Flexible intelligent thermal control device and preparation method and regulation and control method thereof

Abstract

The invention relates to the technical field of intelligent thermal control, in particular to a flexible intelligent thermal control device and a preparation method and a regulation and control method thereof. The device comprises a transparent upper substrate, a top electrode structure, an electrolyte layer, a bottom electrode layer and a transparent lower substrate which are sequentially stacked, the top electrode structure is a multi-layer composite structure comprising a conductive layer, a deposition catalyst layer and a surface structure layer; and the electrolyte layer contains metal salt capable of generating reversible electrodeposition reaction. According to the invention, a metal reversible electro-deposition mechanism is combined with a unique multi-layer top electrode structure, so that independent, collaborative and dynamic regulation and control of visible light and infrared dual wavebands are realized; the problems that an existing intelligent thermal control technology is single in function, or regulation and control of the solar absorptivity and the infrared emissivity are seriously coupled, and the dynamic thermal environment is difficult to independently optimize and adapt are solved.

Description

Technical Field

[0001] This invention relates to the field of intelligent thermal control technology, and in particular to a flexible intelligent thermal control device and its preparation and control methods. Background Technology

[0002] Spacecraft face extreme and dynamically changing thermal environments during operation in orbit. Their external heat input mainly comes from solar radiation in the 0.3-3μm band, while heat dissipation into deep space mainly relies on infrared thermal radiation in the 8-14μm band. Therefore, the optical properties of the thermal control materials on the spacecraft surface, especially the solar absorptivity (α) and infrared emissivity (ε), directly determine its thermal equilibrium state.

[0003] Traditional passive thermal control materials, such as thermal control coatings and insulating felts, have fixed α and ε values. Designers select different fixed α / ε combinations to match specific mission expectations. However, when spacecraft experience periodic changes between sunny and shadowed areas during orbital operation, this static characteristic becomes a significant drawback: in sunny areas, excessive solar absorption can lead to equipment overheating; in shadowed areas, insufficient solar absorption makes it impossible to maintain temperature using solar radiation, necessitating reliance on less energy-efficient active heating systems and increasing the energy burden.

[0004] To cope with dynamic thermal environments, intelligent thermal control technologies with optical performance adjustment capabilities have been developed. For example, intelligent devices based on electrochromic, thermochromic, or phase-change principles can achieve a certain degree of dynamic adjustment of infrared emissivity (ε). However, these existing intelligent thermal control solutions still have significant shortcomings: First, the control function is singular; most technologies focus only on adjusting infrared emissivity and fail to manage solar radiation absorptivity (α) synchronously and independently, which may lead to failure due to excessive heat absorption under strong irradiation conditions. Second, the few technologies that attempt multi-band adjustment typically have highly coupled changes in solar absorptivity and infrared emissivity, making it difficult to decouple and independently optimize them according to the actual thermal environment. Third, some devices also suffer from limited spectral adjustment range, slow response speed, or difficulty in adapting to flexible and deployable aerospace structures.

[0005] In summary, current technologies lack a flexible, intelligent thermal control method capable of rapid, independent, wide-range, and coordinated regulation of solar radiation absorptivity and infrared radiation emissivity. This technological gap restricts the adaptive thermal management capabilities of spacecraft facing complex orbital thermal environments, limiting further improvements in their operational energy efficiency and reliability. Summary of the Invention

[0006] The purpose of this invention is to address the problems existing in the prior art by providing a flexible intelligent thermal control device and its preparation and control methods. By combining the reversible metal electrodeposition mechanism with a unique multilayer top electrode structure, independent, coordinated and dynamic control of visible light and infrared dual bands is achieved. This solves the problems of existing intelligent thermal control technologies having single functions or severe coupling between solar absorptivity and infrared emissivity control, making it difficult to independently optimize and adapt to dynamic thermal environments.

[0007] To achieve the above objectives, the present invention provides a flexible intelligent thermal control device, comprising a transparent upper substrate, a top electrode structure, an electrolyte layer, a bottom electrode layer, and a transparent lower substrate stacked sequentially. The top electrode structure is a multi-layer composite structure comprising a conductive layer, a deposited catalytic layer, and a surface structure layer; The electrolyte layer contains a metal salt capable of undergoing a reversible electrodeposition reaction.

[0008] The top electrode structure is key to achieving dual-band modulation. It is a multi-layer composite structure directly facing the electrolyte layer, consisting of a conductive layer, a deposited catalytic layer, and a surface structure layer from top to bottom (from the upper substrate to the electrolyte layer).

[0009] The main function of the conductive layer is to ensure good in-plane conductivity and visible light transmittance.

[0010] In one optional embodiment, the conductive layer is made of at least one of Ag, Cu, Pt, Au, and Al, and has a thickness of 2-100 nm.

[0011] The main function of the deposited catalyst layer is to enhance the reaction kinetics, reversibility, and cycle stability of the reversible metal electrodeposition / dissolution process.

[0012] In one optional embodiment, the material of the deposited catalyst layer is selected from at least one of Ge, Cu, Ti, and Pt, and its thickness is 2-50 nm.

[0013] The surface structure layer is the outermost layer of the top electrode, which is in direct contact with the electrolyte layer. Its main function is to provide an interface with a specific micro-nano morphology for metal deposition, guide the directional nucleation and growth of metal ions, and thus control the morphology (dense film or discrete particles) and size of the deposited metal.

[0014] In one optional embodiment, the material of the surface structure layer is selected from at least one of Ge, Ti, and Pt, and its thickness is 2-100 nm.

[0015] In one optional embodiment, the surface structure layer has a preset micro / nano morphology, including but not limited to porous structures, island structures, sheet structures, nanowire arrays, or nanocone arrays. This micro / nano morphology is formed in situ by controlling physical vapor deposition process parameters, or by subsequent etching, imprinting, or template processing to create a preset pattern. The micro / nano morphology is used to guide the directional nucleation and growth of metal ions during electrodeposition, and by controlling the size distribution and dispersion of the deposited metal particles through the local electric field enhancement effect and confined space, the size of the metal particles is controlled within the range of 10-100 nm.

[0016] In one optional embodiment, the conductive layer, the deposited catalytic layer, and the surface structure layer are all prepared on a transparent substrate using physical vapor deposition methods (such as magnetron sputtering, electron beam evaporation, or vacuum resistance evaporation). Taking magnetron sputtering as an example, the preparation process is as follows: the transparent substrate is placed in the vacuum chamber of the magnetron sputtering equipment, and the vacuum is evacuated to a background vacuum level not exceeding 5 × 10⁻⁶. -3 Pa. High-purity argon gas is then introduced as the working gas, and the gas flow rate is adjusted to maintain the working pressure at 0.5-2 Pa. Depending on the material, a corresponding target is selected, and the conductive layer, catalytic layer, and surface structure layer are sequentially sputtered and deposited. During the deposition process, the sputtering power, deposition time, and distance between the substrate and the target are adjusted according to the target thickness of each layer to achieve precise control of the film thickness. For the surface structure layer, the formation of its surface micro / nano morphology can also be controlled by adjusting parameters such as sputtering power and deposition time.

[0017] The electrolyte layer is the site where reversible electrochemical reactions occur, and it must contain a metal salt (such as Ag) capable of undergoing reversible electrodeposition reactions. + Cu 2+ (Salt); Metal salts provide metal ions, which undergo reversible electrochemical deposition and dissolution on the surface of the top electrode under the action of an electric field.

[0018] In an optional embodiment, the electrolyte layer further includes a redox medium to improve the reversibility of the reaction, suppress side reactions, and enhance cycle stability; the redox medium is selected from at least one of copper chloride, decamethylferrocene (CAS No.: 12126-50-0), decamethylferrocene tetrafluoroborate (CAS No.: 111087-08-7), and (ferrocenemethyl)tri-tert-butyltetrafluoroborate ammonium (CAS No.: 135348-61-7).

[0019] In an optional embodiment, the electrolyte layer further includes salts other than metal salts as a supporting electrolyte to improve ionic conductivity; the supporting electrolyte is selected from tetrabutylammonium bromide (TBABr).

[0020] In an optional embodiment, the electrolyte layer further comprises a polymer matrix for forming a stable gel electrolyte, imparting flexibility to the device and preventing electrolyte leakage; the polymer matrix is ​​selected from at least one of polyvinyl butyral (PVB), polyvinyl alcohol (PVA), and polyethylene oxide (PEO).

[0021] In an optional embodiment, the electrolyte layer further comprises a solvent for dissolving the components and forming an ionicly conductive medium; the solvent is selected from at least one of water, organic solvents (such as dimethyl sulfoxide (DMSO)), ionic liquids (such as 1-ethyl-3-methylimidazolium tetrafluoroborate), polyionic liquids (such as poly(1-vinyl-3-ethylimidazolium bromide)), and eutectic solvents (such as choline chloride-urea).

[0022] The above components are mixed in proportion to form a uniform, viscous gel electrolyte precursor. The precursor is coated into a mold and treated by a high-temperature hydrothermal method or a freeze-thaw method to obtain a quasi-solid gel electrolyte with good mechanical properties and low-temperature resistance, which is the electrolyte layer.

[0023] The bottom electrode layer is disposed between the electrolyte layer and the transparent substrate, serving as the counter electrode, and is used in conjunction with the top electrode structure to apply a driving voltage.

[0024] In one optional embodiment, the bottom electrode layer is made of at least one of gold (Au), metal nanowires, metal meshes, and modified metal oxides, and has a thickness of 10-500 nm. The metal nanowires are selected from silver nanowires; the metal mesh is selected from gold metal meshes; and the modified metal oxide is selected from at least one of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), and antimony-doped tin dioxide (ATO).

[0025] In an optional embodiment, the bottom electrode layer is prepared on a transparent substrate using physical vapor deposition methods (such as magnetron sputtering, electron beam evaporation, or vacuum resistance evaporation). Taking magnetron sputtering as an example, the preparation process is as follows: the transparent substrate is placed in the vacuum chamber of the magnetron sputtering equipment, and the vacuum is evacuated to a background vacuum level not exceeding 5 × 10⁻⁶. -3 Pa. High-purity argon gas is then introduced as the working gas, and the gas flow rate is adjusted to maintain the working pressure at 0.5-2 Pa. A target material of appropriate material is selected for sputtering deposition. During the deposition process, the sputtering power, deposition time, and distance between the substrate and the target are adjusted according to the target thickness to achieve precise control of the film thickness.

[0026] In an optional embodiment, the transparent upper substrate and the transparent lower substrate are used for support and encapsulation, and are respectively selected from a rigid transparent substrate or a flexible polymer film. The rigid transparent substrate is selected from quartz glass or polycarbonate (PC) sheet; the flexible polymer film is selected from polyethylene (PE), polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), or polyimide (PI).

[0027] The present invention also provides a method for preparing the aforementioned flexible intelligent thermal control device, comprising the following steps: S1. Form a top electrode structure on a transparent upper substrate; form a bottom electrode layer on a transparent lower substrate; prepare an electrolyte layer; S2. An electrolyte layer is placed between the top electrode structure and the bottom electrode layer and then encapsulated to obtain a flexible intelligent thermal control device.

[0028] In an optional implementation, in S2, the encapsulation process is as follows: conductive terminals are provided at the edge of the bottom electrode layer; an electrolyte layer is covered on the top of the bottom electrode layer; subsequently, a transparent upper substrate with a pre-prepared top electrode structure is carefully covered on top, so that the top electrode structure is in close contact with the electrolyte layer; pressure is applied and the device is sealed around the perimeter with encapsulation material to obtain a flexible intelligent thermal control device.

[0029] The present invention also provides a method for controlling the aforementioned flexible intelligent thermal control device, comprising the following steps: A driving voltage is applied between the top electrode structure and the bottom electrode layer of the device; By controlling the polarity of the driving voltage, metal ions in the electrolyte layer are driven to undergo reversible electrochemical deposition or electrochemical dissolution on the surface structure layer. Furthermore, the morphology and / or size of the metal formed during the electrochemical deposition process can be controlled by controlling at least one of the amplitude, waveform, and duration of the driving voltage.

[0030] In this invention, the dual-band modulation mechanism and implementation strategy are as follows: I. Mid- and far-infrared band modulation: (1) Mechanism: Relying on the reversible switching between the high infrared reflectivity of the metal deposition state and the intrinsic high infrared emissivity of the electrolyte.

[0031] (2) Implementation strategy: Apply a reverse voltage (e.g., negative voltage) to drive metal ions to deposit on the top electrode surface structure layer, forming a dense metal film or highly reflective discrete particles. Utilize the high infrared reflectivity (reflectivity >90%) of metals (e.g., Ag, Cu) to significantly reduce the emissivity of the device surface in the mid-to-far infrared band (e.g., 8-14 μm), entering a "thermal insulation state". Apply a forward voltage, and the deposited metal is rapidly dissolved, restoring the device to a high infrared emissivity state, entering a "heat dissipation state". By optimizing voltage parameters, surface morphology of the surface structure layer, and polymer matrix in the electrolyte layer, the emissivity modulation range can be expanded.

[0032] II. Visible Light (Solar) Band Modulation: (1) Mechanism: Based on the local surface plasmon resonance (LSPR) effect of deposited metal nanoparticles, the position of the resonance absorption peak strongly depends on the particle size and morphology.

[0033] (2) Implementation strategy: The core is to precisely control the size of the deposited metal particles within the range of 10-100 nm. This is mainly achieved through the following collaborative methods: Voltage strategy control: Programmable control is achieved by using specific combinations of pulse or step voltages. For example, short pulses (1-100ms) combined with low voltage (1-2V) can promote the nucleation of small particles (10-30nm), corresponding to the control of short-wavelength visible light; while long pulses (5-15s) combined with higher voltage (2-4V) induce particles to grow to a larger size (50-100nm), corresponding to the control of long-wavelength visible light.

[0034] Electrode structure guidance: Using the preset morphology of the top electrode surface structure layer as a template, the orderly nucleation and growth of metal particles are guided, and their dispersion and size distribution are controlled.

[0035] Electrolyte-assisted processes: By adjusting the concentration of metal salts (e.g., 0.1-1 mol / L), or by adding trace amounts of surfactants (e.g., sodium dodecyl sulfate) or ligands (e.g., disodium EDTA), the kinetics of particle growth can be regulated to ensure size uniformity.

[0036] The beneficial effects of this invention are as follows: (1) This invention creatively combines a reversible metal electrodeposition mechanism with a unique multilayer top electrode structure. By applying a driving voltage, the morphology and size of the deposited metal can be independently controlled within the same device and electrochemical process. The high infrared reflectivity of the dense metal film enables wide-range control of emissivity in the mid- and far-infrared bands, while the local surface plasmon resonance (LSPR) effect of metal nanoparticles of specific sizes (10-100 nm) enables dynamic adjustment of absorption / transmission characteristics in the visible light band. This invention achieves independent, synergistic, and dynamic control of both visible and infrared bands, solving the problems of existing intelligent thermal control technologies having limited functionality or severe coupling between solar absorptivity and infrared emissivity control, making independent optimization and adaptation to dynamic thermal environments difficult.

[0037] (2) The flexible intelligent thermal control device prepared by this invention has excellent comprehensive performance indicators: Large controllability: The transmittance of the device in the visible light band can be switched between about 80.1% (high transmittance) and about 12.7% (low transmittance); in the mid- and far-infrared band, the average emissivity can be switched between about 21.2% (low emissivity) and about 83.4% (high emissivity), with a significant controllability range and strong thermal control capability.

[0038] Fast response speed: The deposition and dissolution process of metals is rapid, and the state switch can be completed within tens of seconds, meeting the requirements of dynamic thermal environment for rapid response.

[0039] Excellent cycle stability: The optimized electrolyte composition and top electrode structure work synergistically to ensure high reversibility of the electrochemical reaction. After multiple deposition-dissolution cycles, the dual-band optical modulation amplitude attenuation is slight, demonstrating good long-term operational reliability.

[0040] Possesses active temperature control potential: Based on the aforementioned dual-band modulation capability, the device can actively adjust its radiative heat exchange with the environment by changing its own optical properties, thereby achieving effective surface temperature management.

[0041] (3) By designing a multilayer composite top electrode with a conductive layer, a deposited catalytic layer, and a surface structure layer, multiple functions such as current conduction, reaction catalysis, and morphology guidance are integrated into one. This structure is not only a working electrode, but also a "template" and "controller" for regulating the morphology of metal deposition, thereby determining the final optical performance. This integrated design makes the device structure relatively simple, but achieves complex spectral control functions, reducing system complexity and fabrication cost.

[0042] (4) The voltage control strategy proposed in this invention is well adapted to the device structure. By programming the polarity, amplitude, waveform and duration of the driving voltage, the metal deposition process (such as nucleation and growth) can be actively and precisely controlled, so as to achieve "on-demand" regulation of the final deposition morphology (dense film or nanoparticles) and particle size, thereby flexibly matching different spectral regulation requirements and having a high degree of intelligence.

[0043] (5) Flexible materials and suitable fabrication processes can be used in each layer of the device to achieve overall device flexibility. This makes the present invention not only applicable to traditional spacecraft platforms, but also easier to integrate with next-generation flexible deployable aerospace structures, conformal surfaces and flexible electronic devices, providing innovative device solutions for efficient and adaptive thermal management in aerospace, flexible electronics, smart wearables, building energy conservation and other fields. Attached Figure Description

[0044] Figure 1 This is a spectrum of transmittance variation of the flexible intelligent thermal control device in the deposition and dissolution states in Embodiment 1 of the present invention; Figure 2 This is the infrared emission power variation spectrum of the flexible intelligent thermal control device in the deposition and dissolution states in Embodiment 1 of the present invention; Figure 3 This is a SEM characterization image of the top electrode surface structure layer in the deposition state of the flexible intelligent thermal control device in Embodiment 1 of the present invention. Detailed Implementation

[0045] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0046] Where specific experimental steps or conditions are not specified in the examples, they can be performed according to the conventional experimental steps or conditions described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0047] Example 1 This embodiment provides a flexible intelligent thermal control device and its fabrication method.

[0048] 1. Device Structure The device fabricated in this embodiment has a five-layer structure, which, from top to bottom, includes: a transparent upper substrate, a top electrode structure, an electrolyte layer, a bottom electrode layer, and a transparent lower substrate. The top electrode structure is a multilayer composite structure, consisting of a conductive layer, a deposited catalytic layer, and a surface structure layer, from top to bottom (from the upper substrate towards the electrolyte layer).

[0049] 2. Preparation steps (1) Base preparation A polyethylene (PE) film with a size of 40mm×40mm and a thickness of 0.01mm was selected as the transparent upper substrate and the transparent lower substrate, respectively.

[0050] (2) Fabrication of the top electrode structure On a transparent PE film, three functional films are sequentially deposited using magnetron sputtering to form a top electrode structure. The specific process is as follows: The transparent substrate was placed in the vacuum chamber of the magnetron sputtering equipment, and the vacuum was evacuated to a background vacuum level of 5 × 10⁻⁶. -3 Pa; High-purity argon gas is introduced as the working gas, and the gas flow rate is adjusted to maintain the working gas pressure at 2 Pa.

[0051] Conductive layer: Using an aluminum (Al) target, with a sputtering power of 30W, a deposition time of 1.2 min, and a distance of 3 cm between the substrate and the target, a conductive layer with a thickness of 10 nm was formed. Catalytic layer: Using a platinum (Pt) target, with a sputtering power of 50W, a deposition time of 3 min, and a distance of 3 cm between the substrate and the target, a catalytic layer with a thickness of 20 nm was formed. Surface structure layer: Using a germanium (Ge) target, with a sputtering power of 50W, a deposition time of 1 min, and a distance of 3 cm between the substrate and the target, a surface structure layer with a thickness of 10 nm was formed.

[0052] Through the control of the above parameters, the surface structure layer forms a self-assembled island-like micro-nano morphology in situ.

[0053] (3) Preparation of the bottom electrode layer On another PE film serving as a transparent substrate, a bottom electrode layer is deposited using magnetron sputtering. The specific process is as follows: The transparent substrate was placed in the vacuum chamber of the magnetron sputtering equipment, and the vacuum was evacuated to a background vacuum level of 5 × 10⁻⁶. -3 Pa; High-purity argon gas was introduced as the working gas, and the gas flow rate was adjusted to maintain the working gas pressure at 1 Pa. A gold (Au) target was selected, and the sputtering power was set to 60 W, the deposition time to 10 min, and the distance between the substrate and the target to 3 cm to form a bottom electrode layer with a thickness of 200 nm.

[0054] (4) Preparation of electrolyte layer Silver bromide (AgBr, a metal salt capable of reversible electrodeposition), tetrabutylammonium bromide (TBABr, a supporting electrolyte), and copper chloride (a redox medium) were dissolved together in dimethyl sulfoxide (DMSO) to obtain a mixed solution. The concentrations of AgBr and TBABr in the solution were both 0.5 mol / L, and the concentration of copper chloride was 1 mol / L. Subsequently, 10% by mass of polyvinyl butyral (PVB, as a polymer matrix) was added to the solution, and the mixture was stirred continuously until homogeneous, forming a uniform, viscous gel-like electrolyte precursor. The precursor was coated into a mold and frozen at -20°C for 20 h, followed by thawing for 10 h, to solidify the electrolyte precursor into a quasi-solid gel electrolyte with low-temperature resistance, which is the electrolyte layer.

[0055] (5) Device packaging and assembly At the edge of the prepared bottom electrode layer (Au layer), a small gold electrode sheet is bonded as a wire terminal using conductive silver paste. The electrolyte layer is then placed over the bottom electrode layer. Subsequently, the transparent upper substrate with the prepared top electrode structure is carefully placed on top, ensuring close contact between the surface structure layer of the top electrode structure and the electrolyte layer. Pressure is applied, and the device is sealed around its perimeter using an encapsulation material (epoxy resin), resulting in a flexible intelligent thermal control device.

[0056] Example 2 This embodiment provides a flexible intelligent thermal control device and its fabrication method. The difference from Embodiment 1 lies in the fabrication of the top electrode structure. The specific fabrication process of the top electrode structure in this embodiment is as follows: The transparent substrate was placed in the vacuum chamber of the magnetron sputtering equipment, and the vacuum was evacuated to a background vacuum level of 5 × 10⁻⁶. -3 Pa; High-purity argon gas is introduced as the working gas, and the gas flow rate is adjusted to maintain the working gas pressure at 0.5 Pa.

[0057] Conductive layer: An aluminum (Al) target was used, with a sputtering power of 30W, a deposition time of 2.4 min, and a distance of 3 cm between the substrate and the target, to form a conductive layer with a thickness of 20 nm. Catalytic layer: A platinum (Pt) target was used, with a sputtering power of 50W, a deposition time of 3.75 min, and a distance of 3 cm between the substrate and the target, to form a catalytic layer with a thickness of 25 nm. Surface structure layer: A germanium (Ge) target was used, with a sputtering power of 50W, a deposition time of 1.5 min, and a distance of 3 cm between the substrate and the target, to form a surface structure layer with a thickness of 5 nm.

[0058] Through the control of the above parameters, the surface structure layer forms a self-assembled sheet structure micro-nano morphology in situ.

[0059] Example 3 This embodiment provides a flexible intelligent thermal control device and its preparation method. The difference from Embodiment 1 is that in the preparation of the electrolyte layer, 10% of the total mass of polyvinyl butyral (PVB) is replaced with 12% of the total mass of polyvinyl alcohol (PVA).

[0060] Experimental Example 1 The flexible intelligent thermal control device prepared in Example 1 was connected to an external power supply and an optical testing system, respectively, and the following voltage strategy was used for regulation to verify the dual-band independent regulation capability described in this invention.

[0061] Switching to the deposition state: A -1V step pulse is applied for 100 milliseconds (ms) between the top electrode structure and the bottom electrode layer of the device, followed by a -3V step pulse for 10 seconds (s). This process drives the electrochemical reduction deposition of silver ions in the electrolyte onto the surface structure layer of the top electrode.

[0062] Switch to the dissolved state: Apply a +3V step pulse for 10 seconds (s). This process drives the electrochemical oxidation and dissolution of the deposited metallic silver.

[0063] (1) Visible light band modulation performance test The transmittance spectra of the device in the visible-near-infrared band (350-2500 nm) in both the deposited and dissolved states were measured using a UV-Vis-NIR spectrophotometer. This yielded the transmittance variation spectra of the flexible intelligent thermal control device in Example 1 in both the deposited and dissolved states, as shown below. Figure 1 As shown. From Figure 1 As can be seen, the device in Example 1 exhibits significant spectral switching characteristics in the visible-near-infrared band: at a wavelength of 550 nm, the transmittance is approximately 80.1% in the dissolved state and decreases to approximately 12.7% in the deposited state, with a transmittance modulation range of 67.4%. This result demonstrates that a wide range of dynamic adjustment of the transmittance characteristics in the visible light band can be achieved by voltage-controlled metal deposition / dissolution.

[0064] (2) Mid- and far-infrared band modulation performance test The infrared emission power (8-14 μm band) of the device in the deposited and dissolved states was measured using a Fourier transform infrared spectrometer. Simultaneously, the infrared emission power of the device was compared with the radiation power curve of an ideal blackbody (emissivity ε=1) at the same temperature. The infrared emission power variation spectra of the flexible intelligent thermal control device in Example 1 in the deposited and dissolved states are shown below. Figure 2 As shown. According to Kirchhoff's radiation law, at a given thermodynamic temperature, the ratio of the actual monochromatic emission power per unit area of ​​an object in the mid-infrared band to the theoretical monochromatic emission power of a blackbody at the same temperature and band is calculated, and the result is the mid-infrared emissivity of the object at that temperature. Combined with... Figure 2It is evident that the device also exhibits excellent controllability in the mid- and far-infrared bands: in the deposited state, its average infrared emissivity is approximately 21.2%, far below the blackbody radiation level, indicating that it is in a low-radiation "heat-preserving state"; in the dissolved state, the average infrared emissivity increases to approximately 83.4%, approaching the blackbody radiation level, indicating that it is in a high-radiation "heat-dissipating state." This confirms that efficient infrared radiation "switching" control can be achieved through metal deposition / dissolution.

[0065] (3) Morphological characteristics Example 1: SEM characterization image of the top electrode surface structure layer in the deposited state in the flexible intelligent thermal control device, as shown. Figure 3 As shown. From Figure 3 As can be seen, uniformly sized metallic silver particles were successfully deposited on the top electrode surface structure layer.

[0066] Therefore, the present invention adopts the above-mentioned flexible intelligent thermal control device and its preparation and control methods. By combining the metal reversible electrodeposition mechanism with a unique multilayer top electrode structure, it realizes independent, coordinated and dynamic control of visible light and infrared dual bands. This solves the problems of existing intelligent thermal control technologies having single functions or severe coupling between solar absorptivity and infrared emissivity control, making it difficult to independently optimize and adapt to dynamic thermal environments.

[0067] Finally, it should be noted that the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A flexible intelligent thermal control device, characterized in that, It includes a transparent upper substrate, a top electrode structure, an electrolyte layer, a bottom electrode layer, and a transparent lower substrate, which are stacked sequentially. The top electrode structure is a multi-layer composite structure comprising a conductive layer, a deposited catalytic layer, and a surface structure layer; The electrolyte layer contains a metal salt capable of undergoing a reversible electrodeposition reaction.

2. The flexible intelligent thermal control device according to claim 1, characterized in that, The conductive layer is made of at least one of Ag, Cu, Pt, Au, and Al, and its thickness is 2-100 nm.

3. The flexible intelligent thermal control device according to claim 1, characterized in that, The material of the deposited catalyst layer is selected from at least one of Ge, Cu, Ti, and Pt, and its thickness is 2-50 nm.

4. The flexible intelligent thermal control device according to claim 1, characterized in that, The material of the surface structure layer is selected from at least one of Ge, Ti, and Pt, and its thickness is 2-100 nm.

5. The flexible intelligent thermal control device according to claim 1, characterized in that, The electrolyte layer also contains a redox medium; the redox medium is selected from at least one of copper chloride, decamethylferrocene, decamethylferrocene tetrafluoroborate, and (ferrocenemethyl)tri-tert-butyltetrafluoroborate ammonium.

6. The flexible intelligent thermal control device according to claim 1 or 5, characterized in that, The electrolyte layer further comprises a polymer matrix; the polymer matrix is ​​selected from at least one of polyvinyl butyral, polyvinyl alcohol, and polyethylene oxide.

7. The flexible intelligent thermal control device according to claim 1, characterized in that, The bottom electrode layer is made of at least one of indium-doped tin oxide, fluorine-doped tin oxide, gold, aluminum-doped zinc oxide, metal nanowires, metal meshes, and modified metal oxides, and its thickness is 10-500 nm.

8. The flexible intelligent thermal control device according to claim 1, characterized in that, The transparent upper substrate and the transparent lower substrate are respectively selected from rigid transparent substrates or flexible polymer films.

9. A method for preparing a flexible intelligent thermal control device as described in any one of claims 1 to 8, characterized in that, Includes the following steps: S1. Form a top electrode structure on a transparent upper substrate; form a bottom electrode layer on a transparent lower substrate; prepare an electrolyte layer; S2. An electrolyte layer is placed between the top electrode structure and the bottom electrode layer and then encapsulated to obtain a flexible intelligent thermal control device.

10. A method for controlling a flexible intelligent thermal control device as described in any one of claims 1 to 8, characterized in that, Includes the following steps: A driving voltage is applied between the top electrode structure and the bottom electrode layer of the device; By controlling the polarity of the driving voltage, metal ions in the electrolyte layer are driven to undergo reversible electrochemical deposition or electrochemical dissolution on the surface structure layer. Furthermore, the morphology and / or size of the metal formed during the electrochemical deposition process can be controlled by controlling at least one of the amplitude, waveform, and duration of the driving voltage.

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