All-solid-state dynamic temperature regulation film, preparation method and application thereof

Abstract

The present application relates to a kind of all-solid-state dynamic temperature regulation film and its preparation method and application, the all-solid-state film includes successively: infrared regulation film layer, solid electrolyte layer, ion storage layer film, wherein infrared regulation layer, all-solid-state electrolyte layer between being equipped with conductive current collector, the solid electrolyte layer, ion storage layer between being equipped with conductive current collector.The all-solid-state dynamic temperature regulation film device structure prepared by the present application is simple, can be realized scale preparation, temperature regulation effect is excellent, can be applied in building, outdoor equipment, human temperature and spacecraft temperature management, infrared camouflage and other fields.

Description

Technical Field

[0001] This invention belongs to the field of functional composite materials, and specifically relates to an all-solid-state dynamic temperature-controlled thin film, its preparation method, and its application. Background Technology

[0002] Regulating the energy efficiency of buildings, outdoor equipment, human body temperature, and spacecraft is crucial for the development of a sustainable society. For example, spacecraft rely solely on thermal radiation for heat transfer in space. When facing the sun, a spacecraft must reflect and dissipate heat; when facing away, it must retain it. This transition involves temperatures as high as 200°C and sometimes occurs within tens of seconds (spacecraft rotation). Spacecraft components have limited operating temperatures and cannot withstand such changes, thus requiring temperature control to protect them from variations in external thermal radiation. Building surfaces require high reflectivity in summer to reflect additional solar radiation, thus cooling the interior; in winter, high reflectivity on interior surfaces is needed to keep the interior warm. Regulating surface emissivity is a simple and efficient method. Traditional strategies typically use phase change materials or semiconductor cooling elements to regulate the temperature of target surfaces, but these methods suffer from drawbacks such as passive regulation, high energy consumption, large size, and heavy weight, limiting their application in thermal radiation control. In recent years, several applications have adopted this strategy, including ambient radiative coolers, radiative cooling fabrics, and energy-efficient coatings. However, a fixed high infrared long-wave emissivity only provides cooling in warm weather and is not suitable for regions with fluctuating temperatures during hot / cold seasons. This necessitates thermal radiation modulation devices adapted to different seasonal weather conditions. Power-reversibly adjustable thermal radiation modulation materials offer advantages such as low power consumption and high controllability, making them a simple and efficient method in the field of thermal radiation modulation. For example, the emissivity of the outermost surface of the device can be tuned by sandwiching a porous electrolyte layer filled with an ion-conductive electrolyte between two modulation material films. Although some optical modulation devices have been studied, these devices are limited to the visible light band, have small effective areas, rigid structures, and use liquid / semi-solid electrolytes, which restricts their application in vacuum, flexible wearable devices, and other fields. Developing simple, scalable fabrication methods to construct large-area thermal radiation modulation devices with wide-band switching and all-solid-state device structures remains a highly challenging task. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide an all-solid-state dynamic temperature control thin film, its large-scale preparation method and application.

[0004] The present invention provides an all-solid-state thin film, which comprises, in sequence, an infrared modulation thin film layer, a solid electrolyte layer, and an ion storage thin film, wherein a conductive current collector is provided between the infrared modulation layer and the all-solid-state electrolyte layer, and a conductive current collector is provided between the solid electrolyte layer and the ion storage layer.

[0005] Preferably, the all-solid-state film further includes a polymer substrate film, wherein the infrared modulation material layer is disposed on the surface of the polymer substrate film;

[0006] Preferably, the polymer substrate film includes a porous film or a dense film; the polymer substrate film material includes one or more of the following: polyethylene film, polyvinyl chloride film, polyvinylidene fluoride film, polycarbonate film, polystyrene film, polymethyl methacrylate, methyl methacrylate-acrylonitrile-butadiene-styrene plastic film, polyethylene terephthalate film, and polyurethane film.

[0007] Preferably, the thickness of the polymer substrate is 0.05 μm to 1000 μm.

[0008] Preferably, the infrared modulation material includes one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanotube derivatives, graphene, graphene derivatives, polyaniline, polyaniline derivatives, poly(3,4-ethylenedioxythiophene), and poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid.

[0009] Preferably, the thickness of the infrared modulation material is 0.01 μm to 500 μm.

[0010] Preferably, the all-solid-state electrolyte layer material comprises: inorganic salt powder, additive powder, polymer powder or particles; wherein the inorganic salt includes one or more of lithium salt, sodium salt, potassium salt, aluminum salt, and magnesium salt; the additive includes perovskite ceramic powder (calcium barium titanate, copper calcium titanate, etc.) and sodium superionic conductor ceramic powder (Na3Zr2Si2PO4). 12 ), LISICON type ceramic powder (Li 9.4 Si 1.74 P 1.44 S 11.7 C l0.3 ), Garnet-type ceramic powder (Li7La3Zr2O) 12 One or more of the following: ethylene oxide (PEO), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polymethyl methacrylate (PMMA), polyurethane (PU), phenolic resin, polyvinylidene fluoride (PVDF), polypropylene oxide (PPO), polyacrylonitrile (PAN), polyvinyl chloride (PVC), and polyvinylidene chloride (PVDC).

[0011] Furthermore, the lithium salt includes one or more of lithium perchlorate, lithium titanate, lithium chloride, lithium fluoride, and lithium hexafluorophosphate; the sodium salt includes one or more of sodium perchlorate, sodium chloride, and sodium fluoride; the potassium salt includes potassium chloride, etc.; the aluminum salt includes aluminum chloride, etc.; and the magnesium salt includes magnesium chloride, magnesium sulfate, etc.

[0012] Preferably, the thickness of the solid electrolyte layer is between 1 μm and 1000 μm.

[0013] Preferably, the ion storage layer film comprises a flexible substrate and an ion storage material layer; wherein the flexible substrate material comprises one or more of polyethylene terephthalate, polyimide, polyethylene film, polyvinyl chloride film, polyvinylidene fluoride film, polycarbonate film, polystyrene film, polymethyl methacrylate, methyl methacrylate-acrylonitrile-butadiene-styrene plastic film, and polyurethane film; the ion storage material comprises one or more of conductive materials such as carbide-derived carbon materials, porous carbon materials, activated carbon materials, graphene, electrospun carbon nanofibers, conductive polymers, and carbon nanotubes.

[0014] Preferably, the thickness of the ion storage layer is 1 μm to 1000 μm; the thickness of the flexible substrate is 0.05 μm to 2000 μm.

[0015] Preferably, the conductive current collector includes one or more of fiber-type current collectors and sheet-type current collectors; the fiber-type current collector is one or more of metal fiber, carbon nanotube fiber, nickel-plated yarn, copper-plated metal fiber, gold-plated metal fiber, and carbon fiber; the sheet-type current collector is one or more of metal sheet, graphene conductive sheet, and conductive fiber braided sheet.

[0016] Preferably, the diameter of the fiber-type current collector is 5μm to 1000μm; the width of the sheet-type current collector is 1μm to 1500μm, and the thickness is 1μm to 100μm.

[0017] The present invention provides a method for preparing an all-solid-state thin film, comprising:

[0018] (1) An infrared modulation layer is coated on a polymer substrate and dried to obtain a polymer infrared modulation substrate film.

[0019] (2) The ion storage material is coated on the substrate film and dried to obtain the ion storage layer film.

[0020] (3) Mix inorganic salts, additives and polymers, heat, and cast film to obtain an all-solid electrolyte film;

[0021] (4) The polymer infrared modulated substrate film, the conductive current collector, the all-solid electrolyte film, the conductive current collector and the ion storage layer film are hot-pressed to obtain an all-solid film.

[0022] The preferred embodiment of the above preparation method is as follows:

[0023] Preparation of polymer infrared modulation substrate film in step (1): The polymer substrate film is transported by a transmission device, coated with infrared modulation slurry by a coating device, dried by a drying device, and finally obtained by a collection device.

[0024] The solvent used in the infrared-controlled slurry is one or more of the following: isopropanol (IPA), water (H2O), N-methylpyrrolidone (NMP), acetone, N,N-dimethylformamide (DMF), butyl acrylate (BA), and propylene carbonate (PC); the solid content of the infrared-controlled material in the slurry is 0.05–80 wt.%; the coating device for the slurry includes one or both of the following: a coating device and a spraying device; the length of the drying device is 0.1 m–10 m, the drying temperature is 30 °C–150 °C, and the transmission speed is 0.01 m / min–100 m / min.

[0025] The infrared-controlled slurry is specifically prepared by ultrasonically dispersing infrared-controlled materials and solvents after they are stirred evenly.

[0026] In step (2), the ion storage layer film is prepared by: transporting the flexible substrate film through a transmission device, coating it with ion storage layer slurry through a coating device, drying it through a drying device, and finally collecting it through a collection device to obtain the ion storage layer film.

[0027] The dispersant in the ion storage layer slurry includes one or more of the following: isopropanol (IPA), water (H2O), N-methylpyrrolidone (NMP), acetone, N,N-dimethylformamide (DMF), butyl acrylate (BA), and propylene carbonate (PC). The solid content of the ion storage material in the slurry is 0.05–80 wt.%. The coating device for the slurry includes one or both of the following: a coating device and a spraying device. The drying device has a length of 0.1 m–10 m, a drying temperature of 30 °C–150 °C, and a conveying speed of 0.01 m / min–100 m / min.

[0028] In step (3), the preparation of the all-solid electrolyte film is as follows: first, inorganic salts, additives and polymers are added to the screw extruder and mixed evenly by heating. Then, the all-solid electrolyte film is extruded through the fixed mold of the casting press.

[0029] The mass ratio of inorganic salt to polymer in the all-solid electrolyte film is 1:19 to 9:1, and the solid content of the additive is 0 wt.% to 50 wt.% of the previous mixture (inorganic salt and polymer mixture); the screw extruder heating temperature is 110℃ to 250℃.

[0030] Steps (1) to (3) are parallel steps and there is no sequential relationship between them.

[0031] In step (4), the all-solid dynamic temperature control film is assembled on a large scale: the polymer infrared control substrate film, the conductive current collector and the all-solid electrolyte film are passed together through the hot roller pressing device through the transmission device, and the all-solid dynamic temperature control film is prepared on a large scale through heating and pressure. Finally, the product is collected by the correction device and the collection roller; the transmission speed of the transmission device is 0.5m / min~20m / min; the temperature of the hot roller is 100℃~220℃ and the pressure of the hot roller is 100Pa~2MPa.

[0032] An apparatus for the method of the present invention includes a first device for outputting a polymer infrared-controlled substrate film, a second device for outputting an ion storage layer film, a third device for outputting an all-solid-state electrolyte film, a fourth device for conveying a first conductive current collector, a fifth device for outputting a second conductive current collector, and a hot press roller. The polymer infrared-controlled substrate film, the first conductive current collector, the all-solid-state electrolyte film, the second conductive current collector, and the ion storage layer film output by the first device, the fourth device, the third device, the fifth device, and the second device are stacked together from top to bottom and fed into the hot press roller for pressing, and collected by a collecting roller.

[0033] The first device is described as being conveyed through a web guide, a first coating device, and a first drying device before being output to a hot press roller.

[0034] In the second device, the material is conveyed through a second coating device and a second drying device in sequence before being output to a hot press roller.

[0035] The third device outputs the film after passing through the casting press to the hot press roller;

[0036] In devices 4 and 5, the hot press rollers are directly fed in via a conveying device.

[0037] Furthermore, tensioners are respectively provided in the fourth and fifth devices.

[0038] An air-cooling device is provided between the hot pressing roller and the collecting roller.

[0039] The conveying device includes a feeder or feed roller at the head end, several guide wheels, and a collection roller at the tail end that provides transfer power.

[0040] The present invention relates to the application of the all-solid film in the fields of building, outdoor equipment, human body temperature, temperature management of spacecraft, or infrared camouflage.

[0041] The preparation of the all-solid-state dynamic temperature-controlled film in this invention includes the following structures: preparation of a polymer infrared-controlled substrate film, preparation of an all-solid-state electrolyte layer, preparation of an ion storage layer film, and large-scale assembly of the all-solid-state dynamic temperature-controlled film. First, an infrared-controlled layer is coated onto a polymer substrate using a transmission device, and after drying, a polymer infrared-controlled substrate film is obtained. Then, an ion storage material is coated onto the substrate film using a transmission device, and after drying, a polymer infrared-controlled substrate film is obtained. Next, an electrolyte salt and polymer are mixed using a screw extruder, and an all-solid-state electrolyte film is prepared using a casting and pressing device. Finally, the infrared-controlled substrate film, conductive current collector, ion storage layer film, and solid electrolyte film are mass-produced using hot roller pressing to create the all-solid-state dynamic temperature-controlled film, and the product is collected using a collecting roller.

[0042] This invention provides a method for the large-scale preparation of all-solid-state dynamic temperature-controlled thin films. This method not only allows for large-scale production but also features a simple process, enabling the fabrication of large-area all-solid-state temperature-controlled thin films. Furthermore, the optimized process produces thermal radiation devices with rapid thermal radiation switching modes and high temperature control performance.

[0043] Beneficial effects

[0044] (1) This invention utilizes customized equipment to construct a large-scale, large-area all-solid dynamic temperature control film production line, realizing large-area, large-scale production of all-solid dynamic temperature control films.

[0045] (2) The all-solid electrolyte prepared by this invention serves as the electrolyte layer, overcoming the volatility problem of liquid components in extreme environments such as high vacuum and high temperature;

[0046] (3) The present invention utilizes a current collector as a long-range conductor to ensure the uniformity of electric field distribution when the all-solid dynamic temperature control film is used over a large area, which can effectively improve the reflectivity switching speed of the film.

[0047] (4) The all-solid dynamic temperature control film prepared by the present invention has excellent flexibility. The film can be cut and assembled in any shape. By assembling with other equipment, it can be used in the fields of building, outdoor equipment, human body temperature and spacecraft temperature management, infrared camouflage and other fields. Attached Figure Description

[0048] Figure 1 Example 1: Optical photographs taken after disassembly of an all-solid-state dynamically temperature-controlled thin film prepared on a large scale;

[0049] Figure 2Example 1: Schematic diagram of the process for large-scale preparation of all-solid dynamic temperature-controlled thin films: 1 is a casting press, 2 is a wire feeder 1, 3 is a feeding roller 1, 4 is a coating device 1, 5 is a drying device 1, 6 is a hot press roller, 7 is a collecting roller, 8 is a web guide, 9 is a tensioner, 10 is a guide wheel, 11 is an air cooling device, 12 is a feeding roller 2, 13 is a coating device 2, 14 is a drying device 2, and 15 is a wire feeder 2;

[0050] Figure 3 Thermal imaging images of the all-solid-state dynamic temperature-controlled thin film prepared in Example 1 before and after switching infrared emission states under different voltages; (left) low reflection state, (right) high reflection state;

[0051] Figure 4 Infrared reflectance spectra of the all-solid-state dynamic temperature-controlled thin film prepared in Example 1 under different voltages;

[0052] Figure 5 Temperature change curves of the all-solid-state dynamic temperature-controlled thin film prepared in Example 1 under different voltage switching conditions;

[0053] Figure 6 Thermal imaging images of the all-solid-state dynamic temperature-controlled thin film prepared in Example 2 before and after switching infrared emission states under different voltages; (left) low reflectance state, (right) high reflectance state;

[0054] Figure 7 Infrared reflectance spectra of the all-solid-state dynamic temperature-controlled thin film prepared in Example 2 under different voltages;

[0055] Figure 8 Temperature change curves of the all-solid-state dynamic temperature-controlled thin film prepared in Example 2 under different voltage switching conditions;

[0056] Figure 9 Thermal imaging images of the all-solid-state dynamic temperature-controlled thin film prepared in Example 3 before and after switching infrared emission states under different voltages; (left) low reflection state, (right) high reflection state;

[0057] Figure 10 Infrared reflectance spectra of the all-solid-state dynamic temperature-controlled thin film prepared in Example 3 under different voltages;

[0058] Figure 11 Temperature change curves of the all-solid dynamic temperature-controlled thin film prepared in Example 3 under different voltage switching.

[0059] Figure 12 It is a large-area all-solid-state dynamic temperature control thin film (0.3m × 0.6m). Detailed Implementation

[0060] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0061] Polyvinylidene fluoride (PVDF), polypropylene oxide (PPO), polyacrylonitrile (PAN), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), ethylene oxide (PEO), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and polymethyl methacrylate (PMMA) were purchased from Arkema, France. Polyurethane (PU) and phenolic resin were purchased from Shunjie Plastics Co., Ltd. Carbon nanotube fibers, carbon nanotubes, graphene, and carbon nanotubes were provided by Chengdu Organic Chemistry Co., Ltd., Chinese Academy of Sciences. Carbon fiber, copper-clad nickel metal fiber, conductive yarn, polyethylene film, polyvinyl chloride film, polyvinylidene fluoride film, polycarbonate film, polystyrene film, polymethyl methacrylate, methyl methacrylate-acrylonitrile-butadiene-styrene plastic film, polyethylene terephthalate film, polyurethane film, polyaniline, polyaniline derivatives, poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, sodium superionic conductor ceramic powder (Na3Zr2Si2PO4). 12 ), LISICON type ceramic powder (Li 9.4 Si 1.74 P 1.44 S 11.7 C l0.3 ) and garnet-type ceramic powder (Li7La3Zr2O) 12 The following were provided by Shanghai Keyan Optoelectronic Technology Co., Ltd.: Isopropanol (IPA), water (H2O), N-methylpyrrolidone (NMP), acetone, N,N-dimethylformamide (DMF), butyl acrylate (BA), and propylene carbonate (PC), lithium perchlorate, lithium titanate, lithium chloride, lithium fluoride, lithium hexafluorophosphate, sodium perchlorate, barium calcium titanate, calcium copper titanate, sodium chloride, sodium fluoride, potassium chloride, aluminum chloride, magnesium chloride, and magnesium sulfate were purchased from Sinopharm Group.

[0062] Temperature changes and thermal images of the all-solid-state dynamically temperature-controlled thin film were measured using a FLIRA 625 thermal imager with the substrate temperature of the film set to 50°C. Infrared reflectance spectra were measured using an EQUINOX 55 Fourier transform infrared spectrometer equipped with an infrared integrating sphere (048-12XX, PIKE) accessory.

[0063] Example 1

[0064] First, prepare the infrared-controlled slurry: weigh 5g of graphene and 500g of deionized water, stir evenly, and then ultrasonically disperse for 3 hours to obtain the infrared-controlled slurry for later use.

[0065] Then, prepare the ion storage layer slurry: weigh 10g of activated carbon and 500g of deionized water, stir evenly, and then ultrasonically disperse for 3 hours to obtain the ion storage layer slurry for later use.

[0066] Finally, an all-solid-state electrolyte membrane was prepared by mixing 1000g of lithium perchlorate powder, 4000g of polyurethane powder, and 1000g of garnet-type ceramic powder (Li7La3Zr2O). 12 After mixing the powder by adding it to a screw extruder and setting the heating temperature to 150°C, the powder is then fed into a casting press to obtain a fully solid electrolyte membrane.

[0067] use Figure 2 The coating apparatus shown uses the 7 collecting roller as a power unit. While the 7 collecting roller rotates, the 3 feeding roller conveys a 6μm thick porous polyethylene film, which passes through the 10 guide roller and the 8 guide roller into the 4 coating unit 1. A scraping device coats the film with a dispersed infrared control slurry to a thickness of 200μm, and then it enters the 5 drying unit 1 for drying at 80°C. While the 7 collecting roller rotates, the 12 feeding roller 2 conveys a 125μm thick polyethylene terephthalate film, which passes through the 10 guide roller into the 13 coating unit 2. A scraping device coats the film with a dispersed ion storage layer slurry to a thickness of 200μm, and then it enters the 14 drying unit 2 for drying at 80°C. Simultaneously, while the 7 collecting roller rotates, the 2 wire feeders 1 and 15 wire feeders 2 convey a 0.1mm diameter copper wire to the 6 hot press roller. The coated polymer infrared control film, ion storage film, and solid electrolyte film are also conveyed to the 6 hot press roller at a speed of 2m / min. The polymer infrared control film, conductive current collector, solid electrolyte layer, conductive current collector, and ion storage film are pressed together into a whole by 6 hot press rollers at a temperature of 200°C and a pressure of 10 kPa. After cooling by 11 air cooling devices, the all-solid dynamic temperature control film is finally collected by 7 collecting rollers.

[0068] like Figure 1 As shown, the all-solid dynamic temperature control film exhibits good film properties, with a uniform and smooth surface without any granular protrusions, and shows obvious delamination after disassembly.

[0069] like Figure 3 The switching state of the all-solid dynamic temperature control film under different voltages is shown. When the voltage is -2V, the film is in a high temperature state of 34.3℃, and when the voltage is 3.5V, the film is in a low temperature state of 27.2℃, with a temperature difference of 7.1℃.

[0070] like Figure 4 The infrared reflectance spectra of the all-solid-state dynamic temperature-controlled thin film under different voltages are shown. At -2V, it is in a low reflectance state with a reflectance of 28.6% at around 10μm. At 3.5V, it is in a high reflectance state with a reflectance of 53.7% at around 10μm. The reflectance control range is 25.1%.

[0071] like Figure 5 The results show that the all-solid-state dynamic temperature control film has a fast temperature switching speed, with a voltage application time of 2.8s to switch from a high temperature state to a low temperature state at -2.5V and a voltage application time of 0.9s to switch from a low temperature state to a high temperature state at 3.5V.

[0072] Example 2

[0073] First, prepare the infrared-controlled slurry: weigh 5g of graphene, 5g of carbon nanotubes and 500g of deionized water, stir evenly and then ultrasonically disperse for 3 hours to obtain the infrared-controlled slurry for later use.

[0074] Then, prepare the ion storage layer slurry: weigh 10g of graphene and 500g of deionized water, stir evenly, and then ultrasonically disperse for 3 hours to obtain the red ion storage layer slurry for later use.

[0075] Finally, an all-solid-state electrolyte membrane was prepared by mixing 500g of lithium hexafluorophosphate powder, 4000g of polyvinyl chloride, and 500g of garnet-type ceramic powder (Li7La3Zr2O). 12 After mixing the powder by adding it to a screw extruder and setting the heating temperature to 150°C, the powder is then fed into a casting press to obtain a fully solid electrolyte membrane.

[0076] use Figure 2The coating apparatus shown uses a collection roller (7) as its power source. While the collection roller (7) rotates, a 12μm porous polyethylene film is fed by a feeding roller (3), passing through a guide roller (10) and a web guide (8) into a coating unit (4). A scraping device coats the film with a dispersed infrared control slurry to a thickness of 1000μm, and then the film enters a drying unit (5) for drying at 40°C. While the collection roller (7) rotates, a 125μm polyethylene terephthalate film is fed by a feeding roller (12), passing through a guide roller (10) into a coating unit (13). A scraping device coats the film with a dispersed ion storage layer slurry to a thickness of 500μm, and then the film enters a drying unit (14) for drying at 40°C. Simultaneously, while the collection roller (7) rotates, a 0.1mm diameter copper wire is fed to a hot press roller (6) using wire feeders (2) and (15). The coated polymer infrared control film, ion storage film, and solid electrolyte film are also fed to the hot press roller (6) at a speed of 10m / min. The polymer infrared control film, conductive current collector, solid electrolyte layer, conductive current collector, and ion storage film are pressed together into a whole by 6 hot press rollers at a temperature of 140°C and a pressure of 450 kPa. After cooling by 11 air cooling devices, the all-solid dynamic temperature control film is finally collected by 7 collection rollers.

[0077] like Figure 6 The display shows the switching state of the all-solid-state dynamic temperature-controlled thin film under different voltages. When the voltage is -2V, the film is in a high-temperature state at 28.7℃, and when the voltage is 3.5V, the film is in a low-temperature state at 26.6℃, with a temperature difference of 2.1℃. Figure 7 The infrared reflectance spectra of the all-solid-state dynamically temperature-controlled thin film at different voltages are shown. At -2V, it is in a low-reflectance state with a reflectance of 55.2% at approximately 10μm; at 3.5V, it is in a high-reflectance state with a reflectance of 69.7% at approximately 10μm. The reflectance tuning range is 14.5%. Figure 8 The results show that the all-solid-state dynamic temperature control film has a fast temperature switching speed, with a voltage application time of 2.5s to switch from a high temperature state to a low temperature state at -2.5V and a voltage application time of 0.7s to switch from a low temperature state to a high temperature state at 3.5V.

[0078] Example 3

[0079] First, prepare the infrared-controlled slurry: weigh 5g of graphene, 0.5g of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid and 500g of isopropanol, stir evenly and then ultrasonically disperse for 3 hours to obtain the infrared-controlled slurry for later use.

[0080] Then, prepare the ion storage layer slurry: weigh 20g of carbide-derived carbon material and 500g of deionized water, stir evenly, and then ultrasonically disperse for 3 hours to obtain the red ion storage layer slurry for later use.

[0081] Finally, an all-solid-state electrolyte membrane was prepared: 1000g of lithium perchlorate powder, 4000g of polyurethane powder, and 1000g of LISICON-type ceramic powder (Li... 9.4 Si 1.74 P 1.44 S 11.7 Cl 0.3 After mixing the powder by adding it to a screw extruder and setting the heating temperature to 150°C, the powder is then fed into a casting press to obtain a fully solid electrolyte membrane.

[0082] use Figure 2 The coating apparatus shown uses the 7 collecting roller as a power unit. While the 7 collecting roller rotates, the 3 feeding roller conveys a 12μm dense PVC film, which passes through the 10 guide roller and the 8 guide wheel to the 4 coating unit 1. There, a dispersed infrared control slurry is coated using a spraying device to a thickness of 200μm, and then the film enters the 5 drying unit 1 for drying at 80°C. While the 7 collecting roller rotates, the 12 feeding roller 2 conveys a 500μm polyvinylidene fluoride (PVDF) film, which passes through the 10 guide roller to the 13 coating unit 2. There, a dispersed ion storage layer slurry is coated using a spraying device to a thickness of 500μm, and then the film enters the 14 drying unit 2 for drying at 80°C. Simultaneously, while the 7 collecting roller rotates, 2 wire feeders 1 and 15 wire feeders 2 convey a 0.1mm diameter copper wire to the 6 hot press roller. The coated polymer infrared control film, ion storage film, and solid electrolyte film are also conveyed to the 6 hot press roller at a speed of 5m / min. The polymer infrared control film, conductive current collector, solid electrolyte layer, conductive current collector, and ion storage film are pressed together into a whole by 6 hot press rollers at a temperature of 150°C and a pressure of 200 kPa. After cooling by 11 air cooling devices, the all-solid dynamic temperature control film is finally collected by 7 collecting rollers.

[0083] like Figure 9 The display shows the switching state of the all-solid-state dynamic temperature-controlled thin film under different voltages. When the voltage is -2V, the film is in a high-temperature state at 39.2℃, and when the voltage is 3.5V, the film is in a low-temperature state at 35.3℃, with a temperature difference of 3.9℃. Figure 10 The infrared reflectance spectra of the all-solid-state dynamically temperature-controlled thin film at different voltages are shown. At -2V, it is in a low-reflectance state with a reflectance of 22.5% at approximately 10μm; at 3.5V, it is in a high-reflectance state with a reflectance of 28.8% at approximately 10μm. The reflectance tuning range is 7.3%. Figure 11The results show that the all-solid-state dynamic temperature control film has a fast temperature switching speed, with a voltage application time of 7.3s to switch from a high temperature state to a low temperature state at -2.5V and a voltage application time of 8.9s to switch from a low temperature state to a high temperature state at 3.5V.

Claims

1. A fully solid-state dynamic temperature control thin film, characterized in that, The all-solid dynamic temperature control film sequentially comprises: an infrared control film layer, an all-solid electrolyte layer, and an ion storage layer film, wherein a conductive current collector is provided between the infrared control film layer and the all-solid electrolyte layer, and a conductive current collector is provided between the all-solid electrolyte layer and the ion storage layer; wherein the all-solid electrolyte layer material composition comprises: inorganic salt, additives, and polymer; wherein the inorganic salt is one or more of lithium salt, sodium salt, potassium salt, aluminum salt, and magnesium salt; the additive is one or more of perovskite ceramic powder, sodium superionic conductor ceramic powder, LISICON type ceramic powder, and garnet type ceramic powder; the polymer is one or more of polyethylene oxide (PEO), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polymethyl methacrylate (PMMA), polyurethane (PU), phenolic resin, polyvinylidene fluoride (PVDF), polypropylene oxide (PPO), polyacrylonitrile (PAN), polyvinyl chloride (PVC), and polyvinylidene chloride (PVDC).

2. The all-solid-state dynamic temperature control film according to claim 1, characterized in that, The all-solid dynamic temperature control film also includes a polymer substrate film, wherein the infrared control film layer is disposed on the surface of the polymer substrate film. The polymer substrate film includes a porous film or a dense film; the polymer substrate film material is one or more of the following: polyethylene film, polyvinyl chloride film, polyvinylidene fluoride film, polycarbonate film, polystyrene film, polymethyl methacrylate, methyl methacrylate-acrylonitrile-butadiene-styrene plastic film, polyethylene terephthalate film, and polyurethane film. The infrared modulation material is one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanotube derivatives, graphene, graphene derivatives, polyaniline, polyaniline derivatives, poly(3,4-ethylenedioxythiophene), and poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid. The thickness of the polymer substrate is 0.05μm to 1000μm; the thickness of the infrared modulation material is 0.01μm to 500μm.

3. The all-solid-state dynamic temperature control film according to claim 1, characterized in that, The thickness of the all-solid electrolyte layer is 1μm to 1000μm.

4. The all-solid-state dynamic temperature control film according to claim 1, characterized in that, The ion storage layer thin film comprises a flexible substrate and an ion storage material layer; wherein the flexible substrate material is one or more of polyethylene terephthalate, polyimide, polyethylene film, polyvinyl chloride film, polyvinylidene fluoride film, polycarbonate film, polystyrene film, polymethyl methacrylate, methyl methacrylate-acrylonitrile-butadiene-styrene plastic film, and polyurethane film; and the ion storage material is one or more of carbide-derived carbon materials, porous carbon materials, activated carbon materials, graphene, electrospun carbon nanofibers, conductive polymers, and carbon nanotubes. The thickness of the ion storage layer ranges from 1 μm to 1000 μm; the thickness of the flexible substrate ranges from 0.05 μm to 2000 μm. The conductive current collector includes one or more of fiber-type current collectors and sheet-type current collectors; the fiber-type current collector is one or more of metal fiber, carbon nanotube fiber, nickel-plated yarn, copper-plated metal fiber, gold-plated metal fiber, and carbon fiber; the sheet-type current collector is one or more of metal sheet, graphene conductive sheet, and conductive fiber braided sheet. The diameter of the fiber-type current collector is 5μm~1000μm; the width of the sheet-type current collector is 1μm~1500μm, and the thickness is 1μm~100μm.

5. A method for preparing an all-solid-state dynamic temperature-controlled thin film as described in claim 1, comprising: (1) An infrared modulation layer is coated on a polymer substrate and dried to obtain a polymer infrared modulation substrate film; (2) The ion storage material is coated on the substrate film and dried to obtain the ion storage layer film; (3) Mix inorganic salts, additives and polymers, heat, cast and press into a film to obtain an all-solid electrolyte film; (4) The polymer infrared modulated substrate film, the conductive current collector, the all-solid electrolyte film, the conductive current collector and the ion storage layer film are hot-pressed to obtain an all-solid dynamic temperature modulated film.

6. The preparation method according to claim 5, characterized in that, In step (1), the polymer substrate film is transported and moved by the transmission device, coated with infrared modulation slurry by the coating device, dried by the drying device, and finally obtained by the collection device. The infrared-controlled slurry uses one or more of the following solvents: isopropanol (IPA), water (H2O), N-methylpyrrolidone (NMP), acetone, N,N-dimethylformamide (DMF), butyl acrylate (BA), and propylene carbonate (PC); the solid content of the infrared-controlled material in the slurry is 0.05~80 wt.%; the coating device for the slurry includes one or two of the following: a coating device and a spraying device; the length of the drying device is 0.1m~10m, the drying temperature is 30℃~150℃, and the transmission speed is 0.01m / min~100m / min.

7. The preparation method according to claim 5, characterized in that, In step (2), the flexible substrate film is transported and moved by the transmission device, coated with ion storage layer slurry by the coating device, dried by the drying device, and finally obtained by the collection device. The dispersant in the ion storage layer slurry is one or more of the following: isopropanol (IPA), water (H2O), N-methylpyrrolidone (NMP), acetone, N,N-dimethylformamide (DMF), butyl acrylate (BA), and propylene carbonate (PC). The solid content of the ion storage material in the ion storage layer slurry is 0.05~80 wt.%. The coating device for the slurry includes one or two of the following: a coating device and a spraying device. The drying device has a length of 0.1m~10m, a drying temperature of 30℃~150℃, and a conveying speed of 0.01m / min~100m / min. In step (3), inorganic salts, additives and polymers are first added to the screw extruder and mixed evenly by heating. Then, the all-solid electrolyte film is extruded through the fixed die of the casting press. The mass ratio of inorganic salt to polymer in the all-solid electrolyte film is 1:19 to 9:1, and the solid content of the additive is 0 wt.% to 50 wt.% of the mixture of inorganic salt and polymer; the screw extruder heating temperature is 110℃ to 250℃.

8. The preparation method according to claim 5, characterized in that, In step (4), the polymer infrared-controlled substrate film, the conductive current collector and the all-solid electrolyte film are passed together through the hot roller pressing device by the transmission device to prepare the all-solid dynamic temperature-controlled film, which is then collected. The transmission speed of the transmission device is 0.5m / min to 20m / min; the temperature of the hot roller is 100℃ to 220℃; and the pressure of the hot roller is 100 Pa to 2MPa.

9. An apparatus used in the preparation method of claim 5, characterized in that, The device includes a first device for outputting a polymer infrared-controlled substrate film, a second device for outputting an ion storage layer film, a third device for outputting an all-solid-state electrolyte film, a fourth device for conveying a first conductive current collector, a fifth device for outputting a second conductive current collector, and a hot press roller. The polymer infrared-controlled substrate film, the first conductive current collector, the all-solid-state electrolyte film, the second conductive current collector, and the ion storage layer film output by the first, fourth, third, fifth, and second devices are respectively fed into the hot press roller for pressing and collected by a collecting roller. The first device is described as being conveyed through a first coating device and a first drying device before being output to a hot press roller. In the second device, the material is conveyed through a second coating device and a second drying device in sequence before being output to a hot press roller. In the third device, the product is output to the hot press roller after passing through the casting and pressing machine; In devices 4 and 5, the hot press rollers are directly fed in via a conveying device.

10. The application of the all-solid-state dynamic temperature control film of claim 1 in the fields of temperature management of buildings, outdoor equipment, human body temperature, spacecraft, or infrared camouflage.

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