Long-life electrochromic intelligent window and preparation method thereof

Abstract

The invention relates to the technical field of electrochromic materials, in particular to a long-life electrochromic intelligent window and a preparation method thereof. Comprising a conductive substrate and an electrochromic device, the electrochromic device is arranged above the conductive substrate and comprises a transparent conductive film, an anode electrochromic film, a cathode electrochromic film and an electrolyte layer, and a plurality of layers of visible near-infrared anti-reflection infrared high-emission multilayer films are arranged above the electrochromic device. According to the structure, the optical regulation and control amplitude of the electrochromic device can be increased, visible infrared rays, near infrared rays and middle and far infrared rays are effectively blocked, the temperature of the colored electrochromic device is reduced, and the service life of the electrochromic intelligent window is prolonged.

Description

Technical Field

[0001] This invention patent relates to the field of electrochromic materials technology, and in particular to a long-life electrochromic smart window and its preparation method. Background Technology

[0002] Electrochromic smart windows, with their excellent and reversible optical properties, have shown great promise in fields such as architectural smart windows and automotive sunroofs. Because electrochromic materials can control light energy and reduce energy loss, aligning with future trends in smart materials, they have attracted increasing attention. Especially now, with growing awareness of energy conservation and environmental protection, the application of electrochromic materials in smart windows has become a research hotspot. However, the high absorption of visible light by the electrochromic colored state causes the device temperature to rise, radiating energy and increasing indoor and vehicle interior temperatures. This also severely impacts the device's lifespan, gradually becoming a bottleneck restricting its further application.

[0003] To address the above problems, this invention prepares a visible-near-infrared anti-reflection and infrared high-emission multilayer film on the surface of an electrochromic device using a physicochemical vapor deposition method. When used in conjunction with the electrochromic device, this increases the optical control amplitude of the electrochromic device, reduces the temperature of the colored electrochromic device, and improves the service life of the electrochromic smart window. Summary of the Invention

[0004] (a) Problems to be solved This invention is mainly used to solve the problem of high absorption of visible light by electrochromic colored states, which causes the device temperature to rise and radiate energy, resulting in increased indoor and vehicle interior temperatures. It provides a long-life electrochromic smart window and its preparation method.

[0005] (II) Technical Solution The present invention discloses a long-life electrochromic smart window, comprising a conductive substrate and an electrochromic device, characterized in that: the electrochromic device is located above the conductive substrate, comprising a transparent conductive film, an anodic electrochromic film, a cathode electrochromic film, and an electrolyte layer; above the electrochromic device are several layers of visible and near-infrared anti-reflection and infrared high-emission multilayer films; and above the visible and near-infrared anti-reflection and infrared high-emission multilayer films is a protective layer.

[0006] As a preferred technical solution, the structure of the visible and near-infrared anti-reflection and high-emission multilayer film consists of an Al2O3 film, a TiO2 film, and a SiO2 film from bottom to top, with the thickness of each film being 100-1000 nm.

[0007] As a preferred technical solution, the structure of the electrochromic device, from bottom to top, consists of a transparent conductive film, a cathode electrochromic film, an electrolyte layer, an anode electrochromic film, and a transparent conductive film.

[0008] As a preferred technical solution, the thickness of the transparent conductive film is 100-1000nm, and the material is either ITO film or AZO film.

[0009] As a preferred technical solution, the thickness of the cathode electrochromic film is 100-1000 nm, and the material is any one of tungsten oxide film, titanium dioxide film, or molybdenum oxide film; the thickness of the anode electrochromic film is 100-1000 nm, and the material is any one of nickel oxide film or vanadium oxide film.

[0010] As a preferred technical solution, the thickness of the electrolyte layer is 100-1000nm, and the material is any one of lithium, magnesium, or aluminum or a compound film thereof.

[0011] As a preferred technical solution, the conductive substrate material is any one of ITO thin film, AZO thin film, CNT thin film, Ag nanowire thin film, quartz glass, PET or PMMA.

[0012] As a preferred technical solution, the thickness of the protective layer is 100-1000 nm, and the material is a germanium film.

[0013] This invention discloses a method for preparing a long-life electrochromic smart window, comprising the following steps: S1. Preparation of conductive substrate: The conductive substrate was ultrasonically cleaned with isopropanol, ethanol and deionized water for 15 min in sequence, and then dried. S2. Fabrication of electrochromic devices: Transparent conductive films, cathode electrochromic films, electrolyte layers and anode electrochromic films are all fabricated by physical vapor deposition at a rate of 0.1-1 Å / s and a film thickness of 100-1000 nm. S3. Preparation of visible and near-infrared antireflection and high-emission multilayer films: ①Al2O3 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.1-1 Å / s, with a film thickness of 100-1000 nm; ②TiO2 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.1-1 Å / s, with a film thickness of 100-1000 nm; ③SiO2 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.1-1 Å / s, with a film thickness of 100-1000 nm; S4. Repeat the above process S3 0-10 times to prepare a multilayer visible and near-infrared antireflection infrared high emission multilayer film. S5. Preparation of protective layer: Prepared by physical or chemical vapor deposition at a rate of 0.1-1 Å / s and a film thickness controlled at 100-1000 nm.

[0014] (III) Beneficial Effects The beneficial effects of this invention are as follows: This invention provides a long-life electrochromic smart window. The smart window is created by first fabricating a traditional all-solid-state electrochromic device, and then using physicochemical vapor deposition to prepare a visible / near-infrared anti-reflection and high-emission multilayer film on the surface of the electrochromic device. This film, combined with the electrochromic device, increases the optical modulation amplitude of the electrochromic device, effectively blocks visible, near-infrared, and mid-to-far-infrared light, reduces the temperature of the colored electrochromic device, and improves the lifespan of the electrochromic smart window. Comparative analysis shows that the smart window with the multilayer film exhibits a 5-8% increase in optical modulation amplitude, a 3-5°C lower surface temperature for the colored device, and a 1000-cycle increase in lifespan compared to the smart window without the multilayer film. Attached Figure Description

[0015] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0016] Figure 1 This is a schematic diagram of the overall structure of the present invention; Figure 2 This is a schematic diagram of the electrochromic device structure of the present invention; Figure 3 This is a schematic diagram of the visible and near-infrared anti-reflection and high-emission multilayer film structure of the present invention; Figure 4 This is a schematic diagram illustrating the application principle of the present invention; 1-Conductive substrate; 2-Electrochromic device; 21-Transparent conductive film; 22-Cathode electrochromic film; 23-Electrolyte layer; 24-Anode electrochromic film; 3-Visible and near-infrared anti-reflection infrared high-emission multilayer film; 31-Al2O3 film; 32-TiO2 film; 33-SiO2 film; 4-Protective layer. Detailed Implementation

[0017] The invention provides a long-life electrochromic smart window and its preparation method, with reference to the accompanying drawings.

[0018] As shown in the attached figure, a long-life electrochromic smart window includes a conductive substrate 1 and an electrochromic device 2. The electrochromic device 2 is located on top of the conductive substrate 1 and includes a transparent conductive film 21, an anodic electrochromic film 24, a cathode electrochromic film 22, and an electrolyte layer 23. Several layers of visible and near-infrared anti-reflection and infrared high-emission multilayer films 3 are located on top of the electrochromic device 2, and a protective layer 4 is located on top of the visible and near-infrared anti-reflection and infrared high-emission multilayer films 3.

[0019] Furthermore, the visible and near-infrared anti-reflection and high-emission multilayer film 3 has an Al2O3 film 31, a TiO2 film 32, and a SiO2 film 33 from bottom to top, and the film thickness of the Al2O3 film 31, the TiO2 film 32, and the SiO2 film 33 is 100-1000 nm.

[0020] Furthermore, the electrochromic device 2 has the following structure from bottom to top: a transparent conductive film 21, a cathode electrochromic film 22, an electrolyte layer 23, an anode electrochromic film 24, and a transparent conductive film 21. The present invention will now be described in further detail. It should be noted that the following embodiments are intended to facilitate understanding of the present invention and are not intended to limit it in any way. Specific Implementation Method 1 This invention provides a long-life electrochromic smart window and its preparation method, which is implemented according to the following steps: 1. Treatment of conductive substrate 1: The ITO conductive substrate 1 was ultrasonically cleaned with acetone, isopropanol and deionized water for 15 minutes in sequence, and then dried. II. Fabrication of Traditional All-Solid-State Electrochromic Devices: ① Preparation of cathode electrochromic thin film 22: Molybdenum oxide layer was prepared by physical vapor deposition; the preparation rate was 0.3 Å / s, and the film thickness was controlled at 600 nm; ② Electrolyte layer 23 preparation: LiF layer was prepared by physical vapor deposition; the preparation rate was 0.4 Å / s, and the film thickness was controlled at 200 nm; ③ Preparation of anodic electrochromic thin film 24: Nickel oxide layer was prepared by physical vapor deposition; the preparation rate was 0.4 Å / s, and the film thickness was controlled at 200 nm; ④ Preparation of transparent conductive film 21: ITO film preparation, ITO film was prepared by physical vapor deposition; the preparation rate was 0.5 Å / s, and the film thickness was controlled at 200 nm.

[0022] III. Preparation of Visible and Near Infrared Antireflection Infrared High Emission Multilayer Film 3: ① Al2O3 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.4 Å / s, with the film thickness controlled at 30 nm; ②TiO2 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.3 Å / s, with the film thickness controlled at 50 nm; ③ Preparation of SiO2 thin film 33: Prepared by physical or chemical vapor deposition at a rate of 0.2 Å / s, with the film thickness controlled at 80 nm.

[0023] IV. Preparation of protective layer 4: Germanium film is prepared by physical or chemical vapor deposition at a rate of 0.3 Å / s and the film thickness is controlled at 100 nm. Specific Implementation Method Two This invention provides a long-life electrochromic smart window and its preparation method, which is implemented according to the following steps: 1. Treatment of conductive substrate 1: The ITO conductive substrate 1 was ultrasonically cleaned with acetone, isopropanol and deionized water for 15 minutes in sequence, and then dried. II. Fabrication of Traditional All-Solid-State Electrochromic Devices: ① Preparation of cathode electrochromic thin film 22: Tungsten oxide thin film was prepared by physical vapor deposition; the preparation rate was 0.4 Å / s, and the film thickness was controlled at 600 nm; ② Electrolyte layer 23 preparation: MgF2 layer was prepared by physical vapor deposition; the preparation rate was 0.6 Å / s, and the film thickness was controlled at 200 nm; ③ Preparation of anodic electrochromic thin film 24: Nickel oxide thin film was prepared by physical vapor deposition; the preparation rate was 0.4 Å / s, and the film thickness was controlled at 200 nm; ④ Preparation of transparent conductive film 21: Transparent ITO film was prepared by physical vapor deposition; the preparation rate was 0.5 Å / s, and the film thickness was controlled at 200 nm; III. Preparation of Visible and Near Infrared Antireflection Infrared High Emission Multilayer Film 3: ① Al2O3 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.4 Å / s, with the film thickness controlled at 30 nm; ②TiO2 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.3 Å / s, with the film thickness controlled at 50 nm; ③ Preparation of SiO2 thin film 33: Prepared by physical or chemical vapor deposition at a rate of 0.2 Å / s, with the film thickness controlled at 80 nm.

[0025] IV. Preparation of protective layer 4: Germanium film is prepared by physical or chemical vapor deposition at a rate of 0.3 Å / s and the film thickness is controlled at 100 nm. Specific Implementation Method 3 This invention provides a long-life electrochromic smart window and its preparation method, which is implemented according to the following steps: 1. Treatment of conductive substrate 1: The ITO conductive substrate 1 was ultrasonically cleaned with acetone, isopropanol and deionized water for 15 minutes in sequence, and then dried. II. Fabrication of Traditional All-Solid-State Electrochromic Devices: ① Preparation of cathode electrochromic thin film 22: Tungsten oxide thin film was prepared by physical vapor deposition; the preparation rate was 0.4 Å / s, and the film thickness was controlled at 600 nm; ② Electrolyte layer 23 preparation: LiF layer was prepared by physical vapor deposition; the preparation rate was 0.6 Å / s, and the film thickness was controlled at 200 nm; ③ Preparation of anodic electrochromic thin film 24: Nickel oxide thin film was prepared by physical vapor deposition; the preparation rate was 0.4 Å / s, and the film thickness was controlled at 200 nm; ④ Preparation of transparent conductive film 21: Transparent ITO film was prepared by physical vapor deposition; the preparation rate was 0.5 Å / s, and the film thickness was controlled at 200 nm; III. Preparation of Visible and Near Infrared Antireflection Infrared High Emission Multilayer Film 3: ① Al2O3 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.4 Å / s, with the film thickness controlled at 30 nm; ②TiO2 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.3 Å / s, with the film thickness controlled at 50 nm; ③ Preparation of SiO2 thin film 33: Prepared by physical or chemical vapor deposition at a rate of 0.2 Å / s, with the film thickness controlled at 80 nm.

[0027] ④ Preparation of Al2O3 thin film 31: The film was prepared by physical or chemical vapor deposition at a rate of 0.4 Å / s and the film thickness was controlled at 40 nm. ⑤TiO2 thin film preparation: prepared by physical or chemical vapor deposition at a rate of 0.3 Å / s, with the film thickness controlled at 60 nm; ⑥ Preparation of SiO2 thin film 33: Prepared by physical or chemical vapor deposition at a rate of 0.2 Å / s, with the film thickness controlled at 70 nm.

[0028] Preparation of protective layer 4: Germanium film is prepared by physical or chemical vapor deposition at a rate of 0.3 Å / s and the film thickness is controlled at 100 nm.

[0029] The combined use of visible and near-infrared anti-reflection and high-emissivity multilayer films with electrochromic devices can increase the optical modulation amplitude of the electrochromic devices, effectively block visible infrared, near-infrared, and mid-far-infrared light, reduce the temperature of the colored electrochromic devices, and improve the service life of electrochromic smart windows. Comparative studies show that smart windows with multilayer films exhibit a 5-8% increase in optical modulation amplitude, a 3-5°C lower surface temperature for the colored devices, and a 1000-cycle increase in service life compared to those without.

[0030] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the concept and scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the design concept of the present invention should fall within the protection scope of the present invention. The technical content for which protection is sought in the present invention has been fully described in the claims.

Claims

1. A long-life electrochromic smart window, comprising a conductive substrate (1) and an electrochromic device (2), characterized in that: Above the conductive substrate (1) is an electrochromic device (2), which includes a transparent conductive film (21), an anode electrochromic film (24), a cathode electrochromic film (22), and an electrolyte layer (23). Above the electrochromic device (2) are several layers of visible and near-infrared anti-reflection infrared high-emission multilayer films (3), and above the visible and near-infrared anti-reflection infrared high-emission multilayer films (3) is a protective layer (4).

2. The long-life electrochromic smart window according to claim 1, characterized in that: The visible and near-infrared anti-reflection infrared high emission multilayer film (3) has an Al2O3 film (31), a TiO2 film (32) and a SiO2 film (33) from bottom to top. The thickness of the Al2O3 film (31), TiO2 film (32) and SiO2 film (33) is 100-1000nm.

3. The long-life electrochromic smart window according to claim 1, characterized in that: The electrochromic device (2) has a structure from bottom to top consisting of a transparent conductive film (21), a cathode electrochromic film (D), an electrolyte layer (23), an anode electrochromic film (24), and a transparent conductive film (21).

4. The long-life electrochromic smart window according to claim 3, characterized in that: The thickness of the transparent conductive film (21) is 100-1000 nm, and the material is either ITO film or AZO film.

5. A long-life electrochromic smart window according to claim 3, characterized in that: The cathode electrochromic film (22) has a thickness of 100-1000 nm and is made of any one of tungsten oxide film, titanium dioxide film, or molybdenum oxide film; the anode electrochromic film (24) has a thickness of 100-1000 nm and is made of any one of nickel oxide film or vanadium oxide film.

6. A long-life electrochromic smart window according to claim 3, characterized in that: The electrolyte layer (23) has a thickness of 100-1000 nm and is made of any one of lithium, magnesium or aluminum or a compound film thereof.

7. A long-life electrochromic smart window according to claim 1, characterized in that: The conductive substrate (1) material is any one of ITO film, AZO film, CNT film, Ag nanowire film, quartz glass, PET or PMMA.

8. A long-life electrochromic smart window according to claim 1, characterized in that: The protective layer (4) has a thickness of 100-1000 nm and is made of germanium film.

9. A method for preparing a long-life electrochromic smart window according to any one of claims 1-8, characterized in that, Includes the following steps: S1. Preparation of conductive substrate (1): The conductive substrate (1) was ultrasonically cleaned with isopropanol, ethanol and deionized water for 15 min in sequence and then dried. S2. Preparation of electrochromic device (2): The transparent conductive film (21), the cathode electrochromic film (22), the electrolyte layer (23) and the anode electrochromic film (24) were all prepared by physical vapor deposition at a rate of 0.1-1 Å / s and a film thickness of 100-1000 nm. S3. Preparation of visible and near-infrared antireflection and high-emission multilayer film (3): (1) Preparation of Al2O3 thin film (31): Prepared by physical or chemical vapor deposition at a rate of 0.1-1 Å / s, with a film thickness of 100-1000 nm; (2) Preparation of TiO2 thin film (32): The film is prepared by physical or chemical vapor deposition at a rate of 0.1-1 Å / s and the film thickness is 100-1000 nm. (3) Preparation of SiO2 thin film (33): Prepared by physical or chemical vapor deposition at a rate of 0.1-1 Å / s, with a film thickness of 100-1000 nm; S4. Repeat the above process S3 0-10 times to prepare a multilayer visible and near-infrared anti-reflection infrared high-emission multilayer film (3). S5. Preparation of protective layer (4): Prepared by physical or chemical vapor deposition at a rate of 0.1-1 Å / s and a film thickness of 100-1000 nm.

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