CN114805941A - Directional heat-conducting porous radiation refrigeration film material and preparation method thereof - Google Patents
Directional heat-conducting porous radiation refrigeration film material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a directional heat-conducting porous radiation refrigeration film material and a preparation method thereofThe oriented heat conducting film is prepared by dispersing MXene oriented heat conducting materials into cellulose and performing oriented freeze drying. The reflectivity of the material to sunlight is 95-99%, the emissivity of the material in an atmospheric window of 8-13 mu m is 94-98%, and the emissivity in solar irradiance is 700-1200W/m 2 The temperature can be reduced by 10-25 ℃, so that the internal heat can be quickly and directionally transferred to the outside, and the directional regulation and control of the internal heat of the building can be realized. The invention solves the problems that heat transfer is reduced only from the outside without paying attention to internal heat regulation and control and the like in the prior art, has excellent daytime cooling performance, and can be applied to the fields of building energy conservation, wearable equipment, photovoltaics, 5G base stations, mobile intelligent terminals and the like.
Description
Technical Field
The invention belongs to the technical field of radiation refrigeration materials, and particularly relates to a directional heat conduction porous radiation refrigeration film material and a preparation method thereof.
Background
Traditional refrigeration equipment such as air conditioners, fans and the like are driven by electric power, and although a certain cooling effect can be achieved, the consumption of electric power energy is increased in the use process, so that negative effects such as greenhouse effect, air pollution and even acid rain are caused. Therefore, it is of great significance to develop green materials with good cooling effect. The novel radiation refrigeration technology has the advantages of zero energy consumption, no pollution, high cooling performance and the like, and is considered as an ideal choice for replacing an energy-intensive refrigeration mode at the present stage. Various materials and new preparation methods play a great role in promoting the development of refrigeration materials, so that the passive radiation refrigeration technology is expected to be widely applied to the fields of building energy conservation, wearable equipment, photovoltaics, 5G base stations, mobile intelligent terminals and the like.
The cellulose has a unique three-dimensional gap network structure, multiple-scale optical fibers and channels exist in the cellulose as disordered scattering units to scatter sunlight, and the fibersThe absorption of vibration of chemical bonds in the vitamin generates higher infrared emissivity, but cannot perfectly cover the whole atmosphere transparent window (8-13 mu m), so that the high infrared emissivity can be realized at the position of 8-13 mu m only by realizing the aggregation of various characteristic functional groups through reasonable molecular structure design and synthesis. Nanoparticles (SiO) with special hollow structure 2 、HfO 2 、TiO 2 、ZrO 2 Etc.) can further improve the infrared emissivity of the material, the semiconductor nano-particles have special surface plasmon polariton effect, after the infrared radiation is absorbed by the material, the electron collective oscillation on the surface of the particles is caused, the high emissivity can be obtained in the middle and far infrared wave bands, the hollow microspheres with good sealing degree can also improve the scattering of the solid phase phonons of the shell, thereby reducing the heat transfer of the solid phase phonons, and the heat transfer to the spherical shell needs to pass through the inside of the hollow microspheres and undergo one-time gas phase heat transfer, thereby greatly reducing the heat conductivity coefficient. The nano particles are uniformly dispersed in the cellulose substrate, so that the cooling effect can be efficiently realized.
Patent CN110317521A discloses a selective radiation refrigeration coating, which includes a radiation refrigeration functional layer with a particulate filler with a special structure, for reflecting ultraviolet light and/or visible light and/or near infrared light in sunlight, and emitting heat through an atmospheric window in an infrared radiation manner, the radiation refrigeration functional layer includes a particulate filler with a rod-like structure and a radiation refrigeration functional layer resin, the particulate filler is distributed in the radiation refrigeration functional layer resin, and finally, the reflectivity of > 80% and the infrared emissivity of > 80% are realized. Patent CN113372612A discloses a method for preparing a cellulose-based radiation temperature-regulating material, which is to prepare cellulose aerogel with a three-dimensional porous structure by performing functional modification on cellulose, and shows near 94% of solar reflectance and 95% of infrared emissivity. However, the currently developed radiation refrigeration materials only focus on reducing the heat input from the outside, and lack an effective regulation means for the heat radiation generated in the inner space (the back side of the solar radiation). The key to solving the problem lies in developing a material which can realize the rapid directional heat conduction from the inside to the outside, thereby achieving the ideal cooling effect of the inner space.
Patent CN106631082A discloses a carbon nanotube composite material with high oriented thermal conductivity and a preparation method thereof, wherein the thermal conductivity of the composite material in the axial direction is greater than 100W/m.k and the thermal conductivity difference in the non-axial direction exceeds more than 50W/m.k by magnetically regulating and controlling the oriented arrangement of the carbon nanotubes. However, the method for preparing the aligned carbon nanotube array is complicated in operation and is harsh in conditions. The two-dimensional transition metal carbide (MXene) not only has the excellent performance of the traditional two-dimensional nano material, but also has the high electrical conductivity (8000S/cm) of metal, and according to the Weldmann-Franz law, the ratio of the thermal conductivity to the electrical conductivity is in direct proportion to the temperature, so that the MXene also shows high thermal conductivity. The single-layer MXene material has the characteristics of large sheet, single layer, low defect and the like, and due to the reduction of structural defects, the heat conductivity parallel to the direction of the heat conduction material is improved, the distance between material sheet layers is increased, the heat conductivity perpendicular to the direction of the heat conduction material is reduced, and the anisotropy of the heat conductivity is caused.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a directional heat-conducting porous radiation refrigeration film material and a preparation method thereof, aiming at solving the problems that the existing radiation refrigeration material only focuses on reflection of sunlight, and lacks an effective regulation and control means for heat radiation generated by an internal space (a solar radiation back surface). The inner side face with high directional heat conduction capacity is constructed, heat is rapidly transferred from inside to outside, the outer side face with high solar reflectivity and high infrared emissivity is constructed, external heat enters the inside as little as possible and selectively emits the internal heat to the outer space in a heat radiation mode, the inner and outer two layers of films are effectively combined and act in a synergistic mode, the radiation refrigeration material shows a good cooling effect, and the radiation refrigeration material is an ideal choice of a novel high-efficiency radiation refrigeration material.
The technical scheme is as follows: the directional heat-conducting porous radiation refrigeration film material is formed by laminating an outer side high-reflectivity film and an inner side directional heat-conducting film; the high-reflectivity film is prepared by dispersing hollow nano microspheres into cellulose and performing phase conversion; the oriented heat conducting film is prepared by dispersing MXene oriented heat conducting materials into cellulose and performing oriented freeze drying.
Furthermore, the hollow nano-microsphere takes polystyrene as a template.
Further, the MXene oriented heat conduction material is prepared by selectively etching a MAX precursor by an in-situ growth hydrofluoric acid method, ultrasonically stripping and carrying out vacuum filtration.
The invention also discloses a preparation method of the directional heat conduction porous radiation refrigeration film material, which comprises the following steps:
step 1, preparing a directional heat conduction material: adding MAX precursor, LiF and 37 wt% of dilute hydrochloric acid into a reaction kettle at room temperature according to the mass ratio of 1:2: 20-1: 3:60, uniformly mixing, reacting for 24-48 h, centrifuging, washing the precipitate with deionized water until the pH value of the washing solution is greater than 6, adding deionized water into the precipitate according to the mass ratio of 1: 2-1: 3, carrying out ultrasonic treatment at 900-1320W for 6-12 h, carrying out vacuum filtration, and drying the filter cake at 60-80 ℃ for 12-24 h to obtain the MXene oriented heat conduction material;
step 2, preparing an oriented heat-conducting film: the mixed solution is NaOH, urea and water solution in a mass ratio of 1:2: 4-1: 4:10, MXene directional heat conduction materials, cellulose and the mixed solution prepared in the step 1 are added into a reaction kettle at room temperature according to a mass ratio of 1:5: 30-1: 10:80, the cellulose and the mixed solution are uniformly mixed, absolute ethyl alcohol is added into the mixture according to a mass ratio of the mixture to the absolute ethyl alcohol of 1: 2-1: 4, standing for 8-16 h to obtain wet gel, adding deionized water into the wet gel according to the mass ratio of the wet gel to the deionized water of 1: 2-1: 3, standing for 2-4 h, filtering to obtain hydrogel, transferring the hydrogel into a mold, freezing at-80 to-20 ℃ for 1 to 3 hours, and drying at-80 to-40 ℃ for 24 to 48 hours to obtain an oriented heat-conducting film with the film thickness of 0.2 to 0.5 mm;
step 3, preparing hollow nano microspheres: at room temperature, adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle according to the mass ratio of 1:1: 10-1: 2:30, uniformly mixing to obtain a mixture, adding azodiisobutyronitrile and styrene into the mixture according to the mass ratio of 1:5: 25-1: 7:50, reacting at 60-80 ℃ for 10-14 h, filtering, washing the filter cake with absolute ethyl alcohol for 3-4 times according to the mass ratio of 1: 2-1: 3, and drying at 60-80 ℃ for 24-48 h to obtain polystyrene microspheres; adding ammonia water, an ester precursor and absolute ethyl alcohol into a reaction kettle at room temperature according to the volume ratio of 1:2: 30-1: 3:50 of the ammonia water, the ester precursor and the absolute ethyl alcohol, uniformly mixing to obtain a mixed solution, adding a surfactant and the prepared polystyrene microspheres into the mixed solution according to the mass ratio of the surfactant, the polystyrene microspheres and the mixed solution of 1:3: 40-1: 5:80, reacting for 24-48 h, filtering, washing the filter cake with deionized water according to the mass ratio of the filter cake to the deionized water of 1:2, drying, heating to 400-700 ℃ at the heating rate of 1-5 ℃/min, calcining for 1-3 h, and cooling to room temperature to obtain hollow nano microspheres;
step 4, preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent in a volume ratio of 1: 2-1: 9, the hollow nano microspheres and cellulose prepared in the step 3 are added into the mixed solvent according to a mass ratio of 1: 10-1: 30 at room temperature, the mixture is stirred uniformly to obtain a mixture, the mixture is poured into a glass mold, the bottom of the glass mold is covered with the directional heat conduction membrane prepared in the step 2, acetone is volatilized to obtain a laminated membrane, the laminated membrane is placed in absolute ethyl alcohol to be soaked for 2-6 hours, the laminated membrane is taken out and dried for 3-6 hours at a temperature of 60-80 ℃, and the membrane material has a membrane thickness of 0.3-1.1 mm.
Further, in step 1, the MAX precursor is Ti 3 AlC 2 Or Ti 2 AlC。
Further, in step 3, the ester precursor is ethyl orthosilicate or tetrabutyl titanate.
Further, in step 3, the surfactant is cetyl trimethyl ammonium bromide or sodium dodecyl sulfate.
Further, in step 3, the cellulose is bacterial cellulose or lignocellulose.
The invention principle is as follows: the invention is formed by superposing a high-reflectivity film and an oriented heat-conducting film, wherein the high-reflectivity film is prepared by uniformly dispersing hollow nano microspheres into cellulose, is used for reflecting or scattering sunlight as much as possible and reducing the input of heat, has high emissivity in an atmosphere transparent window, and can selectively emit self heat to outer space. The oriented heat conduction film is prepared by dispersing oriented heat conduction materials into cellulose and performing oriented freeze drying, and is used for absorbing infrared heat radiation in an inner space and directionally transferring energy to an outer side film to reduce inward-emitted infrared radiation. The synergistic effect of the two films improves the reflectivity of the composite material to sunlight, reduces the inward emission energy of the composite material, improves the orientation of the outward transmission heat radiation of the composite material, and realizes the rapid directional transmission of heat from the inner side of the material to the outer side, so that the composite material shows excellent daytime cooling performance and is an ideal choice for novel high-efficiency radiation refrigeration materials.
The invention induces the directional heat conduction materials to be highly oriented and arranged in the cellulose by controlling the freezing and solidifying direction, strengthens the outward heat transfer efficiency, weakens the inward heat radiation effect, and obtains the directional heat conduction film by freezing and drying. On the basis, the characteristic structure design is carried out on the cellulose, the hollow nano microspheres with matched performance are selected as filling media, the outer side face with high solar reflectivity and high infrared emissivity is constructed, the reflectivity of the material to sunlight is improved, and the capability of the material to emit heat radiation to the space is enhanced. The synergistic effect of the two films is beneficial to the directional conduction of internal heat and enhances the passive radiation cooling effect.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
1. the invention adopts an in-situ hydrofluoric acid generation method to etch Ti 3 AlC 2 The prepared two-dimensional transition metal carbide (MXene) has the characteristics of large sheet, single layer, low defect and the like, the heat conductivity parallel to the MXene direction is improved, and the heat conductivity perpendicular to the MXene direction is reduced by controlling the interlayer distance of the material layers, so that the heat conductivity of the MXene is anisotropic. MXene is used as the oriented heat conduction material, so that the problems that the traditional preparation process using graphene and other carbon materials is complex and the preparation conditions are severe are solved. More active groups such as hydroxyl groups and the like are introduced to the surface of the single-layer MXene sheet, so that the surface presents negative charges, and electrostatic repulsion exists between the sheets, so that the MXene sheet can be kept for a long timeThe oriented heat-conducting film is in a stable state, and is added into cellulose, so that the heat conductivity and the mechanical strength of the oriented heat-conducting film are improved.
2. The MXene directional heat conduction material is dispersed in the cellulose, a film with directional heat conduction is obtained by utilizing a directional freeze drying technology and serves as an inner side face, the directional heat conduction material directionally grows in the vertical direction by controlling the temperature gradient in the freezing process, the heat is transferred to the outside from the inside in a directional mode due to the anisotropy of the heat conductivity, the ideal cooling effect of the inside is achieved, the problem that the heat accumulation is formed by excessive heat radiation due to the fact that the existing radiation refrigeration material is lack of directional heat conduction is solved, and the inward heat radiation is reduced.
3. Cellulose is selected as a polymer substrate, a porous structure is obtained by utilizing a phase conversion technology, the pore size is adjusted and controlled to be distributed in a concentrated mode to be about 5 micrometers, sunlight with all wavelengths can be effectively scattered by perfect matching of the pore size, solar radiation heat is reduced to a greater extent, the defect that the reflectivity of sunlight is improved by sputtering a metal layer in a traditional radiation refrigeration material is overcome, and the reflectivity of the material to the sunlight is improved by the existence of the porous structure.
4. The nano-microsphere with the hollow structure is obtained through a polystyrene template method, the microsphere has a special surface plasmon polariton effect, infrared radiation is absorbed by a material to cause surface electron collective oscillation, high emissivity can be obtained in middle and far infrared wave bands, and the hollow structure performs multiple reflection and scattering on incident sunlight, so that the solar radiation absorption is weakened, the refrigeration effect is improved, and the problems of low reflectivity, poor refrigeration effect and the like caused by the fact that the sunlight with a certain specific wavelength is absorbed by the original nano-microsphere are solved. The hollow nano-microspheres are dispersed in the cellulose substrate as a filling medium, so that the infrared emissivity and the solar reflectivity of the material are further improved.
5. The cellulose is activated by adopting a sodium hydroxide solution, hydrogen bonds in a cellulose crystallization area are damaged, the accessibility of cellulose hydroxyl groups is increased, an electrostatic effect exists between the cellulose hydroxyl groups and a dispersion medium, the dispersion medium can be uniformly loaded in cellulose molecules, the defect that free hydroxyl groups in the cellulose molecular crystallization area are few is overcome, active side chain hydroxyl groups are added, the side chain hydroxyl groups are designed and modified by utilizing a material with special properties, the mechanical property of the cellulose is enhanced, new functions are given to the cellulose, and the cellulose-derived polymer base material with high infrared emissivity and high directional thermal conductivity is obtained.
6. The surface of the directional heat-conducting film is constructed into a high-reflectivity film which takes cellulose as a high-molecular base material, hollow nano microspheres as a filling medium with high refractive index and high infrared emissivity, and a cavity with a specific size as a scattering filling medium by a phase conversion method, so that the directional heat-conducting film is laminated with the inner side directional heat-conducting film. The same cellulose is used as a substrate, the cellulose molecular chains at the interface are combined through hydrogen bonds, the two layers of membranes are tightly combined through mechanical interweaving acting force, meanwhile, the dispersion state and the content of the hollow nano microspheres in the cellulose are regulated and controlled, an ideal micro/nano rough structure surface is constructed, and the interface bonding strength is further enhanced by means of the surface roughness between the interfaces. The process that the heat is transmitted to the outer side face from the inner side face in an oriented mode and then is transmitted to the outer space in a heat radiation mode through the outer side face is achieved, the problem that the existing radiation refrigeration material only focuses on reflecting sunlight but neglects heat radiation generated by the inner space so that efficient radiation refrigeration cannot be achieved is solved, and cooling power and efficiency of the radiation refrigeration material are improved.
Drawings
FIG. 1 is a microscopic topography (SEM) of a directional heat-conducting porous radiation refrigeration thin film material;
fig. 2 is an actual cooling diagram of the directional heat-conducting porous radiation refrigeration film material.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
a) Preparing an oriented heat conduction material: at room temperature, putting MAX precursor, LiF and 37 wt% of dilute hydrochloric acid into a reaction kettle according to the mass ratio of 1:2:20, uniformly mixing, reacting for 24h, centrifuging, washing with deionized water until the pH value is greater than 6, adding deionized water into the precipitate according to the mass ratio of 1:2, carrying out ultrasonic treatment at 900W for 6h, carrying out vacuum filtration, and drying a filter cake at 60 ℃ for 12h to obtain the MXene oriented heat conduction material;
b) preparing an oriented heat-conducting film: the mixed solution is NaOH, urea and water solution with the mass ratio of 1:2:4, the MXene directional heat conduction material, the cellulose and the mixed solution prepared in the step a) are added into a reaction kettle and uniformly mixed at room temperature according to the mass ratio of 1:5:30, absolute ethyl alcohol is added into the mixture according to the mass ratio of 1:2 of the mixture to absolute ethyl alcohol, the mixture is kept stand for 12 hours to obtain wet gel, deionized water is added into the wet gel according to the mass ratio of 1:2 of the wet gel to the deionized water, the wet gel is kept stand for 2 hours and filtered to obtain hydrogel, the hydrogel is transferred into a mold, the hydrogel is frozen for 1 hour at minus 80 ℃, the hydrogel is dried for 24 hours at minus 80 ℃ to obtain a directional heat conduction membrane, and the membrane thickness is 0.24 mm;
c) preparing hollow nano microspheres: adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle at room temperature according to the mass ratio of 1:1:10, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile and styrene into the mixed solution according to the mass ratio of azobisisobutyronitrile, styrene and the mixed solution of 1:5:25, reacting for 10 hours at 60 ℃, filtering, washing the filter cake for 3 times by using absolute ethyl alcohol according to the mass ratio of the filter cake to the absolute ethyl alcohol, and drying for 24 hours at 60 ℃ to obtain polystyrene microspheres; adding ammonia water, a lipid precursor and absolute ethyl alcohol into a reaction kettle at room temperature according to the volume ratio of 1:2:30, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of 1:3:40 of the surfactant, the polystyrene microspheres and the mixed solution, reacting for 24 hours, filtering, washing the filter cake with deionized water according to the mass ratio of 1:2 of the filter cake to the deionized water, drying, and calcining for 1 hour at 400 ℃ at the heating rate of 1 ℃/min to obtain hollow nano microspheres;
d) preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone with the volume ratio of 1:2, the hollow nano microspheres and the cellulose prepared in the step c) are added into the mixed solvent at room temperature according to the mass ratio of 1:10, the mixture is uniformly stirred to obtain a mixture, the mixture is poured into a glass mold, the bottom of the glass mold is covered with the directional heat conducting film prepared in the step b), the acetone is volatilized to obtain a laminated film, the laminated film is placed into absolute ethyl alcohol for soaking for 2 hours, the laminated film is taken out and dried for 3 hours at 60 ℃, and the porous radiation refrigeration film material is prepared, wherein the film thickness of the film material is 0.6mm as shown in figure 1.
The refrigeration performance of the obtained material is tested by a temperature tester and a solar irradiance tester. The reflectivity of the material to sunlight is 95%, and the emissivity of the material in an atmospheric window of 8-13 mu m is 94%, as shown in figure 2, the film is in solar irradiance of 700W/m 2 The temperature can be reduced by 13 ℃.
Comparative example 1
a) Preparing hollow nano microspheres: adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle at room temperature according to the mass ratio of the polyvinylpyrrolidone to the water to the absolute ethyl alcohol of 1:1:10, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile and styrene into the mixed solution according to the mass ratio of the azobisisobutyronitrile to the styrene to the mixed solution of 1:5:25, reacting for 10 hours at 60 ℃, filtering, washing the filter cake for 3 times by using the absolute ethyl alcohol according to the mass ratio of the filter cake to the absolute ethyl alcohol of 1:2, and drying for 24 hours at 60 ℃ to obtain polystyrene microspheres; adding ammonia water, a lipid precursor and absolute ethyl alcohol into a reaction kettle at room temperature according to the volume ratio of 1:2:30, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of 1:3:40 of the surfactant, the polystyrene microspheres and the mixed solution, reacting for 24 hours, filtering, washing the filter cake with deionized water according to the mass ratio of 1:2 of the filter cake to the deionized water, drying, and calcining for 1 hour at 400 ℃ at the heating rate of 1 ℃/min to obtain hollow nano microspheres;
b) preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone with the volume ratio of 1:2, the hollow nano microspheres and the cellulose prepared in the step a) are added into the mixed solvent at room temperature according to the mass ratio of 1:10, the mixture is stirred evenly to obtain a mixture, the mixture is poured into a glass mold, acetone is volatilized to obtain a film, the film is placed into absolute ethyl alcohol to be soaked for 2 hours, the film is taken out and dried for 3 hours at the temperature of 60 ℃, the porous radiation refrigeration film material is obtained, and the film thickness of the film material is 0.36 mm.
The refrigeration performance of the obtained material is tested by a temperature tester and a solar irradiance tester. The reflectivity of the material to sunlight is 86%, the emissivity of the material in an atmospheric window of 8-13 mu m is 88%, and the film is in solar irradiance of 700W/m 2 The temperature can be reduced by 4 ℃. Therefore, the structure of the porous radiation refrigeration film material is changed, the directional heat conduction film is lacked, internal heat cannot be directionally transferred to the outside, heat accumulation is formed by inward excessive heat radiation, and the radiation refrigeration effect is greatly reduced.
Example 2
a) Preparing oriented heat conduction materials: at room temperature, putting MAX precursor, LiF and 37 wt% of dilute hydrochloric acid into a reaction kettle according to the mass ratio of 1:2:30, uniformly mixing, reacting for 30h, centrifuging, washing with deionized water until the pH value is more than 6, adding deionized water into the precipitate according to the mass ratio of 1:3, carrying out 1000W ultrasonic treatment for 7h, carrying out vacuum filtration, and drying a filter cake at 60 ℃ for 14h to obtain the MXene oriented heat conduction material;
b) preparing an oriented heat-conducting film: the mixed solution is NaOH, urea and water solution with the mass ratio of 1:3:5, the MXene directional heat conduction material, the cellulose and the mixed solution prepared in the step a) are added into a reaction kettle and uniformly mixed at room temperature according to the mass ratio of 1:6:40, absolute ethyl alcohol is added into the mixture according to the mass ratio of 1:3 of the mixture to absolute ethyl alcohol, the mixture is kept stand for 10 hours to obtain wet gel, deionized water is added into the wet gel according to the mass ratio of 1:2 of the wet gel to the deionized water, the wet gel is kept stand for 2 hours and filtered to obtain hydrogel, the hydrogel is transferred into a mold, the hydrogel is frozen for 1 hour at the temperature of minus 60 ℃, the hydrogel is dried for 24 hours at the temperature of minus 80 ℃ to obtain a directional heat conduction film with the film thickness of 0.3 mm;
c) preparing hollow nano microspheres: adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle at room temperature according to the mass ratio of the polyvinylpyrrolidone to the water to the absolute ethyl alcohol of 1:1:15, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile and styrene into the mixed solution according to the mass ratio of the azobisisobutyronitrile to the styrene to the mixed solution of 1:5:30, reacting for 12 hours at 60 ℃, filtering, washing the filter cake for 3 times by using the absolute ethyl alcohol according to the mass ratio of the filter cake to the absolute ethyl alcohol of 1:2, and drying for 30 hours at 60 ℃ to obtain polystyrene microspheres; adding ammonia water, a lipid precursor and absolute ethyl alcohol into a reaction kettle at room temperature according to the volume ratio of 1:2:35 of the ammonia water, the lipid precursor and the absolute ethyl alcohol, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of 1:3:50 of the surfactant, the polystyrene microspheres and the mixed solution, reacting for 30 hours, filtering, washing the filter cake with deionized water according to the mass ratio of 1:2 of the filter cake to the deionized water, drying, and calcining for 1 hour at 500 ℃ according to the heating rate of 2 ℃/min to obtain hollow nano microspheres;
d) preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone with the volume ratio of 1:8, the mass ratio of the hollow nano microspheres to the cellulose is 1:15 at room temperature, the hollow nano microspheres and the cellulose prepared in the step c) are added into the mixed solvent, the mixture is stirred evenly to obtain a mixture, the mixture is poured into a glass mold, the bottom of the glass mold is covered with the directional heat conduction membrane prepared in the step b), the acetone is volatilized to obtain a laminated membrane, the laminated membrane is placed in absolute ethyl alcohol to be soaked for 3 hours and taken out, the laminated membrane is dried for 4 hours at 60 ℃, and the thickness of the membrane material is 0.5 mm.
The refrigeration performance of the obtained material is tested by a temperature tester and a solar irradiance tester. The reflectivity of the material to sunlight is 96%, the emissivity of the material in an atmospheric window of 8-13 mu m is 95%, and the emissivity is 800W/m in solar irradiance 2 The temperature can be reduced by 14 ℃.
Comparative example 2
a) Preparing oriented heat conduction materials: at room temperature, putting MAX precursor, LiF and 37 wt% of dilute hydrochloric acid into a reaction kettle according to the mass ratio of 1:1:10, uniformly mixing, reacting for 20h, centrifuging, washing with deionized water until the pH value is more than 6, adding deionized water into the precipitate according to the mass ratio of 1:3, carrying out 1000W ultrasonic treatment for 7h, carrying out vacuum filtration, and drying a filter cake at 60 ℃ for 14h to obtain the MXene oriented heat conduction material;
b) preparing a directional heat conduction film: the mixed solution is NaOH, urea and water solution in a mass ratio of 1:1:1, the MXene directional heat conduction material, the cellulose and the mixed solution prepared in the step a) are added into a reaction kettle and uniformly mixed at room temperature according to the mass ratio of 1:3:5, absolute ethyl alcohol is added into the mixture according to the mass ratio of 1:3 of the mixture to absolute ethyl alcohol, the mixture is kept stand for 10 hours to obtain wet gel, deionized water is added into the wet gel according to the mass ratio of 1:2 of the wet gel to the deionized water, the wet gel is kept stand for 2 hours and filtered to obtain hydrogel, the hydrogel is transferred into a mold, the hydrogel is frozen for 1 hour at the temperature of minus 60 ℃, the hydrogel is dried for 24 hours at the temperature of minus 80 ℃ to obtain a directional heat conduction membrane, and the membrane thickness is 0.3 mm;
c) preparing hollow nano microspheres: adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle at room temperature according to the mass ratio of the polyvinylpyrrolidone to the water to the absolute ethyl alcohol of 1:1:5, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile and styrene into the mixed solution according to the mass ratio of the azobisisobutyronitrile to the styrene to the mixed solution of 1:1:10, reacting for 12 hours at 60 ℃, filtering, washing the filter cake for 3 times by using the absolute ethyl alcohol according to the mass ratio of the filter cake to the absolute ethyl alcohol of 1:2, and drying for 30 hours at 60 ℃ to obtain polystyrene microspheres; adding ammonia water, a lipid precursor and absolute ethyl alcohol into a reaction kettle at room temperature according to the volume ratio of 1:1:20, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of 1:3:50 of the surfactant, the polystyrene microspheres and the mixed solution, reacting for 30 hours, filtering, washing the filter cake with deionized water according to the mass ratio of 1:2 of the filter cake to the deionized water, drying, and calcining for 1 hour at 500 ℃ at the heating rate of 2 ℃/min to obtain hollow nano microspheres;
d) preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone with the volume ratio of 1:1, the hollow nano microspheres and the cellulose prepared in the step c) are added into the mixed solvent at room temperature according to the mass ratio of 1:5, the mixture is uniformly stirred to obtain a mixture, the mixture is poured into a glass mold, the bottom of the glass mold is covered with the directional heat conducting membrane prepared in the step b), the acetone is volatilized to obtain a laminated membrane, the laminated membrane is placed into absolute ethyl alcohol to be soaked for 3 hours and taken out, the laminated membrane is dried for 4 hours at 60 ℃, and the porous radiation refrigeration membrane material is prepared, and the membrane thickness of the membrane material is 0.5 mm.
The refrigeration performance of the obtained material is tested by a temperature tester and a solar irradiance tester. The reflectivity of the material to sunlight is 87%, the emissivity of the material in an atmospheric window of 8-13 mu m is 90%, and the emissivity in solar irradiance of 800W/m 2 The temperature can be reduced by 7 ℃. Therefore, under the condition that other conditions are not changed, the preparation proportion of the material is changed, and the refrigeration performance of the porous radiation refrigeration film material prepared according to the proportion outside the protection range of the patent is obviously reduced.
Example 3
a) Preparing oriented heat conduction materials: at room temperature, putting MAX precursor, LiF and 37 wt% of dilute hydrochloric acid into a reaction kettle according to the mass ratio of 1:3:50, uniformly mixing, reacting for 36h, centrifuging, washing with deionized water until the pH value is more than 6, adding deionized water into the precipitate according to the mass ratio of 1:3, performing ultrasonic treatment at 1100W for 10h, performing vacuum filtration, and drying a filter cake at 70 ℃ for 20h to obtain the MXene oriented heat conduction material;
b) preparing an oriented heat-conducting film: the mixed solution is NaOH, urea and aqueous solution in a mass ratio of 1:4:7, the MXene directional heat conduction material, the cellulose and the mixed solution prepared in the step a) are added into a reaction kettle to be uniformly mixed at room temperature according to the mass ratio of 1:8:60, absolute ethyl alcohol is added into the mixture according to the mass ratio of 1:3 of the mixture to absolute ethyl alcohol, the mixture is kept stand for 14 hours to obtain wet gel, deionized water is added into the wet gel according to the mass ratio of 1:2 of the wet gel to the deionized water, the wet gel is kept stand for 3 hours and filtered to obtain hydrogel, the hydrogel is transferred into a mold, the hydrogel is frozen for 2 hours at the temperature of minus 60 ℃, and the hydrogel is dried for 36 hours at the temperature of minus 40 ℃ to obtain a directional heat conduction film with the film thickness of 0.4 mm;
c) preparing hollow nano microspheres: adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle at room temperature according to the mass ratio of the polyvinylpyrrolidone to the water to the absolute ethyl alcohol of 1:2:20, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile and styrene into the mixed solution according to the mass ratio of the azobisisobutyronitrile to the styrene to the mixed solution of 1:6:35, reacting for 12 hours at 70 ℃, filtering, washing the filter cake for 4 times by using the absolute ethyl alcohol according to the mass ratio of the filter cake to the absolute ethyl alcohol of 1:2, and drying for 36 hours at 70 ℃ to obtain polystyrene microspheres; adding ammonia water, a lipid precursor and absolute ethyl alcohol into a reaction kettle at room temperature according to the volume ratio of 1:3:30, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of 1:4:60 of the surfactant, the polystyrene microspheres and the mixed solution, reacting for 36 hours, filtering, washing the filter cake with deionized water according to the mass ratio of 1:2 of the filter cake to the deionized water, drying, and calcining for 2 hours at 600 ℃ according to the heating rate of 3 ℃/min to obtain hollow nano microspheres;
d) preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone with the volume ratio of 1:6, the hollow nano microspheres and the cellulose prepared in the step c) are added into the mixed solvent at room temperature according to the mass ratio of 1:20, the mixture is uniformly stirred to obtain a mixture, the mixture is poured into a glass mold, the bottom of the glass mold is covered with the directional heat conducting membrane prepared in the step b), the acetone is volatilized to obtain a laminated membrane, the laminated membrane is placed into absolute ethyl alcohol to be soaked for 4 hours and taken out, the laminated membrane is dried for 5 hours at 70 ℃, and the porous radiation refrigeration membrane material is prepared, and the membrane thickness of the membrane material is 0.8 mm.
The refrigeration performance of the obtained material is tested by a temperature tester and a solar radiation rate tester. The reflectivity of the material to sunlight is 97%, the emissivity of the material in an atmospheric window of 8-13 mu m is 96%, and the emissivity in solar irradiance of 950W/m 2 The temperature can be reduced by 19 ℃.
Example 4
a) Preparing oriented heat conduction materials: at room temperature, putting MAX precursor, LiF and 37 wt% of dilute hydrochloric acid into a reaction kettle according to the mass ratio of 1:3:60, uniformly mixing, reacting for 48h, centrifuging, washing with deionized water until the pH value is greater than 6, adding deionized water into the precipitate according to the mass ratio of 1:3, carrying out ultrasonic treatment for 12h at 1320W, carrying out vacuum filtration, and drying a filter cake for 24h at 80 ℃ to obtain the MXene oriented heat conduction material;
b) preparing an oriented heat-conducting film: adding the MXene oriented heat conduction material, the cellulose and the mixed solution prepared in the step a) into a reaction kettle at room temperature according to the mass ratio of 1:4:10 to 10 of the aqueous solution to be uniformly mixed, adding absolute ethyl alcohol into the mixture according to the mass ratio of 1:4 to absolute ethyl alcohol, standing for 12 hours to obtain wet gel, adding deionized water into the wet gel according to the mass ratio of 1:3 of the wet gel to the deionized water, standing for 4 hours, filtering to obtain hydrogel, transferring the hydrogel into a mold, freezing for 3 hours at-20 ℃, drying for 48 hours at-40 ℃ to obtain an oriented heat conduction membrane with the membrane thickness of 0.5 mm;
c) preparing hollow nano microspheres: adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle at room temperature according to the mass ratio of the polyvinylpyrrolidone to the water to the absolute ethyl alcohol of 1:2:30, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile and styrene into the mixed solution according to the mass ratio of the azobisisobutyronitrile to the styrene to the mixed solution of 1:7:50, reacting for 14 hours at 80 ℃, filtering, washing the filter cake for 4 times by using the absolute ethyl alcohol according to the mass ratio of the filter cake to the absolute ethyl alcohol of 1:3, and drying for 48 hours at 80 ℃ to obtain polystyrene microspheres; adding ammonia water, a lipid precursor and absolute ethyl alcohol into a reaction kettle at room temperature according to the volume ratio of 1:3:50, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of 1:5:80 of the surfactant, the polystyrene microspheres and the mixed solution, reacting for 48 hours, filtering, washing the filter cake with deionized water according to the mass ratio of 1:2 of the filter cake to the deionized water, drying, and calcining for 3 hours at 700 ℃ at the temperature rise rate of 5 ℃/min to obtain hollow nano microspheres;
d) preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone with the volume ratio of 1:9, the hollow nano microspheres and the cellulose prepared in the step c) are added into the mixed solvent at room temperature according to the mass ratio of 1:30, the mixture is uniformly stirred to obtain a mixture, the mixture is poured into a glass mold, the bottom of the glass mold is covered with the directional heat conducting membrane prepared in the step b), the acetone is volatilized to obtain a laminated membrane, the laminated membrane is placed into absolute ethyl alcohol to be soaked for 6 hours, the laminated membrane is taken out and dried for 6 hours at 80 ℃, and the porous radiation refrigeration membrane material is prepared, wherein the membrane thickness of the membrane material is 1.1 mm.
The refrigeration performance of the obtained material is tested by a temperature tester and a solar irradiance tester. The reflectivity of the material to sunlight is 99%, the emissivity of the material in an atmospheric window of 8-13 mu m is 98%, and the emissivity in solar irradiance of 1200W/m 2 The temperature can be reduced by 25 ℃.
Claims (8)
1. A directional heat conduction porous radiation refrigeration film material is characterized in that the material is formed by overlapping an outer side high-reflectivity film and an inner side directional heat conduction film; the high-reflectivity film is prepared by dispersing hollow nano microspheres into cellulose and performing phase conversion; the oriented heat conducting film is prepared by dispersing MXene oriented heat conducting materials into cellulose and performing oriented freeze drying.
2. The oriented heat conduction porous radiation refrigeration film material as claimed in claim 1, wherein the hollow nano-microspheres are polystyrene templates.
3. The material of claim 1, wherein the MXene oriented thermal conductive material is prepared by selectively etching MAX precursor by in-situ growth hydrofluoric acid method, ultrasonic stripping, and vacuum filtration.
4. A method for preparing a directional heat conduction porous radiation refrigeration film material according to claim 1, which is characterized by comprising the following steps:
step 1, preparing a directional heat conduction material: adding MAX precursor, LiF and 37 wt% of dilute hydrochloric acid into a reaction kettle at room temperature according to the mass ratio of 1:2: 20-1: 3:60, uniformly mixing, reacting for 24-48 h, centrifuging, washing the precipitate with deionized water until the pH value of the washing solution is greater than 6, adding deionized water into the precipitate according to the mass ratio of 1: 2-1: 3, carrying out ultrasonic treatment at 900-1320W for 6-12 h, carrying out vacuum filtration, and drying the filter cake at 60-80 ℃ for 12-24 h to obtain the MXene oriented heat conduction material;
step 2, preparing a directional heat conduction film: the mixed solution is NaOH, urea and water solution in a mass ratio of 1:2: 4-1: 4:10, MXene directional heat conduction materials, cellulose and the mixed solution prepared in the step 1 are added into a reaction kettle at room temperature according to a mass ratio of 1:5: 30-1: 10:80, the cellulose and the mixed solution are uniformly mixed, absolute ethyl alcohol is added into the mixture according to a mass ratio of the mixture to the absolute ethyl alcohol of 1: 2-1: 4, standing for 8-16 h to obtain wet gel, adding deionized water into the wet gel according to the mass ratio of the wet gel to the deionized water of 1: 2-1: 3, standing for 2-4 h, filtering to obtain hydrogel, transferring the hydrogel into a mold, freezing at-80 to-20 ℃ for 1 to 3 hours, and drying at-80 to-40 ℃ for 24 to 48 hours to obtain an oriented heat-conducting film with the film thickness of 0.2 to 0.5 mm;
step 3, preparing hollow nano microspheres: adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle at room temperature according to the mass ratio of 1:1: 10-1: 2:30, uniformly mixing to obtain a mixture, adding azobisisobutyronitrile and styrene into the mixture according to the mass ratio of 1:5: 25-1: 7:50, reacting for 10-14 h at 60-80 ℃, filtering, washing the filter cake with absolute ethyl alcohol for 3-4 times according to the mass ratio of 1: 2-1: 3 of the filter cake to the absolute ethyl alcohol, and drying for 24-48 h at 60-80 ℃ to obtain polystyrene microspheres; adding ammonia water, an ester precursor and absolute ethyl alcohol into a reaction kettle at room temperature according to the volume ratio of 1:2: 30-1: 3:50 of the ammonia water, the ester precursor and the absolute ethyl alcohol, uniformly mixing to obtain a mixed solution, adding a surfactant and the prepared polystyrene microspheres into the mixed solution according to the mass ratio of the surfactant, the polystyrene microspheres and the mixed solution of 1:3: 40-1: 5:80, reacting for 24-48 h, filtering, washing the filter cake with deionized water according to the mass ratio of the filter cake to the deionized water of 1:2, drying, heating to 400-700 ℃ at the heating rate of 1-5 ℃/min, calcining for 1-3 h, and cooling to room temperature to obtain hollow nano microspheres;
step 4, preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent in a volume ratio of 1: 2-1: 9, the hollow nano microspheres and cellulose prepared in the step 3 are added into the mixed solvent according to a mass ratio of 1: 10-1: 30 at room temperature, the mixture is stirred uniformly to obtain a mixture, the mixture is poured into a glass mold, the bottom of the glass mold is covered with the directional heat conduction membrane prepared in the step 2, acetone is volatilized to obtain a laminated membrane, the laminated membrane is placed in absolute ethyl alcohol to be soaked for 2-6 hours, the laminated membrane is taken out and dried for 3-6 hours at a temperature of 60-80 ℃, and the membrane material has a membrane thickness of 0.3-1.1 mm.
5. The method for preparing a directional heat conduction porous radiation refrigeration thin film material according to claim 4, wherein in the step 1, the MAX precursor is Ti 3 AlC 2 Or Ti 2 AlC。
6. The method for preparing a directional heat-conducting porous radiation refrigeration film material according to claim 4, wherein in the step 3, the ester precursor is tetraethoxysilane or tetrabutyl titanate.
7. The method for preparing a directional heat-conducting porous radiation refrigeration film material as claimed in claim 4, wherein in the step 3, the surfactant is cetyl trimethyl ammonium bromide or sodium dodecyl sulfate.
8. The method for preparing a directional heat conduction porous radiation refrigeration film material as claimed in claim 4, wherein in the step 3, the cellulose is bacterial cellulose or lignocellulose.
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