Multi-band dynamic regulation electrochromic smart window and preparation method and application thereof

Abstract

The application provides a multi-band dynamic regulation electrochromic smart window and a preparation method and application thereof, and the multi-band dynamic regulation electrochromic smart window comprises an infrared transparent layer, a PEDOT:PSS electrochromic layer, an electrolyte layer, an ion storage layer and a transparent conductive substrate which are sequentially and layerwisely arranged. The multi-band dynamic regulation electrochromic smart window provided by the application can realize high-performance dynamic regulation of the electrochromic smart window in the visible-near infrared-mid infrared-microwave range based on the transition of the metal state-insulating state of the PEDOT:PSS electrochromic layer before and after voltage application and the ion embedding / extraction principle in the redox process, and the preparation method is simple, and the electrochromic smart window has wide application scenarios in different scenes.

Description

Technical Field

[0001] This invention relates to the field of electrochromic smart window technology, specifically to a multi-band dynamically adjustable electrochromic smart window, its preparation method, and its application. Background Technology

[0002] Windows are the primary channel for energy exchange between indoors and outdoors, and their energy loss accounts for 20% to 40% of building heating and cooling energy consumption, making them a critical factor in building energy efficiency. Therefore, developing energy-efficient windows is crucial for promoting green buildings and achieving zero-carbon building goals. Unlike photochromic and thermochromic smart windows that passively adjust to changes in ambient light or temperature, electrochromic smart windows actively control color and light transmittance by altering voltage. This not only significantly reduces building energy consumption but also effectively improves indoor thermal comfort, achieving energy savings of up to 20% compared to traditional windows. Currently, electrochromic smart windows have made significant progress in both basic electrochemical research and commercial applications, and are expected to play a vital role in building energy conservation.

[0003] In the construction field, heat transfer through windows mainly includes three modes: conduction, convection, and thermal radiation, with thermal radiation accounting for more than 50% of the total heat transfer. Thermal radiation involves wavelengths including visible light (380~780 nm), near-infrared light (780~2500 nm), and mid-infrared light (8~13 μm). The spectral control capability of these wavelengths is crucial for achieving efficient photothermal management of windows. Currently, most research on electrochromic smart windows focuses on the dynamic control of visible and near-infrared wavelengths, with relatively weak dynamic control capabilities for the mid-infrared band, becoming a major bottleneck limiting the performance improvement of energy-efficient smart windows in buildings. Patent CN117348304A discloses an integrated dual-band electrochromic smart window and its fabrication method, which can effectively control the radiation energy of the visible and near-infrared bands under low-voltage driving conditions; however, it lacks adjustment capabilities for the mid-infrared band, thus failing to achieve effective temperature control. Furthermore, most electrochromic devices rely on rigid substrates such as ITO glass, resulting in complex structures and fabrication processes that primarily employ magnetron sputtering and electrodeposition, limiting their large-area fabrication. Patent CN104698716B discloses an adaptive electrochromic smart window, with an electrochromic structure consisting of a bottom electrode layer, an ion storage layer, an electrolyte layer, an electrochromic layer, and a top electrode layer; similarly, a solar cell structure consists of an n-type semiconductor layer, an intrinsic semiconductor layer, a p-type semiconductor layer, a metal electrode layer, and a protective layer. However, the fabrication methods are cumbersome and the equipment is expensive, hindering low-cost, large-area scalable fabrication and posing a significant challenge to the widespread application of electrochromic smart windows in various fields. Therefore, developing a low-cost, scalable fabrication process and achieving multi-band dynamic high-modulation electrochromic smart windows is crucial and urgent. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a multi-band dynamically adjustable electrochromic smart window, its preparation method, and its application.

[0005] The technical solution of this invention is as follows: In a first aspect, the present invention provides a band-dynamically modulated electrochromic smart window, the smart window comprising an infrared transparent layer, a PEDOT:PSS electrochromic layer, an electrolyte layer, an ion storage layer, and a transparent conductive substrate stacked sequentially.

[0006] Furthermore, the material of the infrared transparent layer includes at least one of polyethylene, polyamide 6, polyamide 66, polymethylpentene, polytetrafluoroethylene, polymethyl methacrylate, and styrene-ethylene-butene-styrene block copolymer.

[0007] Furthermore, the method for preparing the PEDOT:PSS electrochromic layer is as follows: Add 3 wt.% to 15 wt.% of a polar solvent and 0.01 wt.% to 0.25 wt.% of a surfactant to a PEDOT:PSS suspension, coat and anneal to form a film, and obtain the PEDOT:PSS electrochromic layer; Alternatively, 0.01 wt.%~0.25 wt.% surfactant is added to the PEDOT:PSS suspension, and after coating and annealing to form a film, post-treatment is performed using organic solvents or inorganic acids to obtain the PEDOT:PSS electrochromic layer. The polar solvent is at least one of methyl sulfoxide, N,N-dimethylformamide, sorbitol, ethylene glycol, methoxyethanol, and diethylene glycol. The surfactant is Triton. TM At least one of X-100, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, quaternary ammonium salt, alkylamine oxide, 2-alkylimidazoline, and polyethylene glycol; The organic solvent is at least one of ethylene glycol, methanol, formic acid, methanesulfonic acid, and toluenesulfonic acid; The inorganic acid is at least one of sulfuric acid, nitric acid, and hydrochloric acid.

[0008] Furthermore, the electrolyte layer is a liquid-phase electrolyte layer or a gel-phase electrolyte layer; The liquid electrolyte layer is a solution of lithium salt electrolyte dissolved in a solvent. The lithium salt electrolyte includes at least one of lithium hexafluoroborate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium dioxaborate, lithium carbonate, and lithium hydroxide. The solvent includes at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, methyl ethyl carbonate, ethyl acetate, methyl propionate, tetrahydrofuran, dioxane, and N,N-dimethylformamide. The gel phase electrolyte layer is a gel composed of a polymer matrix, an electrolyte salt, and an organic solvent; wherein, the polymer matrix includes at least one of polymethyl methacrylate, polyethylene oxide, polyvinylidene fluoride and its copolymers, and polyacrylonitrile; the electrolyte salt includes at least one of lithium hexafluoroborate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, and lithium bis(trifluoromethanesulfonyl)imide; and the organic solvent includes at least one of propylene carbonate, ethyl methyl carbonate, ethyl acetate, and methyl propionate.

[0009] Furthermore, the material of the ion storage layer includes inorganic transition metal oxides or conductive polymers; The inorganic transition metal oxide includes at least one of nickel oxide, titanium dioxide, cerium dioxide, vanadium pentoxide, tungsten trioxide, molybdenum oxide, and niobium oxide. The conductive polymer includes at least one of polyaniline, polypyrrole, polythiophene and its derivative poly(3,4-ethylenedioxythiophene) (PEDOT).

[0010] Furthermore, the transparent conductive substrate includes a flexible substrate material and a conductive film; The flexible substrate material includes polyimide or polyethylene terephthalate; The conductive film includes at least one of indium tin oxide conductive film, fluorine-doped tin dioxide conductive film, silver nanowire conductive film, metal mesh conductive film, conductive polymer conductive film, and graphene conductive film.

[0011] In a second aspect, the present invention provides a method for preparing the above-mentioned multi-band dynamically modulated electrochromic smart window, the method comprising the following steps: A PEDOT:PSS solution is coated onto an infrared transparent layer to form an infrared transparent layer with a PEDOT:PSS electrochromic layer. After assembling the electrolyte layer with the infrared transparent layer with the PEDOT:PSS electrochromic layer, the ion storage layer, and the transparent conductive substrate, the multi-band dynamically modulated electrochromic smart window is obtained.

[0012] Furthermore, the coating includes at least one of spraying, spin coating, and blade coating.

[0013] In a third aspect, the present invention provides an application of the aforementioned multi-band dynamically adjustable electrochromic smart window, wherein the multi-band dynamically adjustable electrochromic smart window has at least the following applications: a. Application in the manufacture of intelligent energy-saving windows; b. Applications in the manufacture of electronic products; c. Application in the preparation of temperature-adaptive greenhouse devices.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. The multi-band dynamically adjustable electrochromic smart window provided by this invention is based on the transition from the metallic to the insulating state of the PEDOT:PSS electrochromic layer before and after voltage application, as well as the principle of ion insertion / extraction during redox processes. This enables high-performance dynamic control of the electrochromic smart window across the visible-near-infrared-mid-infrared-microwave range. The multi-band dynamically adjustable electrochromic smart window provided by this invention exhibits a reflectance change rate ≥0.39 in the 8~13 μm band, a maximum transmittance contrast ratio ≥25.95% in the 250~2500 nm band, and a reflectance change rate ≥22% in the 8.2~12.4 GHz microwave band. It also demonstrates excellent dynamic temperature control performance (≥7 ℃), cycle stability (≥200 cycles), fast response time (coloring 2.9 s / fading 2.7 s), and high coloring efficiency (193.7 cm⁻¹). 2 C -1 Performance such as ).

[0015] 2. The multi-band dynamic control electrochromic smart window provided by this invention has the advantages of flexibility, simple structure, simple manufacturing process and low cost, and has a wide range of applications. Attached Figure Description

[0016] Other features, objects, and advantages of the present invention will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings: Figure 1 A schematic diagram illustrating the structure and working principle of the multi-band dynamically adjustable electrochromic smart window provided by the present invention; Figure 2 This is a schematic diagram showing the color change of the multi-band dynamically adjustable electrochromic smart window before and after a voltage change, as provided in the first embodiment of the present invention. Figure 3 The infrared spectrum of the multi-band dynamically adjustable electrochromic smart window provided in the first embodiment of the present invention. Detailed Implementation

[0017] The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any way. It should be noted that those skilled in the art can make several changes and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention.

[0018] like Figure 1 As shown, this invention provides a multi-band dynamically modulated electrochromic smart window, comprising an infrared transparent layer, a PEDOT:PSS electrochromic layer, an electrolyte layer, an ion storage layer, and a transparent conductive substrate stacked sequentially. The infrared transparent layer aims to achieve efficient transmission of mid-infrared light while also providing protection. Based on the transition of the PEDOT:PSS electrochromic layer from a metallic state (heating mode) to an insulating state (cooling mode) before and after voltage application, and the principle of ion insertion / extraction during redox processes, high-performance dynamic control of the electrochromic smart window across visible, near-infrared, mid-infrared, and microwave ranges can be achieved. Given the high conductivity of PEDOT:PSS, this layer also functions as an electrode. The electrolyte layer provides a transport channel for ions while suppressing direct electron conduction; its state can be liquid, semi-solid, or solid. The ion storage layer is primarily responsible for storing ions or electrons to maintain charge balance. The transparent conductive substrate acts as an electrode, introducing the electric field from the external circuit into the device, driving the redox reaction of the electrochromic layer, and providing structural support for the entire device.

[0019] The infrared transparent layer is made of at least one of polyethylene, polyamide 6, polyamide 66, polymethylpentene, polytetrafluoroethylene, polymethyl methacrylate, and styrene-ethylene-butene-styrene block copolymer.

[0020] The preparation method of PEDOT:PSS electrochromic layer is as follows: 3 wt.%~15 wt.% of polar solvent and 0.01 wt.%~0.25 wt.% of surfactant are added to PEDOT:PSS suspension, and the mixture is coated and annealed to form a film, thereby obtaining the PEDOT:PSS electrochromic layer; Alternatively, the preparation method of PEDOT:PSS electrochromic layer can be as follows: 0.01 wt.%~0.25 wt.% of surfactant is added to PEDOT:PSS suspension, and the mixture is coated and annealed to form a film; then, post-treatment is performed using an organic solvent or inorganic acid to obtain the PEDOT:PSS electrochromic layer. The polar solvent is at least one of methyl sulfoxide, N,N-dimethylformamide, sorbitol, ethylene glycol, methoxyethanol, and diethylene glycol; The surfactant is Triton TM At least one of X-100, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, quaternary ammonium salt, alkylamine oxide, 2-alkylimidazoline, and polyethylene glycol; The organic solvent is at least one of ethylene glycol, methanol, formic acid, methanesulfonic acid, and toluenesulfonic acid; The inorganic acid is at least one of sulfuric acid, nitric acid, and hydrochloric acid.

[0021] The electrolyte layer is either a liquid phase electrolyte layer or a gel phase electrolyte layer. The liquid phase electrolyte layer is a solution of lithium salt electrolyte dissolved in a solvent, wherein the lithium salt electrolyte includes at least one of lithium hexafluoroborate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium dioxaborate, lithium carbonate, and lithium hydroxide; the solvent includes at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, methyl ethyl carbonate, ethyl acetate, methyl propionate, tetrahydrofuran, dioxane, and N,N-dimethylformamide; the gel phase electrolyte layer is a gel composed of a polymer matrix, an electrolyte salt, and an organic solvent; wherein the polymer matrix includes at least one of polymethyl methacrylate, polyethylene oxide, polyvinylidene fluoride and its copolymers, and polyacrylonitrile; the electrolyte salt includes at least one of lithium hexafluoroborate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, and lithium bis(trifluoromethanesulfonyl)imide; and the organic solvent includes at least one of propylene carbonate, methyl ethyl carbonate, ethyl acetate, and methyl propionate.

[0022] The material of the ion storage layer includes inorganic transition metal oxides or conductive polymers; the inorganic transition metal oxides include at least one of nickel oxide, titanium dioxide, cerium dioxide, vanadium pentoxide, tungsten trioxide, molybdenum oxide, and niobium oxide; the conductive polymers include at least one of polyaniline, polypyrrole, polythiophene and its derivative poly(3,4-ethylenedioxythiophene) (PEDOT).

[0023] The transparent conductive substrate includes a flexible substrate and a conductive film; the flexible substrate is made of polyimide or polyethylene terephthalate; the conductive film includes at least one of indium tin oxide conductive film, fluorine-doped tin dioxide conductive film, silver nanowire conductive film, metal mesh conductive film, conductive polymer conductive film, and graphene conductive film.

[0024] The preparation method of a multi-band dynamically modulated electrochromic smart window includes the following steps: A PEDOT:PSS solution is coated onto an infrared transparent layer to form an infrared transparent layer with a PEDOT:PSS electrochromic layer; after assembling the electrolyte layer with the infrared transparent layer with the PEDOT:PSS electrochromic layer, the ion storage layer, and the transparent conductive substrate, the multi-band dynamically modulated electrochromic smart window is obtained.

[0025] Coating includes at least one of spraying, spin coating, and scraping.

[0026] The present invention will now be described in detail with reference to specific embodiments.

[0027] First Embodiment This embodiment provides a multi-band dynamically adjustable electrochromic smart window and its preparation method, as shown below: Composition and preparation of PEDOT:PSS electrochromic layer: 8% polar solvent ethylene glycol and 0.1% surfactant Triton were added to PEDOT:PSS (PH1000, Heraeus, Germany) liquid. TM X-100, after magnetic stirring at room temperature for 30 minutes, yields a PEDOT:PSS modified mixed solution. An electrochromic film with a thickness of 923 nm is prepared using a roll-to-roll coating process. Polyethylene (PE) is used as the material for the infrared transparent layer, and a PE film with a thickness of 10 μm is used as the infrared transparent layer in this embodiment. The PE film is mounted on the feed roller of the roll-to-roll equipment. The PEDOT:PSS modified mixed solution is placed in the feeding zone, and the equipment is started. The PE film is continuously fed from the feed roller into the coating area. Simultaneously, the feed pump delivers the PEDOT:PSS modified mixed solution to the slit-type coating head. The coating head uniformly coats the solution onto the surface of the PE film. After drying in a 40°C oven, the wet film transforms into a dry film, yielding the PEDOT:PSS electrochromic layer.

[0028] Preparation of the gel phase electrolyte layer: Prepare a 1 mol / L lithium tetrafluoroborate (LiBF4) solution with propylene carbonate (PC) as the solvent and stir until completely dissolved. Select a polyvinylidene fluoride (PVDF) porous film with a pore size of 0.22 μm and a thickness of 0.1 mm. Drop a small amount of LiBF4-PC solution onto the PVDF porous film until it is saturated with adsorption. The film will become transparent, and the LiBF4-PC-PVDF gel phase electrolyte layer is then prepared with a thickness of 0.1126 mm.

[0029] Preparation of transparent conductive substrate: Polyethylene terephthalate (PET)-indium tin oxide (ITO) conductive film was selected as the transparent conductive substrate in this embodiment (ITO-PET, Shenzhen Siyu Industrial Products Co., Ltd., 7Ω / sq), with a substrate thickness of 0.125mm.

[0030] Assembly of a multi-band dynamically modulated electrochromic smart window: A PEDOT:PSS modified mixed solution was spin-coated onto the surface of an ITO-PET transparent conductive substrate at a speed of 500 rpm and dried at 50°C to serve as an ion storage layer with a thickness of 200 nm. A gel phase electrolyte layer was then covered on the ion storage layer, and a PEDOT:PSS electrochromic layer coated on a PE film was then placed on top of the gel phase electrolyte layer. A small amount of silicone sealant was applied to the edges for insulation, thus creating a multi-band dynamically modulated electrochromic smart window.

[0031] After applying an external voltage to the multi-band dynamically modulated electrochromic smart window provided in this embodiment, high-performance dynamic control in the visible-near-infrared-mid-infrared-microwave range can be achieved by changing the voltage direction (+1V ~ -3V), as shown in the following figure. Figure 2 As shown, when a negative voltage of 10s is applied to the multi-band dynamically adjustable electrochromic smart window provided in this embodiment using a voltmeter, specifically by applying a negative voltage of -3V to the ITO-PET transparent substrate and the PEDOT:PSS electrochromic layer, at this time, Li + Embedded, the PEDOT:PSS electrochromic layer transforms into a reduced state, exhibiting an insulating state. The overall color of the multi-band dynamically adjustable electrochromic smart window is dark blue, with low transmittance in the visible-near-infrared band and low reflectance in the mid-infrared band. When a positive voltage (+1V) is applied to the multi-band dynamically adjustable electrochromic smart window provided in this embodiment for 10 seconds using a voltmeter, Li... + Upon extraction, the PEDOT:PSS electrochromic layer transforms from a reduced state to an oxidized state, forming bipolarons. The multi-band dynamically modulated electrochromic smart window provided in this embodiment exhibits a light blue overall color, high transmittance in the visible-near-infrared band, and increased reflectivity in the mid-infrared band. This indicates that the formation of bipolarons further enhances the conductivity of the PEDOT:PSS electrochromic layer, leading to increased reflectivity in the mid-infrared band and significantly improved transmittance in the visible-near-infrared band. The results demonstrate that, through potential control and synergistic ion insertion / extraction, the multi-band dynamically modulated electrochromic smart window provided by this invention can achieve modulation of visible-near-infrared-mid-infrared-microwave radiance, showing broad application prospects in the field of building energy conservation.

[0032] The optical performance test results of the multi-band dynamically adjustable electrochromic smart window provided in this embodiment are as follows: Figure 3As shown, the visible-near-infrared transmittance of the PEDOT:PSS electrochromic layer in both colored and faded states was measured using a Lambda 950 UV-Vis-NIR spectrometer with an integrating sphere (90 mm in diameter). A step size of 5 nm was set. A 3 cm × 3 cm multi-band dynamically adjustable electrochromic smart window was placed in the instrument's measurement window. Thin wires were connected to the ITO-PET transparent substrate and the PEDOT:PSS electrochromic layer. A voltmeter was connected to the other side of the thin wires, and a voltage was continuously applied. The measurement was started, and the transmittance was measured at applied voltages of +1V, 0V, -1V, -2V, and -3V, with a measurement wavelength of 250-2500 nm. The results showed that the maximum transmittance contrast of the smart window was ≥25.95%. Measurements were performed using a Fourier transform infrared spectrometer (Nicolet 6700) equipped with an infrared integrating sphere. A 3cm × 3cm multi-band dynamically adjustable electrochromic smart window was placed in the instrument's measurement window. A voltmeter was used to continuously apply voltage to the ITO-PET transparent substrate and the PEDOT:PSS electrochromic layer. Measurements were then taken at applied voltages of +1V, 0V, -1V, 2V, and -3V. Using the formula: emissivity = 1 - reflectivity - transmittance, the reflectivity change rate in the 8~13 μm band was found to be ≥0.39. The results demonstrate that the multi-band dynamically adjustable electrochromic smart window provided by this invention exhibits excellent optical control performance in the visible-near-infrared and mid-infrared bands, enabling precise and continuous spectral adjustment to meet diverse requirements for light and heat transmittance in different scenarios.

[0033] The electromagnetic shielding reflection loss of the multi-band dynamically adjustable electrochromic smart window provided in this embodiment was tested using a vector network analyzer and the waveguide method in the 8.2~12.4 GHz range. A voltmeter was used to apply a voltage of 10s to the ITO-PET transparent conductive layer and the PEDOT:PSS layer of the 2.9mm×10.2mm multi-band dynamically adjustable electrochromic smart window before placing it in the instrument's measurement window. Measurements were taken at applied voltages of +1V, 0V, -1V, -2V, and 3V, and the results were converted to reflectivity. The reflectivity change rate was found to be ≥22%. The results indicate that the multi-band dynamically adjustable electrochromic smart window provided by this invention exhibits excellent dynamic control performance in the 8.2~12.4 GHz microwave band, providing important guidance for microwave shielded smart windows.

[0034] Infrared images of the multi-band dynamically adjustable electrochromic smart window provided in this embodiment were captured using a T630SC infrared camera. The operating wavelength is 8-13 μm. During the measurement process, the predetermined emissivity of the equipment was set to 1.0, the room temperature was maintained at 25℃, and the relative humidity was maintained at 45%. The auxiliary equipment included an electric heating stage for uniformly heating the sample and a FLIR calculation software package for apparent temperature analysis. The results show that the multi-band dynamically adjustable electrochromic smart window provided in this embodiment has excellent infrared dynamic temperature control performance (≥7℃). When a square wave voltage ranging from -1 V to +1 V is applied to the smart window for 20 seconds each time, the infrared temperature cycling stability of the smart window is good (≥200 cycles), indicating that the multi-band dynamically adjustable electrochromic smart window provided in this embodiment possesses the durability required for practical applications. The response time is typically defined as the time required for the transmittance to change by 90% during the electrochromic process. Calculations show that this smart window has a fast coloring response time of 2.9 s and a fading response time of 2.7 s. Utilizing the transmittance under coloring and fading conditions, as well as the amount of charge required during the coloring and fading processes, the calculated coloring efficiency is as high as 193.7 cm⁻¹. 2 C -1 This indicates that the multi-band dynamically adjustable electrochromic smart window provided in this embodiment has a fast response capability and a coloring efficiency of up to 193.7 cm⁻¹. 2 C -1 It is far superior to conventional electrochromic materials (WO3 approximately 30-50 cm²C). -1 This indicates that the redox process of the PEDOT:PSS electrochromic layer has excellent charge-optical conversion efficiency.

[0035] Second Embodiment This embodiment provides a multi-band dynamically adjustable electrochromic smart window and its preparation method, as shown below: Composition and preparation of PEDOT:PSS electrochromic layer: 0.1% of the surfactant Triton was added to PEDOT:PSS (PH1000, Heraeus, Germany) liquid. TMX-100, magnetically stirred for 30 min at room temperature, yields a PEDOT:PSS modified mixed solution. An electrochromic film with a thickness of 923 nm is prepared using a roll-to-roll coating process. Polyethylene (PE) is used as the material for the infrared transparent layer, and a PE film with a thickness of 10 μm is used as the infrared transparent layer in this embodiment. The PE film is mounted on the feed roller of the roll-to-roll equipment. The PEDOT:PSS modified mixed solution is placed in the feeding zone, and the equipment is started. The PE film is continuously fed from the feed roller into the coating area. Simultaneously, a pump delivers the solution to a slit-type coating head. The coating head uniformly coats the solution onto the surface of the PE film. After drying, the wet film becomes a dry film. Then, 16 mol / L sulfuric acid is prepared and drop-coated onto the surface of the dry film. Annealing is performed at 60 °C for 1 h, and the film is rinsed with deionized water to ensure complete removal of any possible solvent residue. After this, annealing is performed again at 60 °C to remove residual water molecules. After drying, a sulfuric acid-treated PEDOT:PSS electrochromic layer is obtained.

[0036] Preparation of the gel phase electrolyte layer: Prepare a 1 mol / L lithium tetrafluoroborate (LiBF4) solution with propylene carbonate (PC) as the solvent and stir until completely dissolved. Select a polyvinylidene fluoride (PVDF) porous film with a pore size of 0.22 μm and a thickness of 0.1 mm. Drop a small amount of LiBF4-PC solution onto the PVDF porous film until it is saturated with adsorption. The film will become transparent, and the LiBF4-PC-PVDF gel phase electrolyte layer is then prepared with a thickness of 0.1126 mm.

[0037] Preparation of transparent conductive substrate: Polyethylene terephthalate (PET)-indium tin oxide (ITO) conductive film was selected as the transparent conductive substrate of this embodiment (ITO-PET, Shenzhen Siyu Industrial Products Co., Ltd., 7Ω / sq), with a thickness of 0.125mm.

[0038] Assembly of a multi-band dynamically modulated electrochromic smart window: A PEDOT:PSS modified mixed solution was spin-coated onto the surface of an ITO-PET transparent conductive substrate at 500 rpm and dried at 50 °C to form an ion storage layer with a thickness of 200 nm. A gel phase electrolyte layer was then coated onto the ion storage layer, and finally, a PEDOT:PSS electrochromic layer coated on a PE film was placed over the gel phase electrolyte layer. A small amount of silicone sealant was applied to the edges for insulation, thus completing the multi-band dynamically modulated electrochromic smart window.

[0039] With an applied voltage, high-performance dynamic control in the visible-near-infrared-mid-infrared-microwave range can be achieved by changing the voltage direction (+1V ~ -3V).

[0040] Third Embodiment This embodiment provides a multi-band dynamically adjustable electrochromic smart window and its preparation method, as shown below: Composition and preparation of PEDOT:PSS electrochromic layer: 8% polar solvent ethylene glycol and 0.1% surfactant Triton were added to PEDOT:PSS (PH1000, Heraeus, Germany) liquid. TM X-100, magnetically stirred for 30 min at room temperature, yields a PEDOT:PSS modified mixed solution. An electrochromic film with a thickness of 923 nm is prepared using a roll-to-roll coating process. Polyethylene (PE) is used as the material for the infrared transparent layer, and a PE film with a thickness of 10 μm is used as the infrared transparent layer in this embodiment. The PE film is mounted on the feed roller of the roll-to-roll equipment. The PEDOT:PSS modified mixed solution is placed in the feeding zone, and the equipment is started. The PE film is continuously fed into the coating area from the feed roller. Simultaneously, a pump delivers the solution to a slit-type coating head. The coating head uniformly coats the solution onto the surface of the PE film. After drying in a 40°C oven, the wet film transforms into a dry film, yielding a sulfuric acid-treated PEDOT:PSS electrochromic layer.

[0041] Preparation of the gel phase electrolyte layer: 30 mL of propylene carbonate (PC) solution was measured into a beaker, and 0.03 mol of lithium perchlorate powder was added. After sealing, the mixture was magnetically stirred at room temperature for 30 min. Then, 20% by mass of polymethyl methacrylate (PMMA) particles were added to the beaker. After sealing, the mixture was heated in a water bath at 90 ℃ until the PMMA particles were completely dissolved. After cooling, a lithium perchlorate-PC-PMMA gel phase electrolyte layer with a thickness of 0.1126 mm was prepared.

[0042] Preparation of transparent conductive substrate: Polyethylene terephthalate (PET)-indium tin oxide (ITO) conductive film was selected as the transparent conductive substrate of this embodiment (ITO-PET, Shenzhen Siyu Industrial Products Co., Ltd., 7Ω / sq), with a thickness of 0.125mm.

[0043] Assembly of a multi-band dynamically modulated electrochromic smart window: A PEDOT:PSS modified mixed solution was spin-coated onto the surface of an ITO-PET transparent conductive substrate at 500 rpm and dried at 50 °C to form an ion storage layer with a thickness of 200 nm. A gel phase electrolyte layer was then coated onto the ion storage layer, and finally, a PEDOT:PSS electrochromic layer coated on a PE film was placed over the gel phase electrolyte layer. A small amount of silicone sealant was applied to the edges for insulation, thus completing the multi-band dynamically modulated electrochromic smart window.

[0044] With an applied voltage, high-performance dynamic control in the visible-near-infrared-mid-infrared-microwave range can be achieved by changing the voltage direction (+1V ~ -3V).

[0045] The multi-band dynamic control electrochromic smart window provided in the above embodiments has the advantages of flexibility, simple structure, simple and low cost of manufacturing process, can be fabricated on a large scale, and has a wide range of applications.

[0046] Application examples The multi-band dynamic control electrochromic smart window provided in the first, second, and third embodiments described above has at least the following applications: a. Application in the manufacture of intelligent energy-saving windows; b. Applications in the manufacture of electronic products; c. Application in the preparation of temperature-adaptive greenhouse devices.

[0047] Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention. Unless otherwise specified, the embodiments and features described in this application can be arbitrarily combined with each other.

Claims

1. A multi-band dynamically adjustable electrochromic smart window, characterized in that, The smart window comprises an infrared transparent layer, a PEDOT:PSS electrochromic layer, an electrolyte layer, an ion storage layer, and a transparent conductive substrate, which are stacked in sequence.

2. The multi-band dynamically adjustable electrochromic smart window according to claim 1, characterized in that, The infrared transparent layer is made of at least one of polyethylene, polyamide 6, polyamide 66, polymethylpentene, polytetrafluoroethylene, polymethyl methacrylate, and styrene-ethylene-butene-styrene block copolymer.

3. The multi-band dynamically adjustable electrochromic smart window according to claim 1, characterized in that, The method for preparing the PEDOT:PSS electrochromic layer is as follows: Add 3 wt.% to 15 wt.% of a polar solvent and 0.01 wt.% to 0.25 wt.% of a surfactant to PEDOT:PSS liquid, coat and anneal to form a film, and obtain the PEDOT:PSS electrochromic layer; Alternatively, 0.01 wt.%~0.25 wt.% surfactant is added to the PEDOT:PSS suspension, and after coating and annealing to form a film, post-treatment is performed using organic solvents or inorganic acids to obtain the PEDOT:PSS electrochromic layer. The polar solvent is at least one of methyl sulfoxide, N,N-dimethylformamide, sorbitol, ethylene glycol, methoxyethanol, and diethylene glycol. The surfactant is Triton. TM At least one of X-100, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, quaternary ammonium salt, alkylamine oxide, 2-alkylimidazoline, and polyethylene glycol; The organic solvent is at least one of ethylene glycol, methanol, formic acid, methanesulfonic acid, and toluenesulfonic acid; The inorganic acid is at least one of sulfuric acid, nitric acid, and hydrochloric acid.

4. The multi-band dynamically adjustable electrochromic smart window according to claim 1, characterized in that, The electrolyte layer is a liquid phase electrolyte layer or a gel phase electrolyte layer; The liquid electrolyte layer is a solution of lithium salt electrolyte dissolved in a solvent. The lithium salt electrolyte includes at least one of lithium hexafluoroborate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium dioxaborate, lithium carbonate, and lithium hydroxide. The solvent includes at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, methyl ethyl carbonate, ethyl acetate, methyl propionate, tetrahydrofuran, dioxane, and N,N-dimethylformamide. The gel phase electrolyte layer is a gel composed of a polymer matrix, an electrolyte salt, and an organic solvent. The polymer matrix includes at least one of polymethyl methacrylate, polyethylene oxide, polyvinylidene fluoride and its copolymers, and polyacrylonitrile. The electrolyte salt includes at least one of lithium hexafluoroborate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, and lithium bis(trifluoromethanesulfonyl)imide. The organic solvent includes at least one of propylene carbonate, ethyl methyl carbonate, ethyl acetate, and methyl propionate.

5. The multi-band dynamically adjustable electrochromic smart window according to claim 1, characterized in that, The material of the ion storage layer includes inorganic transition metal oxides or conductive polymers; The inorganic transition metal oxide includes at least one of nickel oxide, titanium dioxide, cerium dioxide, vanadium pentoxide, tungsten trioxide, molybdenum oxide, and niobium oxide. The conductive polymer includes at least one of polyaniline, polypyrrole, polythiophene and its derivative 3,4-ethylenedioxythiophene.

6. The multi-band dynamically adjustable electrochromic smart window according to claim 1, characterized in that, The transparent conductive substrate includes a flexible substrate and a conductive film; The flexible substrate is made of polyimide or polyethylene terephthalate. The conductive film includes at least one of indium tin oxide conductive film, fluorine-doped tin dioxide conductive film, silver nanowire conductive film, metal mesh conductive film, conductive polymer conductive film, and graphene conductive film.

7. The method for preparing a multi-band dynamically adjustable electrochromic smart window according to claims 1-6, characterized in that, The preparation method includes the following steps: A PEDOT:PSS solution is coated onto an infrared transparent layer to form an infrared transparent layer with a PEDOT:PSS electrochromic layer. After assembling the electrolyte layer with the infrared transparent layer with the PEDOT:PSS electrochromic layer, the ion storage layer, and the transparent conductive substrate, the multi-band dynamically modulated electrochromic smart window is obtained.

8. The method for preparing a multi-band dynamically adjustable electrochromic smart window according to claim 7, characterized in that, The coating includes at least one of spraying, spin coating, and scraping coating.

9. The multi-band dynamically adjustable electrochromic smart window according to claims 1-6 or the multi-band dynamically adjustable electrochromic smart window prepared by the preparation method according to claims 7-8, has at least the following applications: a. Application in the manufacture of intelligent energy-saving windows; b. Applications in the manufacture of electronic products; c. Application in the preparation of temperature-adaptive greenhouse devices.

Images