CN114805941B - Directional heat conduction porous radiation refrigeration film material and preparation method thereof - Google Patents
Directional heat conduction porous radiation refrigeration film material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a directional heat conduction porous radiation refrigeration film material and a preparation method thereof. The material has a reflectivity of 95-99% to sunlight, an emissivity of 94-98% in an atmospheric window of 8-13 μm and a solar irradiance of 700-1200W/m 2 The temperature can be reduced by 10-25 ℃, so that the internal heat is quickly and directionally transferred to the outside, and the directional regulation and control of the internal heat of the building are realized. The invention solves the problems that heat transfer is only reduced from outside, and internal heat regulation is not emphasized in the past, 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-conducting porous radiation refrigeration film material and a preparation method thereof.
Background
The traditional refrigeration equipment such as an air conditioner, an electric fan 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 the negative effects of greenhouse effect, air pollution, acid rain and the like are caused. Therefore, it is important 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 to be an ideal choice of the alternative energy intensive refrigeration mode at the present stage. The development of various materials and new preparation methods plays a great role in promoting the development of refrigeration materials, so that the passive radiation refrigeration technology is expected to be widely applied in 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 void network structure, a multi-scale optical fiber and a multi-scale channel exist in the cellulose as disordered scattering units to scatter sunlight, and absorption vibration of chemical bonds in the cellulose generates higher infrared emissivity, but the cellulose cannot perfectly cover the whole atmosphere transparent window (8-13 mu m), so that the cellulose has high infrared emissivity at the 8-13 mu m position only by reasonable molecular structure design and synthesis to realize aggregation of various characteristic functional groups. Nanoparticles (SiO) with special hollow structure 2 、HfO 2 、TiO 2 、ZrO 2 And the like) can further improve the infrared emissivity of the material, the semiconductor nano particles have a special surface plasmon effect, after infrared radiation is absorbed by the material, the surface electrons of the particles are caused to oscillate collectively, very high emissivity can be obtained in the middle and far infrared wave bands, and the hollow microsphere with good sealing degree can also improve the scattering of solid-phase phonons of the shell, so that the solid-phase phonon heat transfer is reduced, and after the heat is transferred to the spherical shell, the heat is required to pass through the inside of the hollow microsphere and undergo primary gas-phase heat transfer, so that the heat conductivity coefficient is greatly reduced. 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 comprising a radiation refrigeration functional layer having a special structure particle filler 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 comprising a rod-like structure particle filler and a radiation refrigeration functional layer resin, the particle filler being distributed in the radiation refrigeration functional layer resin, eventually achieving a reflectivity of >80% and an infrared emissivity of > 80%. Patent CN113372612a discloses a preparation method of a cellulose-based radiation temperature regulating material, which prepares cellulose aerogel with a three-dimensional porous structure by performing functional modification on cellulose, and shows solar reflectance of approximately 94% and infrared emissivity of 95%. However, the radiation refrigerating materials developed at present only focus on reducing the heat input from the outside, and lack effective regulation means for the heat radiation generated by the internal space (solar radiation back surface). The key to solving this problem is to develop a material that can achieve a rapid directional conduction of heat from the interior to the exterior, thereby achieving an ideal interior space cooling effect.
Patent CN106631082A discloses a directional high-heat-conductivity carbon nano tube composite material and a preparation method thereof, wherein the thermal conductivity of the composite material in the axial direction is more than 100W/m.k, and the thermal conductivity difference in the non-axial direction is more than 50W/m.k through magnetic regulation and control of the directional arrangement of the carbon nano tubes. However, the method for preparing the oriented carbon nanotube array is complicated to operate and has severe 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 the ratio of the thermal conductivity coefficient to the electrical conductivity is proportional to the temperature according to Wei Deman-Franz law, so that the MXene also has high thermal conductivity. The single-layer MXene material has the characteristics of large sheets, single layers, low defects and the like, and the heat conductivity parallel to the direction of the heat conducting material is improved due to the reduction of structural defects, the interlayer spacing of the material sheets is increased, and the heat conductivity perpendicular to the direction of the heat conducting material is reduced, so that the heat conductivity anisotropy is caused.
Disclosure of Invention
The invention aims to: 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, but lacks effective regulation means for heat radiation generated by an inner space (solar radiation back surface) and the like. The inner side surface with high directional heat conduction capability is constructed, so that the heat can be quickly transferred from inside to outside, and the outer side surface with high solar reflectivity and high infrared emissivity is constructed, so that the external heat can enter the interior as little as possible and can be selectively emitted to the outer space in a heat radiation mode, the inner film and the outer film are effectively combined and cooperatively acted, the radiation refrigerating material shows good cooling effect, and the radiation refrigerating material is an ideal choice of novel high-efficiency radiation refrigerating materials.
The technical scheme is as follows: the invention relates to a directional heat-conducting porous radiation refrigeration film material, which is formed by superposing an outside high-reflectivity film and an inside directional heat-conducting film; the high-reflectivity film is prepared by dispersing hollow nano-microspheres into cellulose through phase conversion; the directional heat conduction film is prepared by dispersing an MXene directional heat conduction material into cellulose and performing directional freeze drying.
Further, the hollow nano-microsphere takes polystyrene as a template.
Further, the MXene directional heat conduction material is prepared by selectively etching MAX precursor by using an in-situ growth hydrofluoric acid method, ultrasonic stripping and vacuum suction 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 37wt% of diluted hydrochloric acid into a reaction kettle according to the mass ratio of 1:2:20-1:3:60 at room temperature, uniformly mixing, reacting for 24-48 h, centrifuging, washing the precipitate with deionized water until the pH of the washing solution is more than 6, adding deionized water into the precipitate according to the mass ratio of the precipitate to the deionized water of 1:2-1:3, carrying out ultrasonic treatment for 6-12 h at 900W-1320W, carrying out suction filtration under vacuum, and drying a filter cake for 12-24 h at 60-80 ℃ to obtain the MXene directional heat conducting material;
step 2, preparing an oriented heat conduction film: the mixed solution is NaOH, urea and aqueous solution with the mass ratio of 1:2:4-1:4:10, the mass ratio of MXene directional heat conduction material to cellulose to the mixed solution is 1:5:30-1:10:80 at room temperature, the MXene directional heat conduction material, cellulose and the mixed solution prepared in the step 1 are added into a reaction kettle to be uniformly mixed, the mass ratio of the mixture to absolute ethyl alcohol is 1:2-1:4, the absolute ethyl alcohol is added into the mixture, standing is carried out for 8-16 h to obtain wet gel, deionized water is added into the wet gel with the mass ratio of the wet gel to deionized water being 1:2-1:3, standing is carried out for 2-4 h, hydrogel is obtained after the hydrogel is transferred into a mold, freezing is carried out for 1-3 h at-80 to-20 ℃, the temperature is dried for 24-48 h at-80 to-40 ℃, and the film thickness of the directional heat conduction film is 0.2-0.5 mm;
step 3, hollow nanometer microsphere preparation: at room temperature, adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle according to the mass ratio of polyvinylpyrrolidone to water to absolute ethyl alcohol 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 azobisisobutyronitrile to styrene of 1:5:25-1:7:50, reacting for 10-14 h at 60-80 ℃, filtering, washing a filter cake 3-4 times by absolute ethyl alcohol according to the mass ratio of the filter cake to absolute ethyl alcohol of 1:2-1:3, 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 according to the volume ratio of the ammonia water to the precursor to the absolute ethyl alcohol of 1:2:30-1:3:50 at room temperature, uniformly mixing to obtain a mixed solution, adding a surfactant and the prepared polystyrene microsphere into the mixed solution according to the mass ratio of the surfactant to the polystyrene microsphere to 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 the heating rate of 1-5 ℃/min, calcining for 1-3 h at the temperature of 400-700 ℃, and cooling to room temperature to obtain the hollow nano microsphere;
step 4, preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent with the volume ratio of 1:2-1:9, the mass ratio of the hollow nano-microspheres to the cellulose is 1:10-1:30 at room temperature, the hollow nano-microspheres and the cellulose prepared in the step 3 are added into the mixed solvent, 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 conducting film prepared in the step 2, the acetone is volatilized to obtain a laminated film, the laminated film is placed into absolute ethyl alcohol and soaked for 2-6 h, the laminated film is taken out, the porous radiation refrigeration film material is dried for 3-6 h at the temperature of 60-80 ℃, and the film thickness of the film material is 0.3-1.1 mm.
Further, in step 1, the MAX precursor is Ti 3 AlC 2 Or Ti (Ti) 2 AlC。
Further, in step 3, the ester precursor is tetraethyl orthosilicate or tetrabutyl titanate.
Further, in step 3, the surfactant is cetyltrimethylammonium bromide or sodium dodecyl sulfonate.
Further, in step 3, the cellulose is bacterial cellulose or lignocellulose.
The principle of the invention: the invention is formed by overlapping a high-reflectivity film and a directional heat-conducting film, wherein the high-reflectivity film is prepared by uniformly dispersing hollow nano microspheres into cellulose, and is used for reflecting or scattering sunlight as much as possible, reducing heat input, and simultaneously has high emissivity in an atmospheric transparent window, and can selectively emit self heat to outer space. The directional heat conducting film is prepared by dispersing a directional heat conducting material into cellulose and performing directional freeze drying, and is used for absorbing infrared heat radiation in an inner space and directionally transmitting energy to an outer film so as to reduce inward emission of infrared radiation. The synergistic effect of the two layers of films improves the reflectivity of the composite material to sunlight, reduces the inward emission energy of the composite material, and improves the orientation of the composite material for outward transmission of heat radiation, so that the heat is quickly and directionally transferred from the inner side to the outer side of the material, and the composite material shows excellent daytime cooling performance and is an ideal choice of novel efficient radiation refrigeration materials.
According to the invention, the directional heat conduction material is induced to be arranged in the cellulose in a high orientation mode by controlling the freezing and solidification direction, so that the outward heat transfer efficiency is enhanced, the inward heat radiation effect is weakened, and the directional heat conduction film is obtained through freeze drying. Then, on the basis, the characteristic structure design is carried out on cellulose, hollow nano microspheres with matched performances are selected as filling media, the outer side surface 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 for emitting heat radiation to 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.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
1. the invention etches Ti by adopting an in-situ hydrofluoric acid generation method 3 AlC 2 The prepared two-dimensional transition metal carbide (MXene) has the characteristics of large sheets, single layers, low defects and the like, improves the heat conductivity parallel to the MXene direction, reduces the heat conductivity perpendicular to the MXene direction by controlling the interlayer spacing of the material sheets, and causes the heat conductivity anisotropy. The MXene is used as the directional heat conduction material, so that the problems of complex preparation process, severe preparation conditions and the like of the traditional graphene and other carbon materials are avoided. The surface of the single-layer MXene sheet can introduce more hydroxyl and other active groups, so that the surface presents negative charges, and electrostatic repulsion exists between sheets, so that a long-time stable state can be maintained, and the surface of the single-layer MXene sheet is added into cellulose, so that the heat conductivity and the mechanical strength of the directional heat conducting film are improved.
2. The directional heat conduction film is obtained by dispersing the MXene directional heat conduction material in cellulose and utilizing a directional freeze drying technology to serve as an inner side surface, the directional heat conduction material grows directionally in the vertical direction by controlling the temperature gradient in the freezing process, the heat is transferred directionally from the inner side to the outer side due to the anisotropy of the heat conductivity, the ideal cooling effect is achieved inside the material, the problem that the heat accumulation is formed by excessive heat radiation in the inner side due to the lack of directional heat conduction of the conventional radiation refrigeration material is solved, and the heat radiation in the inner side is reduced.
3. Cellulose is selected as a high polymer substrate, a porous structure is obtained by utilizing a phase conversion technology, the porous structure is concentrated and distributed at about 5 mu m by regulating and controlling the pore size, the perfect matching of the pore size can effectively scatter sunlight with all wavelengths, the solar radiation heat is reduced to a greater extent, the defect that a traditional radiation refrigeration material needs to sputter a metal layer to improve the solar reflectance is overcome, and the existence of the porous structure improves the reflectance of the material to sunlight.
4. The nanometer microsphere with the hollow structure is obtained by a polystyrene template method, the microsphere has a special surface plasmon effect, after infrared radiation is absorbed by a material, surface electrons are caused to oscillate collectively, very high emissivity can be obtained in a middle-infrared band and a far-infrared band, and meanwhile, the hollow structure carries out multiple reflection and scattering on incident sunlight, so that the absorption of solar radiation is weakened, the refrigerating effect is improved, and the problems of low reflectivity, poor refrigerating effect and the like caused by the absorption of sunlight with a certain specific wavelength existing in the original nanometer microsphere are solved. The hollow nano microsphere is used as a filling medium to be dispersed in a cellulose substrate, so that the infrared emissivity and solar reflectance of the material are further improved.
5. The cellulose is activated by adopting sodium hydroxide solution, the hydrogen bond in a cellulose crystallization area is destroyed, the accessibility to cellulose hydroxyl is increased, and an electrostatic effect exists between the cellulose hydroxyl and a dispersion medium, so that the dispersion medium can be uniformly loaded in cellulose molecules, the defect of less free hydroxyl in the cellulose molecular crystallization area is overcome, the active side chain hydroxyl is increased, the mechanical property of the cellulose is enhanced by designing and modifying the side chain hydroxyl by utilizing a material with special properties, and meanwhile, a new function is endowed to the cellulose derivative polymer substrate with high infrared emissivity and high directional thermal conductivity.
6. The surface of the directional heat-conducting film is provided with a high-reflectivity film which uses cellulose as a high-molecular base material, uses hollow nano-microspheres as a filling medium with high refractive index and high infrared emissivity and uses a cavity with specific size as a scattering filling medium by a phase conversion method, so that the superposition with the inner directional heat-conducting film is realized. The same cellulose is used as a substrate, the cellulose molecular chains at the interface are in hydrogen bond combination, the mechanical interweaving acting force enables the two layers of films to be tightly combined, and meanwhile, the ideal micro/nano rough structure surface is constructed by regulating and controlling the dispersion state and the content of the hollow nano microsphere in the cellulose, and the interface bonding strength is further enhanced by means of the surface roughness between the interfaces. The process that heat is directionally transferred from the inner side surface to the outer side surface and then is emitted to the outer space in a heat radiation mode by the outer side surface is realized, the problem that high-efficiency radiation refrigeration cannot be realized due to the fact that the heat radiation generated in the inner space is ignored due to the fact that the existing radiation refrigeration material only focuses on the reflection of sunlight is solved, and the cooling power and efficiency of the radiation refrigeration material are improved.
Drawings
FIG. 1 is a microscopic morphology (SEM) of a directionally conductive porous radiant refrigerant film material;
fig. 2 is an actual temperature reduction diagram of the directional heat conduction porous radiation refrigeration film material.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
a) Preparing a directional heat conduction material: placing MAX precursor, liF and 37wt% of diluted hydrochloric acid into a reaction kettle according to the mass ratio of MAX precursor to LiF to 37wt% of diluted hydrochloric acid of 1:2:20 at room temperature, uniformly mixing, reacting for 24 hours, centrifuging, washing with deionized water until the pH is more than 6, adding deionized water into the precipitate according to the mass ratio of the precipitate to the deionized water of 1:2, performing ultrasonic treatment for 6 hours at 900W, performing suction filtration under vacuum, and drying a filter cake at 60 ℃ for 12 hours to obtain the MXene directional heat conducting material;
b) Preparing an oriented heat conduction film: the mixed solution is NaOH, urea and aqueous solution with the mass ratio of 1:2:4, at room temperature, the mass ratio of the MXene directional heat conduction material to the cellulose to the mixed solution is 1:5:30, 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, the mass ratio of the mixture to the absolute ethyl alcohol is 1:2, the absolute ethyl alcohol is added into the mixture, standing is carried out for 12h, wet gel is obtained, deionized water is added into the wet gel with the mass ratio of the wet gel to the deionized water being 1:2, standing is carried out for 2h, the hydrogel is obtained, the hydrogel is transferred into a mold, after being frozen for 1h at the temperature of 80 ℃ below zero, the directional heat conduction film is obtained by drying for 24h at the temperature of 80 ℃ below zero, and the film thickness is 0.24mm;
c) Preparing hollow nano microspheres: at room temperature, adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle according to the mass ratio of polyvinylpyrrolidone to water to absolute ethyl alcohol of 1:1:10, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile, styrene and styrene into the mixed solution according to the mass ratio of azobisisobutyronitrile to styrene of 1:5:25, reacting for 10 hours at 60 ℃, filtering, washing a filter cake 3 times with absolute ethyl alcohol according to the mass ratio of the filter cake to absolute ethyl alcohol of 1:2, and drying for 24 hours at 60 ℃ to obtain polystyrene microspheres; adding ammonia water, lipid precursors and absolute ethyl alcohol into a reaction kettle according to the volume ratio of the ammonia water to the lipid precursors to the absolute ethyl alcohol of 1:2:30 at room temperature, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of the surfactant to the polystyrene microspheres of 1:3:40, reacting for 24 hours, filtering, washing a filter cake with deionized water according to the mass ratio of the filter cake to the deionized water of 1:2, drying, calcining for 1 hour at the temperature rising rate of 1 ℃/min and the temperature of 400 ℃, and obtaining the hollow nano microspheres;
d) Preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent with the volume ratio of 1:2, the mass ratio of the hollow nano-microspheres to the cellulose is 1:10 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 uniformly, 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 to be soaked for 2h, the laminated film is taken out, and the porous radiation refrigeration film material is dried for 3h at 60 ℃, wherein the film thickness of the film material is 0.6mm as shown in the figure 1.
And testing the refrigerating performance of the obtained material by a temperature tester and a solar irradiance meter. The material has a reflectivity of 95% to sunlight and an emissivity of 94% in an atmospheric window of 8-13 μm, and the film has a solar irradiance of 700W/m as shown in FIG. 2 2 The temperature can be reduced by 13 ℃.
Comparative example 1
a) Preparing hollow nano microspheres: at room temperature, adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle according to the mass ratio of polyvinylpyrrolidone to water to absolute ethyl alcohol of 1:1:10, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile, styrene and styrene into the mixed solution according to the mass ratio of azobisisobutyronitrile to styrene of 1:5:25, reacting for 10 hours at 60 ℃, filtering, washing a filter cake 3 times with absolute ethyl alcohol according to the mass ratio of the filter cake to absolute ethyl alcohol of 1:2, and drying for 24 hours at 60 ℃ to obtain polystyrene microspheres; adding ammonia water, lipid precursors and absolute ethyl alcohol into a reaction kettle according to the volume ratio of the ammonia water to the lipid precursors to the absolute ethyl alcohol of 1:2:30 at room temperature, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of the surfactant to the polystyrene microspheres of 1:3:40, reacting for 24 hours, filtering, washing a filter cake with deionized water according to the mass ratio of the filter cake to the deionized water of 1:2, drying, calcining for 1 hour at the temperature rising rate of 1 ℃/min and the temperature of 400 ℃, and obtaining the hollow nano microspheres;
b) Preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent with the volume ratio of 1:2, the mass ratio of the hollow nano microsphere to the cellulose is 1:10 at room temperature, the hollow nano microsphere and the cellulose prepared in the step a) are added into the mixed solvent, the mixture is stirred uniformly, the mixture is poured into a glass die, the acetone volatilizes to obtain a film, the film is placed into absolute ethyl alcohol to be soaked for 2 hours, the film is taken out, the film is dried at 60 ℃ for 3 hours, and the film thickness of the film material is 0.36mm.
And testing the refrigerating performance of the obtained material by a temperature tester and a solar irradiance meter. The reflectivity of the material to sunlight is 86%, the emissivity of the material to the atmospheric window is 88% at 8-13 mu m, and the film has the irradiance of 700W/m 2 The temperature can be reduced by 4 ℃. Therefore, the structure of the porous radiation refrigeration film material is changed, and the directional heat conduction film is lacked, so that internal heat cannot be directionally transferred to the outside, and excessive heat radiation is inwards formed to accumulate heat, so that the radiation refrigeration effect is greatly reduced.
Example 2
a) Preparing a directional heat conduction material: placing MAX precursor, liF and 37wt% of diluted hydrochloric acid into a reaction kettle according to the mass ratio of MAX precursor to LiF to 37wt% of diluted hydrochloric acid of 1:2:30 at room temperature, uniformly mixing, reacting for 30 hours, centrifuging, washing with deionized water until the pH is more than 6, adding deionized water into the precipitate according to the mass ratio of the precipitate to the deionized water of 1:3, performing 1000W ultrasonic treatment for 7 hours, performing vacuum suction filtration, and drying a filter cake at 60 ℃ for 14 hours to obtain the MXene directional heat conducting material;
b) Preparing an oriented heat conduction film: the mixed solution is NaOH, urea and aqueous solution with the mass ratio of 1:3:5, the mass ratio of MXene directional heat conduction material to cellulose to the mixed solution is 1:6:40 at room temperature, 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, the mass ratio of the mixture to absolute ethyl alcohol is 1:3, the absolute ethyl alcohol is added into the mixture, standing is carried out for 10h, wet gel is obtained, deionized water is added into the wet gel with the mass ratio of the wet gel to deionized water being 1:2, standing is carried out for 2h, the hydrogel is obtained, the hydrogel is transferred into a mold, frozen for 1h at the temperature of minus 60 ℃, and then dried for 24h 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: at room temperature, adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle according to the mass ratio of polyvinylpyrrolidone to water to absolute ethyl alcohol of 1:1:15, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile, styrene and styrene into the mixed solution according to the mass ratio of azobisisobutyronitrile to styrene of 1:5:30, reacting for 12h at 60 ℃, filtering, washing a filter cake 3 times with absolute ethyl alcohol according to the mass ratio of the filter cake to absolute ethyl alcohol of 1:2, and drying for 30h at 60 ℃ to obtain polystyrene microspheres; adding ammonia water, lipid precursors and absolute ethyl alcohol into a reaction kettle according to the volume ratio of the ammonia water to the lipid precursors to the absolute ethyl alcohol of 1:2:35 at room temperature, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of the surfactant to the polystyrene microspheres of 1:3:50, reacting for 30 hours, filtering, washing a filter cake with deionized water according to the mass ratio of the filter cake to the deionized water of 1:2, drying, calcining for 1 hour at the temperature rising rate of 2 ℃/min and the temperature of 500 ℃, and obtaining the hollow nano microspheres;
d) Preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent 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 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 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 to be soaked for 3h, the laminated film is taken out, the porous radiation refrigeration film material is dried for 4h at 60 ℃, and the film thickness of the film material is 0.5mm.
And testing the refrigerating performance of the obtained material by a temperature tester and a solar irradiance meter. The material has a solar reflectance of 96%, an atmospheric window emissivity of 95% at 8-13 μm, and a solar irradiance of 800W/m 2 The temperature can be reduced by 14 ℃.
Comparative example 2
a) Preparing a directional heat conduction material: placing MAX precursor, liF and 37wt% of diluted hydrochloric acid into a reaction kettle according to the mass ratio of MAX precursor to LiF to 37wt% of diluted hydrochloric acid of 1:1:10 at room temperature, uniformly mixing, reacting for 20h, centrifuging, washing with deionized water until the pH is more than 6, adding deionized water into the precipitate according to the mass ratio of the precipitate to the deionized water of 1:3, performing 1000W ultrasonic treatment for 7h, performing vacuum suction filtration, and drying a filter cake at 60 ℃ for 14h to obtain the MXene directional heat conducting material;
b) Preparing an oriented heat conduction film: the mixed solution is NaOH, urea and aqueous solution with the mass ratio of 1:1:1, at room temperature, the mass ratio of MXene directional heat conduction material to cellulose to the mixed solution is 1:3:5, the MXene directional heat conduction material, cellulose and the mixed solution prepared in the step a) are added into a reaction kettle to be uniformly mixed, the mass ratio of the mixture to absolute ethyl alcohol is 1:3, the absolute ethyl alcohol is added into the mixture, standing is carried out for 10h, wet gel is obtained, deionized water is added into the wet gel with the mass ratio of the wet gel to deionized water being 1:2, standing is carried out for 2h, the hydrogel is obtained, the hydrogel is transferred into a mold, frozen for 1h at the temperature of minus 60 ℃, and then dried for 24h 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: at room temperature, adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle according to the mass ratio of polyvinylpyrrolidone to water to absolute ethyl alcohol of 1:1:5, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile, styrene and styrene into the mixed solution according to the mass ratio of azobisisobutyronitrile to styrene of 1:1:10, reacting for 12h at 60 ℃, filtering, washing a filter cake 3 times with absolute ethyl alcohol according to the mass ratio of the filter cake to absolute ethyl alcohol of 1:2, and drying for 30h at 60 ℃ to obtain polystyrene microspheres; adding ammonia water, lipid precursors and absolute ethyl alcohol into a reaction kettle according to the volume ratio of the ammonia water to the lipid precursors to the absolute ethyl alcohol of 1:1:20 at room temperature, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of the surfactant to the polystyrene microspheres of 1:3:50, reacting for 30 hours, filtering, washing a filter cake with deionized water according to the mass ratio of the filter cake to the deionized water of 1:2, drying, calcining for 1 hour at the temperature rising rate of 2 ℃/min and the temperature of 500 ℃, and obtaining the hollow nano microspheres;
d) Preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent with the volume ratio of 1:1, the mass ratio of the hollow nano microsphere to the cellulose is 1:5 at room temperature, the hollow nano microsphere and the cellulose prepared in the step c) are added into the mixed solvent, 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 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 to be soaked for 3h, the laminated film is taken out, the porous radiation refrigeration film material is dried for 4h at 60 ℃, and the film thickness of the film material is 0.5mm.
And testing the refrigerating performance of the obtained material by a temperature tester and a solar irradiance meter. The material has a reflectivity of 87% to sunlight, an emissivity of 90% in an atmospheric window of 8-13 μm, and a solar irradiance of 800W/m 2 The temperature can be reduced by 7 ℃. Therefore, under the condition that other conditions are unchanged, the preparation proportion of the material is changed, and the refrigeration performance of the porous radiation refrigeration film material prepared in proportion outside the protection scope of the patent is obviously reduced.
Example 3
a) Preparing a directional heat conduction material: placing MAX precursor, liF and 37wt% of diluted hydrochloric acid into a reaction kettle according to the mass ratio of MAX precursor to LiF to 37wt% of diluted hydrochloric acid of 1:3:50 at room temperature, uniformly mixing, reacting for 36h, centrifuging, washing with deionized water until the pH is more than 6, adding deionized water into the precipitate according to the mass ratio of the precipitate to the deionized water of 1:3, performing ultrasonic treatment for 10h at 1100W, performing suction filtration under vacuum, and drying a filter cake at 70 ℃ for 20h to obtain the MXene directional heat conducting material;
b) Preparing an oriented heat conduction film: the mixed solution is NaOH, urea and aqueous solution with the mass ratio of 1:4:7, the mass ratio of MXene directional heat conduction material to cellulose to the mixed solution is 1:8:60 at room temperature, 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, the mass ratio of the mixture to absolute ethyl alcohol is 1:3, the absolute ethyl alcohol is added into the mixture, standing is carried out for 14h, wet gel is obtained, deionized water is added into the wet gel with the mass ratio of the wet gel to deionized water being 1:2, standing is carried out for 3h, the hydrogel is obtained, the hydrogel is transferred into a mold, frozen for 2h at minus 40 ℃, and then dried for 36h to obtain a directional heat conduction film with the film thickness of 0.4 mm;
c) Preparing hollow nano microspheres: at room temperature, adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle according to the mass ratio of polyvinylpyrrolidone to water to absolute ethyl alcohol of 1:2:20, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile, styrene and styrene into the mixed solution according to the mass ratio of azobisisobutyronitrile to styrene of 1:6:35, reacting for 12 hours at 70 ℃, filtering, washing a filter cake with absolute ethyl alcohol for 4 times according to the mass ratio of the filter cake to absolute ethyl alcohol of 1:2, and drying at 70 ℃ for 36 hours to obtain polystyrene microspheres; adding ammonia water, lipid precursors and absolute ethyl alcohol into a reaction kettle according to the volume ratio of the ammonia water to the lipid precursors to the absolute ethyl alcohol of 1:3:30 at room temperature, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of the surfactant to the polystyrene microspheres of 1:4:60, reacting for 36h, filtering, washing a filter cake with deionized water according to the mass ratio of the filter cake to the deionized water of 1:2, drying, calcining for 2h at the temperature rising rate of 3 ℃/min and the temperature of 600 ℃, and obtaining the hollow nano microspheres;
d) Preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent with the volume ratio of 1:6, the mass ratio of the hollow nano-microspheres to the cellulose is 1:20 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 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 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 to be soaked for 4 hours, the laminated film is taken out, the porous radiation refrigeration film material is dried for 5 hours at 70 ℃, and the film thickness of the film material is 0.8mm.
And testing the refrigerating performance of the obtained material by a temperature tester and a solar irradiance meter. The material has a reflectivity of 97% to sunlight, an emissivity of 96% in an atmospheric window of 8-13 mu m, and a solar irradiance of 950W/m 2 The temperature can be reduced by 19 ℃.
Example 4
a) Preparing a directional heat conduction material: placing MAX precursor, liF and 37wt% of diluted hydrochloric acid into a reaction kettle according to the mass ratio of MAX precursor to LiF to 37wt% of diluted hydrochloric acid of 1:3:60 at room temperature, uniformly mixing, reacting for 48 hours, centrifuging, washing with deionized water until the pH is more than 6, adding deionized water into the precipitate according to the mass ratio of the precipitate to the deionized water of 1:3, performing 1320W ultrasonic treatment for 12 hours, performing vacuum suction filtration, and drying a filter cake at 80 ℃ for 24 hours to obtain the MXene directional heat conducting material;
b) Preparing an oriented heat conduction film: the mixed solution is NaOH, urea and aqueous solution with the mass ratio of 1:4:10, the mass ratio of MXene directional heat conduction material to cellulose to the mixed solution is 1:10:80 at room temperature, 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, the mass ratio of the mixture to absolute ethyl alcohol is 1:4, the absolute ethyl alcohol is added into the mixture, standing is carried out for 12h, wet gel is obtained, deionized water is added into the wet gel with the mass ratio of the wet gel to deionized water being 1:3, standing is carried out for 4h, the hydrogel is obtained, the hydrogel is transferred into a mold, frozen for 3h at the temperature of minus 20 ℃, and then dried for 48h at the temperature of minus 40 ℃ to obtain a directional heat conduction film with the film thickness of 0.5mm;
c) Preparing hollow nano microspheres: at room temperature, adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle according to the mass ratio of polyvinylpyrrolidone to water to absolute ethyl alcohol of 1:2:30, uniformly mixing to obtain a mixed solution, adding azobisisobutyronitrile, styrene and styrene into the mixed solution according to the mass ratio of azobisisobutyronitrile to styrene of 1:7:50, reacting at 80 ℃ for 14h, filtering, washing a filter cake with absolute ethyl alcohol for 4 times according to the mass ratio of the filter cake to absolute ethyl alcohol of 1:3, and drying at 80 ℃ for 48h to obtain polystyrene microspheres; adding ammonia water, lipid precursors and absolute ethyl alcohol into a reaction kettle according to the volume ratio of the ammonia water to the lipid precursors to the absolute ethyl alcohol of 1:3:50 at room temperature, uniformly mixing to obtain a mixed solution, adding a surfactant and polystyrene microspheres into the mixed solution according to the mass ratio of the surfactant to the polystyrene microspheres of 1:5:80, reacting for 48 hours, filtering, washing a filter cake with deionized water according to the mass ratio of the filter cake to the deionized water of 1:2, drying, calcining for 3 hours at the temperature rising rate of 5 ℃/min and the temperature of 700 ℃, and obtaining the hollow nano microspheres;
d) Preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent with the volume ratio of 1:9, the mass ratio of the hollow nano-microspheres to the cellulose is 1:30 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 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 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 to be soaked for 6h, the laminated film is taken out, the porous radiation refrigeration film material is dried for 6h at 80 ℃, and the film thickness of the film material is 1.1mm.
And testing the refrigerating performance of the obtained material by a temperature tester and a solar irradiance meter. The material has a reflectivity of 99% to sunlight, an emissivity of 98% in an atmospheric window of 8-13 μm, and a solar irradiance of 1200W/m 2 The temperature can be reduced by 25 ℃.
Claims (5)
1. The directional heat-conducting porous radiation refrigeration film material is characterized by being formed by overlapping an outer high-reflectivity film and an inner directional heat-conducting film; the high-reflectivity film is prepared by dispersing hollow nano-microspheres into cellulose through phase conversion; the directional heat conduction film is prepared by dispersing an MXene directional heat conduction material into cellulose and performing directional freeze drying;
the preparation method of the directional heat conduction porous radiation refrigeration film material comprises the following steps:
step 1, preparing a directional heat conduction material: adding MAX precursor, liF and 37wt% of diluted hydrochloric acid into a reaction kettle according to the mass ratio of 1:2:20-1:3:60 at room temperature, uniformly mixing, reacting for 24-48 h, centrifuging, washing the precipitate with deionized water until the pH of the washing solution is more than 6, adding deionized water into the precipitate according to the mass ratio of the precipitate to the deionized water of 1:2-1:3, carrying out ultrasonic treatment for 6-12 h at 900W-1320W, carrying out suction filtration under vacuum, and drying a filter cake for 12-24 h at 60-80 ℃ to obtain the MXene directional heat conducting material;
step 2, preparing an oriented heat conduction film: the mixed solution is NaOH, urea and aqueous solution with the mass ratio of 1:2:4-1:4:10, the mass ratio of MXene directional heat conduction material to cellulose to the mixed solution is 1:5:30-1:10:80 at room temperature, the MXene directional heat conduction material, cellulose and the mixed solution prepared in the step 1 are added into a reaction kettle to be uniformly mixed, the mass ratio of the mixture to absolute ethyl alcohol is 1:2-1:4, the absolute ethyl alcohol is added into the mixture, standing is carried out for 8-16 h to obtain wet gel, deionized water is added into the wet gel with the mass ratio of the wet gel to deionized water being 1:2-1:3, standing is carried out for 2-4 h, hydrogel is obtained after the hydrogel is transferred into a mold, freezing is carried out for 1-3 h at-80 to-20 ℃, the temperature is dried for 24-48 h at-80 to-40 ℃, and the film thickness of the directional heat conduction film is 0.2-0.5 mm;
step 3, hollow nanometer microsphere preparation: at room temperature, adding polyvinylpyrrolidone, water and absolute ethyl alcohol into a reaction kettle according to the mass ratio of polyvinylpyrrolidone to water to absolute ethyl alcohol 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 azobisisobutyronitrile to styrene of 1:5:25-1:7:50, reacting for 10-14 h at 60-80 ℃, filtering, washing a filter cake 3-4 times by absolute ethyl alcohol according to the mass ratio of the filter cake to absolute ethyl alcohol of 1:2-1:3, 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 according to the volume ratio of the ammonia water to the precursor to the absolute ethyl alcohol of 1:2:30-1:3:50 at room temperature, uniformly mixing to obtain a mixed solution, adding a surfactant and the prepared polystyrene microsphere into the mixed solution according to the mass ratio of the surfactant to the polystyrene microsphere to 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 the heating rate of 1-5 ℃/min, calcining for 1-3 h at the temperature of 400-700 ℃, and cooling to room temperature to obtain the hollow nano microsphere;
step 4, preparing a porous radiation refrigeration film material: the mixed solvent is acetone and N-methyl pyrrolidone solvent with the volume ratio of 1:2-1:9, the mass ratio of the hollow nano-microspheres to the cellulose is 1:10-1:30 at room temperature, the hollow nano-microspheres and the cellulose prepared in the step 3 are added into the mixed solvent, 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 conducting film prepared in the step 2, the acetone is volatilized to obtain a laminated film, the laminated film is placed into absolute ethyl alcohol and soaked for 2-6 h, the laminated film is taken out, the porous radiation refrigeration film material is dried for 3-6 h at the temperature of 60-80 ℃, and the film thickness of the film material is 0.3-1.1 mm;
the MAX precursor is Ti 3 AlC 2 Or Ti (Ti) 2 AlC; the ester precursor is tetraethoxysilane or tetrabutyl titanate.
2. The oriented heat conducting porous radiation refrigeration film material as set forth in claim 1, wherein said hollow nano-microspheres are polystyrene-based templates.
3. The directional heat conduction porous radiation refrigeration film material according to claim 1, wherein the MXene directional heat conduction material is prepared by selectively etching MAX precursor by an in-situ growth hydrofluoric acid method, ultrasonic stripping and vacuum filtration.
4. The directional heat conducting porous radiant refrigerant film material as set forth in claim 1, wherein in step 3, the surfactant is cetyltrimethylammonium bromide or sodium dodecyl sulfate.
5. The oriented heat conducting porous radiant refrigerant film material as set forth in claim 1, wherein in step 3, the cellulose is bacterial cellulose or lignocellulose.
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