device regulation capabilities.

[0024] The surface material of the electrochromic layer in contact with the electrolyte layer may include WO 3-x 、MoO 3-x and TiO 2-x At least one of them, 0.2<x≤1, rich in oxygen vacancies; the surface layer thickness can be ≤50nm, preferably ≤20nm. If the value of x in the surface layer material is too large, the stability of the device will be reduced. For example, when the value of x is 1.2, the device after the electrochromic layer is treated by thermal annealing will be over-reduced, the solar regulation ability of the device will be only about 0.1, the infrared emissivity regulation rate will be only about 0.1, the visible-infrared regulation ability selection ratio will be only about 0.2, and the number of stable cycles will be only about 100 times. If the value is too small, the device regulation ability will be insufficient, affecting the visible-infrared selection ratio. For example, when the value of x is 0.2, the device after the electrochromic layer is treated by thermal annealing will find it difficult to preferentially regulate infrared light, but will regulate sunlight and infrared light at the same time, and the visible-infrared regulation ability selection ratio of the device will be only about 0.2. At the same time, if the surface layer is too thick, it will affect the stability of the device, and if it is too thin, it will affect the regulation ability of the device.

[0025] The material of the electrochromic layer other than the surface layer may include WO 3-x 、MoO 3-x and TiO 2-xAt least one of the following, 0≤x≤0.2. A large value of x may affect the cycle performance of the device.

[0026] In some embodiments, the material of the ion conducting layer / electrolyte layer may include LiTaO3, LiNbO3, Li 0.35 La 0.57 At least one of TiO3 and Li2Ti2O5; preferably, the infrared transmittance of the ion conductive layer in the 8-13 μm band is ≥80%. If the transmittance is low, the device's regulation performance will be affected, making it difficult to meet the regulation performance requirements.

[0027] In some embodiments, the thickness of the ion-conducting layer may be 20-60 nm. If the thickness is too thick, the transmittance is low and it is difficult to meet the device performance requirements; if the thickness is too thin, it will lead to insufficient electronic insulation performance, causing the device to short-circuit and lose the electrochromic performance of the device.

[0028] In some embodiments, the material of the ion storage layer may include NiO x 、V2O5、CoO x Preferably, the infrared transmittance of the ion storage layer in the 8-13 μm band is ≥80%. A low transmittance will affect the regulation performance of the device, making it difficult to meet the regulation performance requirements.

[0029] In some embodiments, the thickness of the ion storage layer may be 10-35 nm. If the thickness is too thick, the transmittance is low and cannot meet the requirements, while if the thickness is too thin, the color change performance of the device will be affected.

[0030] In some embodiments, the material of the second transparent electrode can include at least one of a transparent conductive oxide, MXENE, and metal nanowires. Preferably, the second transparent electrode has a solar transmittance of ≥75% in the 0.38-2.5 μm band and a mid-infrared transmittance of ≥75% in the 2.5-25 μm band. Devices that meet these transmittance requirements exhibit good electrochromic performance, namely, solar regulation efficiency and infrared emissivity.

[0031] In some embodiments, the second transparent electrode may have a thickness of 20-50 nm.

[0032] It should be noted that the first and second transparent electrodes used in the present invention both have high transmittance in the sunlight band, which is intended to enable the device to have excellent solar regulation capabilities. The purpose of the first transparent electrode is to reflect thermal radiation from the environment, and the overall infrared absorption capacity varies before and after ions enter and exit the electrochromic layer, thereby regulating the emissivity. The second transparent electrode's high transmittance ensures that thermal radiation from the environment (i.e., mid-infrared light) enters the device, thereby producing regulation.

[0033] Furthermore, when the solar transmittance of the first and second transparent electrodes is low (eg 50%), the solar regulation performance of the entire device decreases significantly (about 0.2), and the mid- and far-infrared emissivity regulation rate of the entire device is about 0.2.

[0034] It can be seen that the present invention addresses the technical difficulty of preparing a large area of ​​a wide-band transparent substrate made of single-crystal material, and avoids the use of a wide-band transparent substrate through structural design. At the same time, the present invention also adjusts the distribution of oxygen vacancies, so that the high concentration of electrons in the surface oxygen vacancies of the device at low voltage produces a localized surface plasmon resonance absorption phenomenon, which has good infrared control capabilities; when the voltage is increased, the electrons in the electrochromic layer and the lattice produce small polarons that polarize and absorb visible light, causing the device to produce strong absorption in the visible light band. In addition, in order to further improve the energy-saving efficiency of the device, the present invention also adjusts the peak position with the greatest control ability to the atmospheric window "8-13μm" through optical design.

[0035] In some embodiments, the ultra-wide band controlled all-solid-state electrochromic device has a stable cycle number of ≥20,000 times, an 8-13um mid-infrared and far-infrared emissivity adjustment rate (mid-infrared and far-infrared emissivity adjustment capability) ≥0.3, a solar band adjustment capability (solar energy adjustment capability) ≥0.5, a visible infrared adjustment capability selectivity ratio (visible-infrared adjustment capability selectivity ratio, visible / infrared selectivity ratio) ≥0.7, and a device effective area ≥100 cm 2 The visible infrared control selectivity ratio refers to the ratio of visible light control relative to the initial stage when infrared is fully controlled. The larger the value, the better the infrared independent control performance.

[0036] In summary, compared with electrochromic devices whose adjustment range is visible light and near-infrared light, the electrochromic layer in the electrochromic device provided by the present invention: first, the oxygen vacancy concentration gradually changes from the surface to the inside, and the carrier concentration in the area with high oxygen vacancy concentration is high, which will diffuse to the low concentration area, but due to the restriction of lattice fixed ions, a space charge region is formed during the diffusion process, and a potential difference is formed at the interface, generating a self-built electric field, which can promote carrier movement; secondly, the high surface oxygen vacancy concentration is conducive to the formation of localized surface plasmon resonance absorption, so that the device has a better visible and near-infrared selectivity; thirdly, the oxygen vacancy concentration is a gradient concentration distribution, which makes the device have better adjustment performance in the range of 2.5-25um.

[0037] The following is an exemplary description of the method for preparing the ultra-wideband regulated all-solid-state electrochromic device provided by the present invention. The method may include the following steps: depositing a first transparent electrode, an ion storage layer, an ion conduction layer, an electrochromic layer, and a second transparent electrode, or a first transparent electrode, an electrochromic layer, an ion conduction layer, an ion storage layer, and a second transparent electrode, on a glass substrate by magnetron sputtering in sequence to obtain the ultra-wideband regulated all-solid-state electrochromic device; After the electrochromic layer is deposited on the surface of the ion conducting layer or the first transparent electrode by magnetron sputtering, heat treatment annealing may be performed.

[0038] Each layer of material in the structure of the electrochromic device provided by the present invention is a thin film deposited by magnetron sputtering and does not contain a gel layer, so the purpose of wide-band regulation can be achieved without using a conventional small-sized wide-band transparent substrate.

[0039] In some embodiments, the process parameters for depositing the electrochromic layer on the surface of the ion conductive layer or the first transparent electrode by magnetron sputtering may include: metal tungsten, molybdenum or titanium as the target material; the sputtering gas is argon and oxygen with a purity of 99.99% or higher, with a total pressure of 0.5-2.0 Pa and an oxygen partial pressure of 0-50%, preferably 0-25%; the vertical distance between the target and the substrate is 10-20 cm; the initial substrate temperature is room temperature; the DC power applied to the target is 30-200 W or the power density is 0.6-3.0 W / cm 2 Too high or too low oxygen partial pressure will affect the initial film structure, and too high or too low power and time will affect the thickness of the film.

[0040] To be more specific, the DC magnetron sputtering system equipment used in the magnetron sputtering deposition in the present invention may include a deposition chamber, a sampling chamber, several target heads, a substrate plate, a DC current and a series of mechanical pumps and vacuum pumps; wherein, the target head and the substrate plate are at a certain angle and a certain distance apart, and the DC power supply is connected to the target head. The substrate is ultrasonically cleaned, and the substrate is ultrasonically cleaned with acetone, anhydrous ethanol, and deionized water for 20 minutes each, and blown dry with compressed air. Cover a certain part of the conductive substrate with high-temperature tape as an electrode, and fix it on the substrate tray, put it into the sampling chamber, turn on the mechanical pump to pump it below 5Pa, and then open the baffle valve to send it into the vacuum degree (background vacuum degree) that has reached 10 -4 Pa and below in the sputtering room.

[0041] The specific sputtering deposition process is as follows: high-purity argon and oxygen are respectively introduced into the sputtering chamber, the purity of the argon and oxygen used is 99.99% or above, the total pressure and oxygen partial pressure in the chamber are controlled to be in the range of 0.5-2.0 Pa and 0-50%, respectively, and the oxygen partial pressure is preferably 0-25%; the vertical distance between the target material and the substrate is controlled to be 10-20 cm, and the initial substrate temperature is room temperature; turn on the DC power supply, control the DC power supply power to 30-200 W, the pre-sputtering time is 5-30 min, the sputtering time is 10-60 min, and the substrate temperature is room temperature; after the sputtering is completed, wait for the substrate temperature to drop to room temperature and take out the substrate.

[0042] In some embodiments, the annealing process performed after depositing the electrochromic layer can be a heat treatment under an inert atmosphere, and the inert atmosphere can be Ar; the gas pressure of the heat treatment can be 2-200 torr; the heat treatment process can be: heating to 300-400°C (for example, 350°C) for 10-40s (for example, 20s) and then keeping warm for 50-200s (for example, 100s), then heating to 350-500°C (for example, 450°C) for 5-20s (for example, 10s) and then keeping warm for 100-1000s (for example, 200s), and naturally cooling to room temperature.

[0043] If the heat treatment temperature is too high or the time is too long, the oxygen vacancy content in the bottom layer outside the surface of the electrochromic layer will be too high, which will reduce the cycling stability of the device. If the heat treatment temperature is too low or the time is too short, the oxygen vacancy content in the surface layer of the electrochromic layer will be too low, which will make the infrared regulation ability of the device insufficient.

[0044] The preparation process involved in the present invention is simple, low in cost, and easy to promote. The high-performance electrochromic device developed by the present invention has broader application prospects.

[0045] This patent proposes a wide-band controllable electrochromic device based on WO3 electrochromic material, achieving an all-solid-state structure through material innovation and structural design. Furthermore, the device possesses ultra-wide-band controllable capabilities by regulating the distribution of oxygen vacancies. Therefore, the ultra-wide-band controllable all-solid-state electrochromic device designed and prepared in this patent is expected to be applied to smart windows, significantly reducing cooling or insulation energy consumption in both summer and winter. According to Energyplus software simulations, this electrochromic smart window demonstrates better energy efficiency than Low-E glass in major regions around the world.

[0046] The following examples are further given to illustrate the present invention in detail. It should be understood that the following examples are only used to further illustrate the present invention and cannot be interpreted as limiting the scope of protection 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 all fall within the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples within a suitable range, and those skilled in the art can make selections within a suitable range through the description herein, and are not limited to the specific numerical values ​​exemplified below. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.

[0047] Example 1

[0048] The method for preparing an ultra-wideband controlled all-solid-state electrochromic device provided in this embodiment comprises the following steps: (1) Using glass as a substrate, a first transparent electrode with high sunlight transmittance (transmittance 78%) and high infrared reflection (reflectivity 75%) is prepared on its surface; (2) The first transparent electrode surface is subjected to magnetron sputtering, with metal tungsten, molybdenum or titanium as the target, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 12%, the distance between the target and the substrate is 15 cm, the initial substrate temperature is room temperature, the DC power applied to the target is 70 W or the power density is 1.55 W / cm 2 A 400nm thick electrochromic layer is deposited on the surface using a DC power supply. Subsequently, the film is rapidly annealed and rapidly heat-treated in an inert atmosphere at a pressure of 50 torr. The heat treatment process is heating to 350°C for 20 seconds, holding for 100 seconds, then heating to 450°C for 10 seconds, holding for 200 seconds, and then naturally cooling to room temperature to obtain the electrochromic layer. (3) A magnetron sputtering process is continued on the electrochromic layer, using a LiTaO3 ceramic target, a total pressure of 2.0 Pa, a pure argon atmosphere, a distance between the target and the substrate of 15 cm, and a radio frequency power of 180 W to deposit an ion conductive layer with a thickness of 40 nm; on the ion conductive layer, a metal Ni target is used, the sputtering gas is argon and oxygen, the total pressure is 1.0 Pa, the oxygen partial pressure is 20%, the distance between the target and the substrate is 15 cm, the DC power is 100 W or the power density is 2 W / cm 2 , a 20nm thick ion storage layer is deposited on the surface using a DC power supply; finally, a second transparent electrode with wide-band high transmittance (transmittance 80%) is deposited on the ion storage layer to obtain the ultra-wide-band regulated all-solid-state electrochromic device.

[0049] Example 2

[0050] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the electrochromic layer thin film is 200 nm.

[0051] Example 3

[0052] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the electrochromic layer thin film is 600 nm.

[0053] Example 4

[0054] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the heat treatment pressure is 2 torr.

[0055] Example 5

[0056] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), the heat treatment pressure is 200 torr.

[0057] Example 6

[0058] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (1), the first transparent electrode has a sunlight transmittance of 75% and an infrared reflectivity of 78%.

[0059] Example 7

[0060] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (3), the broadband transmittance of the second transparent electrode is 75%.

[0061] Example 8

[0062] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (3), the ion conducting layer is 20 nm.

[0063] Example 9

[0064] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (3), the ion conducting layer is 60 nm.

[0065] Example 10

[0066] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (3), the ion storage layer is 10 nm.

[0067] Example 11

[0068] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (3), the ion storage layer is 35 nm.

[0069] Example 12

[0070] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), in the process of annealing the electrochromic film: the heat treatment pressure is 50 torr, and the heat treatment process is heating to 350°C in 20 seconds, keeping warm for 50 seconds, heating to 450°C in 10 seconds, and keeping warm for 250 seconds.

[0071] Example 13

[0072] The preparation method of the ultra-wideband controllable all-solid-state electrochromic device provided in this embodiment refers to that in Example 1, with the following main differences: In step (2), in the process of annealing the electrochromic film: the heat treatment pressure is 50 torr, and the heat treatment process is heating to 350°C in 20 seconds, keeping warm for 200 seconds, heating to 450°C in 10 seconds, and keeping warm for 100 seconds.

[0073] Example 14

[0074] The method for preparing an ultra-wideband controlled all-solid-state electrochromic device provided in this embodiment comprises the following steps: (1) Using glass as a substrate, a first transparent electrode with high sunlight transmittance (transmittance 78%) and high infrared reflection (reflectivity 75%) is prepared on its surface; (2) The first transparent electrode surface is subjected to magnetron sputtering, with metal Ni as the target, argon and oxygen as the sputtering gas, a total pressure of 1.0 Pa, an oxygen partial pressure of 20%, a distance between the target and the substrate of 15 cm, a DC power of 100 W or a power density of 2 W / cm 2 , a 20nm thick ion storage layer was deposited on the surface using a DC power supply; on the ion storage layer, a 40nm thick ion conduction layer was deposited using a LiTaO3 ceramic target at a total pressure of 2.0Pa, a pure argon atmosphere, a distance between the target and the substrate of 15cm, and a radio frequency power of 180W; (3) On the ion conductive layer, metal tungsten, molybdenum or titanium is used as the target, the sputtering gas is argon and oxygen, the total pressure is 2.0 Pa, the oxygen partial pressure is 12%, 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 70 W or the power density is 1.55 W / cm 2 A 400nm electrochromic layer film is deposited on the surface using a DC power supply; subsequently, the film is rapidly annealed and rapidly heat-treated in an inert atmosphere at a heat treatment pressure of 50 torr. The heat treatment process is heating to 350°C for 20 seconds, keeping warm for 100 seconds, then heating to 450°C for 10 seconds, keeping warm for 200 seconds, and then naturally cooling to room temperature to obtain the electrochromic layer; finally, a second transparent electrode with wide-band high transmittance (transmittance 80%) is deposited on the electrochromic layer to obtain the ultra-wide-band regulated all-solid-state electrochromic device.

[0075] Comparative Example 1

[0076] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (1), a BaF2 single crystal is used as a substrate, and a second transparent electrode with a wide band and high transmittance (transmittance 80%) is deposited on its surface; In step (3), a first transparent electrode with high transmittance to sunlight (transmittance 78%) and high reflectance to infrared (reflectivity 75%) is deposited on the ion storage layer.

[0077] Comparative Example 2

[0078] The preparation method of the electrochromic device provided in this comparative example refers to Example 14, with the following main differences: In step (1), a BaF2 single crystal is used as a substrate, and a second transparent electrode with a wide band and high transmittance (transmittance 80%) is deposited on its surface; In step (3), a first transparent electrode with high sunlight transmittance (transmittance 78%) and high infrared reflectivity (reflectivity 75%) is deposited on the electrochromic layer.

[0079] Comparative Example 3

[0080] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (2), in the process of annealing the electrochromic film: the heat treatment pressure is 50 torr, the heat treatment process is heating to 350° C. in 20 seconds and keeping the temperature for 300 seconds.

[0081] Comparative Example 4

[0082] The preparation method of the electrochromic device provided in this comparative example refers to Example 1, with the following main differences: In step (2), in the process of annealing the electrochromic film: the heat treatment pressure is 50 torr, the heat treatment process is heating to 450° C. in 20 seconds and keeping the temperature for 300 seconds.

[0083] The following is a comparison of the experimental parameters and performance of the electrochromic devices in Examples 1-14 and Comparative Examples 1-4: Note: 1. Glass / ITO (high reflection) / NiO / LiTaO3 / WO3 / ITO (high transmittance) is referred to as GINLWI; 2. ITO (high reflective) / NiO / LiTaO3 / WO3 / ITO (high transmittance) / BaF2 referred to as INLWIB; 3. Glass / ITO (high reflection) / WO3 / LiTaO3 / NiO / ITO (high transmittance) is referred to as GIWLNI; 4. ITO (high reflective) / WO3 / LiTaO3 / NiO / ITO (high transmittance) / BaF2, referred to as IWLNIB.

[0084] Although the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description is not intended to limit the present invention. After reading the above description, various modifications and substitutions of the present invention will become apparent to those skilled in the art. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. An ultra-wideband controlled all-solid-state electrochromic device, characterized in that: The structure of the ultra-wideband controlled all-solid-state electrochromic device comprises: a glass substrate, a first transparent electrode, an ion storage layer, an ion conduction layer / electrolyte layer, an electrochromic layer, and a second transparent electrode stacked in sequence, or a glass substrate, a first transparent electrode, an electrochromic layer, an ion conduction layer / electrolyte layer, an ion storage layer, and a second transparent electrode; in: The material of the electrochromic layer includes WO 3-x 、MoO 3-x and TiO 2-x At least one of the above, the surface layer of the electrochromic layer in contact with the electrolyte layer is rich in oxygen vacancies, the surface layer is 0.2<x≤1, and the part outside the surface layer is 0≤x≤0.

2.

2. The ultra-wideband controllable all-solid-state electrochromic device according to claim 1, characterized in that: The material of the first transparent electrode includes at least one of transparent conductive oxide, MXENE, and metal nanowires; Preferably, the sheet resistance of the first transparent electrode is 10 to 400 Ω / cm 2 , the sunlight transmittance in the 0.38~2.5μm band is ≥75%, and the mid-infrared reflectivity in the 2.5~25um band is ≥75%.

3. The ultra-wideband controllable all-solid-state electrochromic device according to claim 1 or 2, characterized in that: The materials of the ion conducting layer / electrolyte layer include LiTaO3, LiNbO3, Li 0.35 La 0.57 At least one of TiO3, Li2Ti2O5; Preferably, the infrared transmittance of the ion conducting layer / electrolyte layer in the 8-13 μm band is ≥80%.

4. The ultra-wideband controllable all-solid-state electrochromic device according to any one of claims 1 to 3, characterized in that: The material of the ion storage layer includes NiO x 、V2O5、CoO x At least one of; Preferably, the infrared transmittance of the ion storage layer in the 8-13 μm band is ≥80%.

5. The ultra-wideband controllable all-solid-state electrochromic device according to any one of claims 1 to 4, characterized in that: The material of the second transparent electrode includes at least one of transparent conductive oxide, MXENE, and metal nanowires; Preferably, the second transparent electrode has a solar transmittance of ≥75% in the 0.38-2.5 μm band and a mid-infrared transmittance of ≥75% in the 2.5-25 μm band.

6. The ultra-wideband controllable all-solid-state electrochromic device according to any one of claims 1 to 5, characterized in that: The ultra-wide band controlled all-solid-state electrochromic device has a stable cycle number of ≥20,000 times, a mid-to-far infrared emissivity adjustment rate of ≥0.3 in the 8-13 μm band, a solar band adjustment capability of ≥0.5, a visible infrared control capability selectivity ratio of ≥0.7, and a device effective area of ​​≥100 cm 2 .

7. A method for preparing an ultra-wideband controllable all-solid-state electrochromic device according to any one of claims 1 to 6, characterized in that: The preparation method comprises: preparing an electrochromic layer on the surface of an ion conducting layer or a first transparent electrode by magnetron sputtering and annealing process; the annealing process is heat treatment in an inert atmosphere, and the heat treatment pressure is 2-200 Torr.

8. The preparation method according to claim 7, characterized in that The process parameters of the magnetron sputtering include: the sputtering gas is argon and oxygen, the total pressure is 0.5-2.0 Pa, and the oxygen partial pressure is 0-50%; Preferably, the vertical distance between the target and the substrate is 10-20 cm; the initial substrate temperature is room temperature; the DC power applied to the target is 30-200 W or the power density is 0.6-3.0 W / cm 2 .

9. The preparation method according to claim 7 or 8, characterized in that The heat treatment process is as follows: heating to 300-400° C. for 10-40 seconds and then keeping the temperature for 50-200 seconds, then heating to 350-500° C. for 5-20 seconds and then keeping the temperature for 100-1000 seconds, and naturally cooling to room temperature.

Images