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CN-122008637-A - Temperature-control composite structure material with photo-thermal absorption and radiation cooling functions and preparation method thereof

CN122008637ACN 122008637 ACN122008637 ACN 122008637ACN-122008637-A

Abstract

The invention provides a temperature control composite structure material with photo-thermal absorption and radiation cooling and a preparation method thereof, and belongs to the technical field of temperature control materials, wherein the temperature control composite structure material comprises an array arrangement of Fe 3 O 4 photo-thermal units formed by combining a high-temperature color-changing layer, an Fe 3 O 4 photo-thermal layer and a basal layer and a BaSO 4 radiation cooling unit formed by combining a low-temperature color-changing layer, a BaSO 4 radiation cooling layer and a basal layer, or comprises an array arrangement of Fe 3 O 4 photo-thermal units formed by combining a high-temperature color-changing layer and an Fe 3 O 4 photo-thermal layer and a BaSO 4 radiation cooling unit formed by combining a low-temperature color-changing layer and a BaSO 4 radiation cooling layer. The invention provides a preparation method of a temperature control composite structure material with photo-thermal absorption and radiation cooling, and the prepared temperature control composite structure material can realize temperature self-adaptive switching so that environmental energy can be efficiently utilized and has good environmental adaptability.

Inventors

  • YUAN MAN
  • LIU BO
  • HUANG FEI
  • GUO ZHI
  • QIAN LONG
  • ZHANG RUNNAN
  • GAO WENYUAN

Assignees

  • 东北大学

Dates

Publication Date
20260512
Application Date
20251226

Claims (10)

  1. 1. The temperature control composite structure material with the functions of photo-thermal absorption and radiation cooling is characterized by comprising a first Fe 3 O 4 photo-thermal unit formed by combining a high-temperature color-changing layer, a Fe 3 O 4 photo-thermal layer and a basal layer and a first BaSO 4 radiation cooling unit formed by combining a low-temperature color-changing layer, a BaSO 4 radiation cooling layer and the basal layer, wherein the first Fe 3 O 4 photo-thermal unit and the first BaSO 4 radiation cooling unit are arranged together in an array manner; The Fe 3 O 4 is Fe 3 O 4 with particle size regulated and controlled, and the BaSO 4 is BaSO 4 with surface modified; the particle size of Fe 3 O 4 is 10-100 nm, and the particle size of BaSO 4 is 0.2-2.5 mu m; The arrangement arrays of the first Fe 3 O 4 photo-thermal unit and the first BaSO 4 radiation cooling unit are geometric arrays which are regularly or irregularly arranged in a plane, including but not limited to a regular hexagonal honeycomb array, a square array, a regular triangle array and a regular hexagonal honeycomb-regular triangle combined array; The high-temperature color-changing layer is in a transparent/high-light-transmission state at the temperature T < T 1 , and is in an opaque/low-light-transmission state at the temperature T being more than or equal to T 1 ; The low-temperature color-changing layer is in an opaque/low light-transmitting state when T is less than T 2 , and is in a transparent/high light-transmitting state when T is more than or equal to T 2 ; the temperature of T 1 、T 2 is 15-65 ℃, and the difference between T 1 and T 2 is not more than 10 ℃.
  2. 2. The temperature-controlled composite structural material with photo-thermal absorption and radiation cooling according to claim 1, wherein the temperature-controlled composite structural material comprises a second Fe 3 O 4 photo-thermal unit formed by combining a high-temperature color-changing layer and a Fe 3 O 4 photo-thermal layer and a second BaSO 4 radiation cooling unit formed by combining a low-temperature color-changing layer and a BaSO 4 radiation cooling layer, which are arranged together in an array; The arrangement array of the second Fe 3 O 4 photo-thermal unit and the second BaSO 4 radiation cooling unit is a geometric array that is regularly or irregularly arranged in a plane, including but not limited to a regular hexagonal honeycomb array, a square array, a regular triangle array, and a regular hexagonal honeycomb-regular triangle combined array.
  3. 3. A method of preparing a temperature controlled composite structure material having photothermal absorption and radiation cooling as claimed in claim 1 or 2, comprising the steps of: According to mass percentage, mixing 10% -30% of thermochromic microcapsules and 10% -30% of thermochromic microcapsules with 40% -80% of matrix, 0.5% -3% of dispersing agent and 0.1% -1% of ultraviolet absorbent at 10-65 ℃ for 10-60 min to obtain a thermochromic mixed system and a thermochromic mixed system; Respectively coating a high-temperature color-changing mixed system and a low-temperature color-changing mixed system on the surface of a polyethylene terephthalate film or glass, and then drying at 50-80 ℃ for 10-30 min to obtain a high-temperature color-changing layer and a low-temperature color-changing layer with the thickness of 50-200 mu m; Adding deionized water and a dispersing agent into Fe 3 O 4 powder and BaSO 4 powder respectively, stirring and dispersing, then dripping a binder into the mixture, performing ultrasonic water bath treatment to form a colloid dispersion liquid, and adding ethanol and acid liquor into the colloid dispersion liquid to obtain Fe 3 O 4 suspension and BaSO 4 suspension with pH values of 3-6; Spraying the Fe 3 O 4 suspension and the BaSO 4 suspension on the surface of the substrate layer for multiple times according to the thickness of 5-100 mu m each time, drying at 60-80 ℃ for 30-90 min after each spraying, and forming a Fe 3 O 4 photo-thermal layer and a BaSO 4 radiation cooling layer with the thickness of 0.05-1.5 mm on the surface of the substrate layer respectively; Combining the high-temperature color-changing layer with the Fe 3 O 4 photo-thermal layer on the basal layer through an adhesive to form a first Fe 3 O 4 photo-thermal composite structural material of the high-temperature color-changing layer, the Fe 3 O 4 photo-thermal layer and the basal layer; Combining the low-temperature color-changing layer with the BaSO 4 radiation cooling layer on the basal layer through an adhesive to form a first BaSO 4 radiation cooling composite structural material of the low-temperature color-changing layer, the BaSO 4 radiation cooling layer and the basal layer; Cutting the first Fe 3 O 4 photo-thermal composite structure material and the first BaSO 4 radiation cooling composite structure material into preset shapes to obtain a first Fe 3 O 4 photo-thermal unit and a first BaSO 4 radiation cooling unit respectively; arranging and bonding the first Fe 3 O 4 photo-thermal unit and the first BaSO 4 radiation cooling unit array to form a temperature control composite structure material with photo-thermal absorption and radiation cooling; The high-temperature color-changing layer is in a transparent/high-light-transmission state at the temperature T < T 1 , and is in an opaque/low-light-transmission state at the temperature T being more than or equal to T 1 ; The low-temperature color-changing layer is in an opaque/low light-transmitting state when T is less than T 2 , and is in a transparent/high light-transmitting state when T is more than or equal to T 2 ; The temperature of T 1 、T 2 is 15-65 ℃, and the difference between T 1 and T 2 is not more than 10 ℃.
  4. 4. A method of preparing a temperature controlled composite structure material with photo-thermal absorption and radiation cooling according to claim 3, comprising the steps of: Spraying the Fe 3 O 4 suspension on the surface of the high-temperature color-changing layer for multiple times according to the thickness of 5-100 mu m sprayed each time, drying at a constant temperature of 40-80 ℃ for 5-90 min after each spraying, and forming a Fe 3 O 4 photo-thermal layer with the thickness of 0.05-1.5 mm on the high-temperature color-changing layer to obtain a second Fe 3 O 4 photo-thermal composite structure material of the high-temperature color-changing layer and the Fe 3 O 4 photo-thermal layer structure; Spraying the BaSO 4 suspension on the surface of the low-temperature color-changing layer for multiple times according to the thickness of 5-100 mu m sprayed each time, drying at a constant temperature of 40-80 ℃ for 5-90 min after each spraying, and forming a BaSO 4 radiation cooling layer with the thickness of 0.05-1.5 mm on the low-temperature color-changing layer to obtain a second BaSO 4 radiation cooling composite structural material with a structure of the low-temperature color-changing layer and the BaSO 4 radiation cooling layer; Cutting the second Fe 3 O 4 photo-thermal composite structural material and the second BaSO 4 radiation cooling composite structural material into preset shapes to obtain a second Fe 3 O 4 photo-thermal unit and a second BaSO 4 radiation cooling unit respectively; Arranging and bonding the second Fe 3 O 4 photo-thermal unit and the second BaSO 4 radiation cooling unit array to form a temperature control composite structure material with photo-thermal absorption and radiation cooling; The high-temperature color-changing layer is in a transparent/high-light-transmission state at the temperature T < T 1 , and is in an opaque/low-light-transmission state at the temperature T being more than or equal to T 1 ; The low-temperature color-changing layer is in an opaque/low light-transmitting state when T is less than T 2 , and is in a transparent/high light-transmitting state when T is more than or equal to T 2 ; The temperature of T 1 、T 2 is 15-65 ℃, and the difference between T 1 and T 2 is not more than 10 ℃.
  5. 5. The preparation method of the temperature-controlled composite structural material with photo-thermal absorption and radiation cooling according to claim 3 or 4, wherein the color-changing temperature of the high-temperature thermochromic microcapsules and the low-temperature thermochromic microcapsules is 15-65 ℃, the matrix is aqueous polyurethane dispersion or acrylic emulsion, the dispersing agent comprises at least one of sodium polyacrylate, polyethylene glycol, polycarboxylate, phosphate, polyethyleneimine, sodium silicate, citric acid, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and sodium hexametaphosphate, and the ultraviolet absorber is at least one of benzotriazole compounds, triazine compounds, zinc oxide and titanium dioxide.
  6. 6. The method for preparing a temperature-controlled composite structural material with photo-thermal absorption and radiation cooling according to claim 3 or 4, wherein the preparation of the Fe 3 O 4 powder comprises the steps of: 1) Dissolving ferrous salt and ferric salt in distilled water according to a molar ratio of 1:1-1:3 to prepare a ferrous salt and ferric salt mixed solution; 2) Dropwise adding an alkaline solution into a mixed solution of ferrous salt and ferric salt to adjust the pH value of the solution to 8.5-10.5, so as to obtain a reaction system; 3) And heating the reaction system to 65-85 ℃ for reaction for 0.75-1.5 h, filtering after the reaction is finished, washing the separated precipitate to be neutral, and drying to obtain Fe 3 O 4 powder with the grain diameter of 10-100 nm and the crystal forms of (220), (311), (400) and the like which are all of inverse spinel structures.
  7. 7. The method for preparing a temperature-controlled composite structural material with photo-thermal absorption and radiation cooling according to claim 3 or 4, wherein the modification of BaSO 4 powder comprises the steps of: 1) Adding 0.5-7wt% of SiO 2 、Al 2 O 3 、ZrO 2 and Y 2 O 3 powder with the particle size of 10-200 nm into BaSO 4 powder with the average particle size of 0.5 mu m to obtain mixed powder; 2) Distilled water is added into the mixed powder, and the mixed powder is stirred and dispersed to obtain mixed slurry; 3) Evaporating and drying the mixed slurry at 60-100 ℃, and performing solid phase heat treatment at 400-1000 ℃ for 0.5-3 hours to obtain a heat treatment block; 4) And grinding the heat-treated material blocks to obtain modified BaSO 4 powder with the particle size of 0.2-2.5 mu m.
  8. 8. The preparation method of the temperature-controlled composite structural material with photo-thermal absorption and radiation cooling according to claim 3, wherein the binder is a polyvinyl alcohol solution with the mass concentration of 4-6wt%, or polyacrylamide or hydroxypropyl methylcellulose, the substrate layer material is a stainless steel sheet, copper foil, titanium foil, glass fiber reinforced plastic, cement, ceramic or other metal or nonmetal base materials with certain mechanical strength and temperature resistance, and the binder is a pressure-sensitive adhesive, polyurethane adhesive or other weather-resistant structural adhesive with the temperature resistance of-20-80 ℃ and the bonding strength of more than or equal to 0.5MPa and resistant to ultraviolet aging.
  9. 9. The method of claim 3 or 4, wherein the Fe 3 O 4 photo-thermal unit is offset from adjacent units in the array of BaSO 4 radiation cooling units by no more than 5 °.
  10. 10. The method for preparing the temperature-controlled composite structural material with photo-thermal absorption and radiation cooling according to claim 9, wherein the Fe 3 O 4 photo-thermal unit and the BaSO 4 radiation cooling unit are bonded together through a temperature-resistant polyurethane structural adhesive or heat-conductive silicone grease with a temperature resistant range of-30-100 ℃ and a shearing strength of more than or equal to 0.6MPa, and are pressed and solidified for 50-70 min at room temperature.

Description

Temperature-control composite structure material with photo-thermal absorption and radiation cooling functions and preparation method thereof Technical Field The invention relates to the technical field of temperature control materials, in particular to a temperature control composite structure material with photo-thermal absorption and radiation cooling and a preparation method thereof. Background Climate change is driven mainly by greenhouse gas emissions, which is closely related to the continued increase in energy consumption worldwide. Conventional heating and cooling techniques consume a significant amount of energy in the thermal management of the human living environment. According to the international energy agency data, about 21.5% of the energy is used for heating or cooling of residential and commercial buildings worldwide, and in developed areas, the energy put into temperature management may exceed 40% of the total consumption of energy in the country. Solar thermal effect heating and passive radiative cooling (PDRC) refrigeration as sustainable thermal management techniques can alleviate current global energy consumption problems without additional energy consumption. Wherein solar heating relies on the absorption of an object into the solar spectrum (300-2500 nm) and converts it into thermal energy. On the other hand, the passive radiation cooling material increases the reflectivity of the solar band (300-2500 nm) and the emissivity of the atmospheric window band (8-13 μm), helping to reduce the heat increase and to transmit out the thermal radiation through the atmospheric window, i.e. to reduce the object temperature by reflecting sunlight and emitting Long Wave Infrared (LWIR) into the cold universe (about 3K). Therefore, the fluctuating ambient temperature is handled through the temperature intelligent self-adaptive thermal management technology, so that the material is switched between heating and cooling modes, and the temperature management requirements in the aspects of production, life and the like can be met. In recent years, researchers have developed a large number of materials with photo-thermal effects to accommodate applications in different circumstances. These photothermal materials can be classified into four functional classes, metal nanoparticles, carbon-based, organic polymers and semiconductor materials, and the photothermal conversion mechanisms of these different classes of materials are greatly different. When the metal nano particles interact with light with proper wavelength, free electrons on the surface of the metal nano particles are excited, conduction band electrons collectively oscillate at the same frequency, and Local Surface Plasmon Resonance (LSPR) is formed. The material has high light-heat conversion efficiency and strong heating capacity, and the most commonly used plasma metals are gold, silver, noble metals with nano structures and the like, so that the material has high cost and is difficult to apply on a large scale. If the low-cost metals such as aluminum, copper and the like are used for replacement, the stability and performance of the material are reduced due to the fact that the nano-material is easy to oxidize, and part of metal nano-particles have biotoxicity and have potential harm to living things. Carbon-based materials (such as carbon nanotubes, graphene, carbon black, graphite, carbon composites, etc.) have strong light absorption and Gao Guangre conversion efficiency in a wide wavelength range, and although such materials have excellent properties and lower raw material cost, they have disadvantages of poor dispersibility and need to rely on chemical modification to be stably dispersed in water or other use environments. In addition, the preparation of high-quality graphene requires high-precision control conditions, and the complex preparation process is also a reason for restricting the application of the high-quality graphene. Organic polymer materials are widely studied for their excellent photo-thermal conversion efficiency and biocompatibility. Typical organic polymers include polyaniline, polypyrrole, metal Organic Frameworks (MOFs), covalent Organic Frameworks (COFs), polydopamine, and polymer molecules of donor-acceptor structure. Although organic materials have been well studied and have excellent properties in some scenes, they have disadvantages such as poor thermal stability, high synthesis difficulty (complex preparation of COF and MOF and harsh chemical reaction conditions), and the like, and cannot be used as materials for large-area applications. For semiconductor materials, photons are absorbed to generate active electron-hole pairs when irradiated with incident light having an energy equal to or greater than the bandgap. Photoexcitation generates electrons in the conduction band and leaves electron vacancies or holes in the valence band. Subsequent relaxation from the higher excited state to the lower energy state ma