CN111793472A - Boron nitride aerogel phase-change film, and preparation method and application thereof - Google Patents
Boron nitride aerogel phase-change film, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a boron nitride aerogel phase-change film, a preparation method and application thereof. The boron nitride aerogel phase-change film is composed of a boron nitride aerogel film and a phase-change material, the boron nitride aerogel film is provided with a three-dimensional porous network formed by winding and lapping boron nitride nanobelts, and the phase-change material is filled in the porous network of the boron nitride aerogel film. The preparation method comprises the following steps: cutting, pressure induction assembling, high-temperature pyrolysis and melting and filling of the phase-change material are carried out on the block melamine borate base material, so that the thinning, densification, pyrolysis purification and composite filling of the material are successively realized, and the boron nitride aerogel phase-change film is obtained. The boron nitride aerogel phase-change film has the function of reversible absorption and release of heat energy, can be used for heat management of portable electronic equipment and wearable electronic equipment under the future 5G technology, creates comfortable use environment and working environment for human bodies and electronic elements, and has simple preparation process.
Description
Technical Field
The invention relates to a boron nitride aerogel phase-change film and a preparation method and application thereof, belonging to the field of energy materials and nanotechnology.
Background
Aerogel is a low-density solid material with a continuous three-dimensional porous network structure, the dispersion medium of which is gas. Since the American chemist Samuel Stephens Kistler first used the supercritical fluid drying technique to prepare a "solid smoke" -silica aerogel in 1932, the aerogel has received attention and research as a new member of the material family. During the last century, a series of aerogels with different materials, structures and properties, such as silica aerogel and metal oxide aerogel (TiO), have been synthesized in succession2、Al2O3、ZrO2Etc.), metal simple substance aerogel (like gold), polymer aerogel (polyaniline, polypyrrole, polyimide etc.), carbon aerogel and novel nanometer carbon aerogel (graphite alkene, carbon nanotube etc.), semiconductor sulfide aerogel, carbide aerogel (carborundum, titanium aluminium carbide etc.), natural polymer aerogel (be cellulose and other polysaccharide and various protein promptly) and boron nitride aerogel etc. very big richened the family of aerogel, expanded the research field and the application direction of aerogel.
The synthesis of the aerogel is based on the process of sol-gel transformation, and most of the aerogel is generated in a three-dimensional space, so that the aerogel is difficult to be subjected to uniform sol-gel transformation in a limited space. Meanwhile, the gel-gel conversion requires a long standing and aging process and is limited by the sol-gel synthesis of the aerogel, and most of the obtained aerogel and the phase-change composite material thereof are macroscopic blocks. It is difficult to achieve sol-gel conversion in a thin space. And the inherent rigidity and stiffness of the block material make the block material difficult to adapt to the existing miniaturized, integrated and intelligent electronic devices and intelligent systems.
On the other hand, the solid-liquid phase change material can absorb and release a large amount of heat through a reversible solid-liquid phase change process in a narrow temperature range. Therefore, it is considered to be a promising thermal management material. However, in the solid-liquid phase change material, the phase change material in a molten state has fluidity during use, and leakage is easy to occur, which causes a series of problems.
Based on the method, the aerogel is used as a carrier with ultralow density, high porosity and strong capillary force to synthesize the shape-stable phase-change composite material. At present, porous materials such as metal foams, carbon aerogels, graphene aerogels, carbon nanotube sponges and carbon nanotube arrays are used in the research of organic phase change energy storage materials, so that the organic phase change energy storage materials are endowed with excellent electric/thermal conductivity and can be subjected to light or electric driving for heat energy conversion and storage. Therefore, the aerogel material is very feasible and has great application prospect for improving the dilemma of the phase change energy storage material.
In addition, with the miniaturization and integration of electronic systems and devices and the embedding of 5G technology, the power of electronic devices is increasing. The heating problem of the electronic components is getting more and more serious. A large amount of heat is dissipated through the heat sink. However, this heat dissipation leads to heat transfer to the body, which brings risks such as thermal discomfort and burning. Therefore, in a narrow and compact space and under a complex application scene, how to realize effective management of heat, new requirements for new materials such as lightness, thinness, flexibility, toughness and the like are provided.
In view of the defects of the traditional aerogel, such as stiffness and rigidity, caused by the bulk and large size, and the demands of the miniaturized electronic system for thin, light, flexible and multifunctional integration of new materials, an aerogel film, a multifunctional phase-change composite film and a simple preparation method are urgently needed and provided, and the structural form, the performance and the application of the aerogel and the composite material are pushed to a new height.
Disclosure of Invention
The invention mainly aims to provide a boron nitride aerogel phase-change film, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a boron nitride aerogel phase-change film, which comprises the following steps:
providing a melamine borate based material comprising a host material comprising boric acid and melamine and an additive;
applying pressure to the melamine borate-based material, and carrying out pressure-induced assembly to obtain a melamine borate-based film;
carrying out high-temperature pyrolysis treatment on the melamine borate-based film to obtain a boron nitride aerogel film;
and filling the boron nitride aerogel film with a phase-change material in a melting filling mode to obtain the boron nitride aerogel phase-change film.
The embodiment of the invention also provides the boron nitride aerogel film prepared by the method, and the boron nitride aerogel film is provided with a three-dimensional porous network formed by winding and lapping the boron nitride nanobelts.
Further, the boron nitride nanobelt mainly consists of boron and nitrogen elements, and the total content of the nitrogen elements and the boron elements in the boron nitride nanobelt is higher than 80 wt%;
further, the thermal conductivity of the boron nitride aerogel film is 0.015-0.5W/mK; the boron nitride aerogel film has mechanical flexibility without temperature dependence and can be bent, folded or twisted, and the density of the boron nitride aerogel film is 15-750 mg/mL.
The embodiment of the invention also provides a boron nitride aerogel phase-change film prepared by the method, which comprises the following components: the boron nitride aerogel film is provided with a three-dimensional porous network formed by winding and lapping boron nitride nanobelts, and the phase-change material is filled and embedded in the three-dimensional porous network.
Further, the boron nitride aerogel phase change film is electrically insulated, and the thermal conductivity of the boron nitride aerogel phase change film is 0.05-5.0W/mK.
Further, the phase change temperature of the boron nitride aerogel phase change film is 10-150 ℃, and the enthalpy value of the boron nitride aerogel phase change film is 10-200J/g.
The invention also provides application of the boron nitride aerogel film or the boron nitride aerogel phase-change film in the fields of heat insulation, thermal energy storage and release, portable electronic devices or heat management of wearable electronic systems under the future 5G technology.
Compared with the prior art, the invention has the advantages that:
(1) the boron nitride aerogel phase-change film provided by the invention has the basic characteristics of flexibility, thinness, lightness and the like, and is composed of a boron nitride aerogel film and a phase-change material, wherein the boron nitride aerogel film is provided with a three-dimensional porous network formed by mutually winding and lapping boron nitride nanobelts, and the phase-change material is filled in the porous network of the boron nitride aerogel film. The boron nitride aerogel phase-change film has adjustable thickness, shape and density;
(2) the preparation process of the boron nitride aerogel phase-change film provided by the invention is simple, the reaction condition is mild, the operation is easy, the energy consumption is low, the cost is low, the method is green and pollution-free, and the large-scale continuous production can be realized;
(3) the boron nitride aerogel phase-change film and the boron nitride aerogel film provided by the invention have good application prospects in the fields of thermal insulation, thermal energy storage and release, thermal management of electronic devices and electronic systems under the future 5G technology and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a phase-change film of a boron nitride aerogel obtained in example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the boron nitride aerogel phase-change film obtained in example 2 of the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of a phase-change film of a boron nitride aerogel obtained in example 3 of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of a boron nitride aerogel phase-change film obtained in example 4 of the present invention.
FIG. 5 is a Scanning Electron Microscope (SEM) photograph of the boron nitride aerogel phase-change film obtained in example 5 of the present invention.
FIG. 6 is a Scanning Electron Microscope (SEM) photograph of a boron nitride aerogel phase-change film obtained in example 6 of the present invention.
FIG. 7 is a Scanning Electron Microscope (SEM) photograph of a boron nitride aerogel phase-change film obtained in example 7 of the present invention.
FIG. 8 is a Scanning Electron Microscope (SEM) photograph of a boron nitride aerogel phase-change film obtained in example 8 of the present invention.
FIG. 9 is a Scanning Electron Microscope (SEM) photograph of the boron nitride aerogel thin film obtained in example 1 of the present invention.
FIG. 10 is a graph showing the nitrogen adsorption and desorption curves of the boron nitride aerogel thin film obtained in example 1 of the present invention.
FIG. 11 is a pore size distribution diagram of the boron nitride aerogel thin film obtained in example 1 of the present invention.
FIG. 12 is a stress-strain curve of the boron nitride aerogel thin film obtained in example 1 of the present invention.
FIG. 13 is a thermogravimetric plot of the boron nitride aerogel phase-change film obtained in example 1 of the present invention.
FIG. 14 is a DSC chart of the boron nitride aerogel phase-change composite film obtained in example 1 of the present invention.
FIG. 15 is an optical photograph of the boron nitride aerogel phase-change composite film obtained in example 1 of the present invention.
FIG. 16 is an optical photograph of the boron nitride aerogel phase-change composite obtained in comparative example 1 of the present invention.
FIG. 17 is a graph comparing the thermogravimetric curves of the melamine borate based aerogel thin film obtained in comparative example 2 of the present invention and the boron nitride aerogel thin film obtained in example 1.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has made long-term research and extensive practice to provide the technical scheme of the present invention, which mainly comprises the steps of cutting the block melamine borate base material into pieces, performing pressure induced assembly, performing high-temperature annealing, and performing melt filling on the phase-change material, thereby successively realizing the treatments of thinning, densification, pyrolysis purification, composite filling and the like on the material, and obtaining the boron nitride aerogel phase-change film. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a method for preparing a boron nitride aerogel phase-change film, including:
providing a melamine borate based material comprising a host material comprising boric acid and melamine and an additive;
applying pressure to the melamine borate-based material, and carrying out pressure-induced assembly to obtain a melamine borate-based film;
carrying out high-temperature pyrolysis treatment on the melamine borate-based film to obtain a boron nitride aerogel film;
and filling the boron nitride aerogel film with a phase-change material in a melting filling mode to obtain the boron nitride aerogel phase-change film.
In some preferred embodiments, the additive includes any one or a combination of two or more of cyanuric acid, biuret, dimethylguanidine, triethylamine, and the like, but is not limited thereto.
In some preferred embodiments, the mass ratio of boric acid to melamine is 1: 10-10: 1.
in some preferred embodiments, the additive is present in the melamine borate based material in an amount of 0 to 50 wt%.
In some preferred embodiments, the method of preparation comprises: the melamine borate based material in bulk form was cut into pieces to obtain light and thin melamine borate based sheets.
Further, the cutting into sheets, the melamine borate based bulk material can be cut into sheets by means of a common cutting tool, resulting in a light and thin melamine borate based sheet. The common cutting tool is a blade.
Furthermore, the thickness of the melamine borate based sheet is 100 mu m-3 mm and is adjustable.
In some preferred embodiments, the method of preparation comprises: and compressing the melamine borate-based sheet under the pressure of 0.01-10 MPa, and performing pressure-induced assembly to further densify and lighten the film, thereby preparing the melamine borate-based film.
Further, the thickness of the melamine borate based film is 50 μm to 500 μm.
In some preferred embodiments, the temperature of the high-temperature pyrolysis treatment is 600-1500 ℃, preferably 1000-1400 ℃, and the time of the high-temperature pyrolysis treatment is 1-24 hours, preferably 3-12 hours.
Further, the preparation method comprises the following steps: the high temperature pyrolysis treatment is carried out under a protective atmosphere.
Further, the protective atmosphere includes any one or a combination of two or more of nitrogen, argon, ammonia, hydrogen, air atmosphere, and the like, but is not limited thereto.
In some preferred embodiments, the method of preparation comprises: and soaking the boron nitride aerogel film in the molten phase change material for 1 min-6 h to obtain the boron nitride aerogel phase change film.
Further, the phase change material is an organic solid-liquid phase change material, and the organic solid-liquid phase change material includes any one or a combination of two or more of polyethylene glycol, paraffin, stearic acid, fatty amine, alkane, polyol, fatty alcohol, and the like, but is not limited thereto.
In conclusion, the preparation process of the boron nitride aerogel phase-change film provided by the invention is simple, the reaction condition is mild, the operation is easy, the energy consumption is low, the cost is low, the method is green and pollution-free, and the large-scale continuous production can be realized.
Another aspect of the embodiments of the present invention provides a boron nitride aerogel film and a boron nitride aerogel phase change film prepared by the foregoing methods.
Another aspect of the embodiments of the present invention provides a boron nitride aerogel thin film having characteristics of flexibility, thinness, lightness, and the like, which has a three-dimensional porous network formed by winding and overlapping boron nitride nanobelts.
Further, the boron nitride nanobelt mainly consists of boron and nitrogen, and the total content of the nitrogen and the boron in the boron nitride nanobelt is higher than 80 wt%.
Furthermore, the boron nitride nanobelt mainly comprises boron and nitrogen, contains trace carbon and oxygen, and contains boron, nitrogen, carbon and oxygen.
Further, the thickness of the boron nitride nanobelt is 1-100 nm, the width of the boron nitride nanobelt is 50-2 μm, and the length of the boron nitride nanobelt is dozens of micrometers to hundreds of micrometers.
Further, the thermal conductivity of the boron nitride aerogel film is 0.015-0.5W/mK.
Further, the thickness of the boron nitride aerogel film is 10-3 mm and is adjustable, and preferably 50-500 μm.
Further, the boron nitride aerogel thin film has mechanical flexibility without temperature dependence, and can be bent, folded or twisted.
Further, the density of the boron nitride aerogel film is 15 mg/mL-750 mg/mL.
In conclusion, the boron nitride aerogel thin film has the advantages of flexible mechanical property without temperature dependence, low thermal conductivity, excellent thermal stability and the like.
The boron nitride aerogel phase-change film provided by the embodiment of the invention has the characteristics of flexibility, thinness, lightness and the like, and is composed of the boron nitride aerogel film and a phase-change material, wherein the boron nitride aerogel film is provided with a three-dimensional porous network formed by mutually winding and lapping boron nitride nanobelts, and the phase-change material is filled and embedded in the three-dimensional porous network of the boron nitride aerogel film.
In some preferred embodiments, the boron nitride aerogel phase-change film can be cut into any one of various shapes, such as a rectangle, a triangle, a circle, a square, a star, an irregular shape, and the like, but is not limited thereto.
Further, the thickness of the boron nitride aerogel phase change film is 10-3 mm and is adjustable, and preferably 50-500 μm.
Further, the boron nitride aerogel phase change film is electrically insulating.
Further, the thermal conductivity of the boron nitride aerogel phase change film is 0.05-5.0W/mK.
Further, the phase change temperature of the boron nitride aerogel phase change film is adjustable at 10-150 ℃, and the enthalpy value of the boron nitride aerogel phase change film is adjustable at 10-200J/g.
Further, in the boron nitride aerogel phase-change film, the content of the boron nitride aerogel film is 1-90 wt%.
Further, in the boron nitride aerogel phase change film, the content of the phase change material is 10-99 wt%.
Further, the phase change material is an organic solid-liquid phase change material.
Further, the organic solid-liquid phase-change material includes any one or a combination of two or more of polyethylene glycol, paraffin, stearic acid (e.g., octadecanoic acid), fatty amine (e.g., hexadecyl amine), alkane (preferably, alkane having carbon atoms of C15-C30), polyol (e.g., pentaerythritol), fatty alcohol (e.g., tetradecyl alcohol), and the like, but is not limited thereto.
Further, the boron nitride aerogel phase-change film has the function of reversible absorption and release of heat energy.
Another aspect of the embodiments of the present invention further provides an application of any one of the boron nitride aerogel phase-change thin films and the boron nitride aerogel thin films in the fields of thermal insulation, thermal energy storage and release, portable electronic devices, and thermal management of wearable electronic systems in future 5G technologies.
Further, the application includes: any of the boron nitride aerogel phase-change films is embedded in an electronic device to achieve thermal management.
Furthermore, the boron nitride aerogel phase change film realizes the absorption of heat energy and reduces the temperature of the electronic element through the solid-liquid transition function of the phase change material.
Further, the application includes: and embedding any boron nitride aerogel film into an electronic device to realize heat management.
Furthermore, the boron nitride aerogel film reduces the dissipation of heat to human skin by cutting off heat flow transmission, and realizes the thermal protection function.
In summary, the boron nitride aerogel thin film and the boron nitride aerogel phase-change thin film can be used for thermal management of portable electronic devices and wearable electronic devices under the future 5G technology, and create comfortable use environments and working environments for human bodies and electronic elements.
By the technical scheme, the boron nitride aerogel phase-change film has the characteristics of flexibility, thinness, lightness and the like, is composed of the boron nitride aerogel film and the phase-change material, is provided with a three-dimensional porous network formed by winding and lapping boron nitride nanobelts, and is filled with the phase-change material. The boron nitride aerogel film has the advantages of no temperature dependence, flexible mechanical property, low heat conductivity coefficient, excellent thermal stability and the like. The boron nitride aerogel phase-change film has the function of reversible absorption and release of heat energy. The boron nitride aerogel film and the boron nitride aerogel phase-change film can be used for thermal management of portable electronic equipment and wearable electronic equipment under the future 5G technology, and a comfortable use environment and a working environment are created for a human body and electronic elements. The preparation process is simple, the reaction condition is mild, the operation is easy, the cost is low, the method is green and pollution-free, and the continuous production can be realized.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
(a) Selecting boric acid: the mass ratio of melamine is 1: 1, a melamine borate based material having a cyanuric acid content of 0.01 wt%.
(b) Cutting the melamine borate based material of step (a) to obtain a melamine borate based sheet having a thickness of 3 mm.
(c) And (c) carrying out pressure assembly on the melamine borate-based sheet in the step (b) at the pressure of 10MPa to obtain the melamine borate-based film.
(d) And (c) annealing the melamine borate-based film in the step (c) at 600 ℃ in an ammonia atmosphere for 24 hours to obtain the boron nitride aerogel film.
(e) And (d) soaking the boron nitride aerogel film in the step (d) in molten paraffin, standing in a 100 ℃ oven for 1h, taking out, cooling and solidifying to obtain the boron nitride phase-change composite film.
Fig. 1 is an SEM photograph of a cross section of the phase-change film of the boron nitride aerogel obtained in the present example, and the structural and performance parameters are shown in table 1. Fig. 9 is an SEM photograph of the inside of the boron nitride aerogel film obtained in the present example, fig. 10 is a nitrogen adsorption/desorption graph of the boron nitride aerogel film obtained in the present example, fig. 11 is a pore size distribution graph of the boron nitride aerogel film obtained in the present example, fig. 12 is a stress-strain graph of the boron nitride aerogel film obtained in the present example, fig. 13 is a TG graph of the boron nitride aerogel phase-change composite film obtained in the present example, and fig. 14 is a DSC graph of the boron nitride aerogel phase-change composite film obtained in the present example. FIG. 15 is an optical photograph of the boron nitride aerogel phase-change film obtained in this example.
Example 2
(a) Selecting boric acid: the mass ratio of melamine is 1: 10 melamine borate based material with a triethylamine content of 50 wt%.
(b) Cutting the melamine borate based material of step a) to obtain melamine borate based sheets having a thickness of 80 μm.
(c) Pressure assembling the melamine borate based sheet of step b) at a pressure of 10kPa to obtain a melamine borate based film.
(d) Annealing the melamine borate-based film in the step c) at 1500 ℃ in an argon/ammonia atmosphere for 3h to obtain the boron nitride aerogel film.
(e) And (d) soaking the boron nitride aerogel film in the step (d) in molten polyethylene glycol, standing in a drying oven at 150 ℃ for 1min, taking out, cooling and solidifying to obtain the boron nitride phase-change composite film.
Fig. 2 is an SEM photograph of a cross section of the boron nitride aerogel phase change film obtained in the present example, and the structural and performance parameters are shown in table 1.
Example 3
(a) Selecting boric acid: the mass ratio of melamine is 10: 1, melamine borate based material with a biuret content of 1 wt%.
(b) Cutting the melamine borate based material of step a) to obtain melamine borate based sheets having a thickness of 10 μm.
(c) Carrying out pressure assembly on the melamine borate-based sheet in the step b) under the pressure of 1MPa to obtain the melamine borate-based film.
(d) Annealing the melamine borate-based film in the step c) at 1400 ℃ in an argon/air atmosphere for 6h to obtain the boron nitride aerogel film.
(e) And (d) soaking the boron nitride aerogel film in the step (d) in molten paraffin, standing in a 90 ℃ oven for 0.5h, taking out, cooling and solidifying to obtain the boron nitride phase-change composite film.
Fig. 3 is an SEM photograph of a cross section of the boron nitride aerogel phase change film obtained in the present example, and the structural and performance parameters are shown in table 1.
Example 4
(a) Selecting boric acid: the mass ratio of melamine is 5: 1, melamine borate based material with a dimethylguanidine content of 15 wt%.
(b) Cutting the melamine borate based material of step a) to obtain melamine borate based sheets with a thickness of 1 mm.
(c) Pressure assembling the melamine borate based sheet of step b) at a pressure of 800kPa to obtain a melamine borate based film.
(d) Annealing the melamine borate-based film in the step c) at 1000 ℃ in an argon/nitrogen atmosphere for 12h to obtain the boron nitride aerogel film.
(e) And (d) soaking the boron nitride aerogel film in the step (d) in molten fatty amine (such as hexadecylamine), standing for 6 hours in a 90 ℃ oven, taking out, cooling and solidifying to obtain the boron nitride phase-change composite film.
Fig. 4 is an SEM photograph of a cross section of the boron nitride aerogel phase change film obtained in the present example, and the structural and performance parameters are shown in table 1.
Example 5
(a) Selecting boric acid: the mass ratio of melamine is 1: 7, a melamine borate based material having a cyanuric acid content of 0.5 wt%.
(b) Cutting the melamine borate based material of step a) to obtain melamine borate based sheets with a thickness of 0.5 mm.
(c) Carrying out pressure assembly on the melamine borate-based sheet in the step b) under the pressure of 2MPa to obtain the melamine borate-based film.
(d) Annealing the melamine borate-based film in the step c) at 700 ℃ in a nitrogen atmosphere for 3h to obtain the boron nitride aerogel film.
(e) And (d) soaking the boron nitride aerogel film in the step (d) in molten fatty acid (such as octadecanoic acid), standing for 2h in a drying oven at the temperature of 110 ℃, taking out, cooling and solidifying to obtain the boron nitride phase-change composite film.
Fig. 5 is an SEM photograph of a cross section of the boron nitride aerogel phase change film obtained in the present example, and the structural and performance parameters are shown in table 1.
Example 6
(a) Selecting boric acid: the mass ratio of melamine is 8: 1, a melamine borate based material with a triethylamine content of 0.09 wt%.
(b) Cutting the melamine borate based material of step a) to obtain melamine borate based sheets having a thickness of 50 μm.
(c) Pressure assembling the melamine borate based sheet of step b) at a pressure of 50kPa to obtain a melamine borate based film.
(d) Annealing the melamine borate-based film in the step c) at 1200 ℃ in an ammonia atmosphere for 4h to obtain the boron nitride aerogel film.
(e) And (d) soaking the boron nitride aerogel film in the step (d) in molten polyol (such as pentaerythritol), standing for 4 hours in a drying oven at 100 ℃, taking out, cooling and solidifying to obtain the boron nitride phase-change composite film.
Fig. 6 is an SEM photograph of a cross section of the boron nitride aerogel phase change film obtained in the present example, and the structural and performance parameters are shown in table 1.
Example 7
(a) Selecting boric acid: the mass ratio of melamine is 1: 2, a melamine borate based material having a biuret content of 0.8 wt%.
(b) Cutting the melamine borate based material of step a) to obtain melamine borate based sheets having a thickness of 200 μm.
(c) Carrying out pressure assembly on the melamine borate-based sheet in the step b) under the pressure of 5MPa to obtain the melamine borate-based film.
(d) Annealing the melamine borate-based film in the step c) at 1100 ℃ in a hydrogen atmosphere for 8h to obtain the boron nitride aerogel film.
(e) And (d) soaking the boron nitride aerogel film in the step (d) in molten fatty alcohol (such as tetradecyl alcohol), standing in a 120 ℃ oven for 10min, taking out, cooling and solidifying to obtain the boron nitride phase-change composite film.
Fig. 7 is an SEM photograph of a cross section of the phase-change film of boron nitride aerogel obtained in this example, please refer to table 1 for structural and performance parameters.
Example 8
(a) Selecting boric acid: the mass ratio of melamine is 1: additive-free melamine borate based materials.
(b) Cutting the melamine borate based material of step a) to obtain a melamine borate based sheet having a thickness of 3 mm.
(c) Carrying out pressure assembly on the melamine borate-based sheet in the step b) under the pressure of 3MPa to obtain the melamine borate-based film.
(d) Annealing the melamine borate-based film in the step c) at 600 ℃ in an argon atmosphere for 24 hours to obtain the boron nitride aerogel film.
(e) And (d) soaking the boron nitride aerogel film in the step (d) in molten paraffin, standing for 4h in a drying oven at 150 ℃, taking out, cooling and solidifying to obtain the boron nitride phase-change composite film.
Fig. 8 is an SEM photograph of a cross section of the boron nitride aerogel phase change film obtained in the present example, and the structural and performance parameters are shown in table 1.
Table 1 structure and performance parameters of boron nitride aerogel phase change films prepared in examples 1-8
Comparative example 1
(a) Selecting boric acid: the mass ratio of melamine is 1: additive-free melamine borate based materials.
(b) Annealing the melamine borate-based material in the step a) at 1400 ℃ in an argon atmosphere for 12h to obtain the boron nitride aerogel.
(c) And (c) soaking the boron nitride aerogel obtained in the step (b) in molten paraffin, standing for 4 hours in a drying oven at 150 ℃, taking out, cooling and solidifying to obtain the boron nitride phase-change composite material.
Fig. 15 is an optical photograph of the resulting boron nitride phase change composite material. The prepared boron nitride aerogel phase-change composite material is a macroscopic block material without being processed by cutting and compressing processes, and has no characteristics of thinness, flexibility and the like.
Comparative example 2
(a) Selecting boric acid: the mass ratio of melamine is 1: additive-free melamine borate based materials.
(b) Cutting the melamine borate based material of step a) to obtain melamine borate based sheets with a thickness of 1 mm.
(c) Carrying out pressure assembly on the melamine borate-based sheet in the step b) under the pressure of 2MPa to obtain the melamine borate-based film.
(d) And (c) dipping the melamine borate-based film in the step (c) into molten paraffin, standing for 4h in a drying oven at 150 ℃, taking out, cooling and solidifying to obtain the melamine borate-based film phase-change composite film.
FIG. 16 is a TG curve of the melamine borate based aerogel film obtained in comparative example 2 and the boron nitride aerogel film obtained in example 1. The comparison shows that the film after high-temperature pyrolysis has good high-temperature thermal stability. The melamine borate aerogel thin film obtained in comparative example 2 started to decompose at about 150 ℃, and was difficult to withstand thermal shock in a high-temperature environment.
In addition, the inventor prepares a series of boron nitride aerogel phase-change films by adopting other raw materials and process conditions listed in the specification and referring to the modes of examples 1-8. Tests show that the boron nitride aerogel phase change film also has the excellent performances mentioned in the specification.
The embodiment proves that the boron nitride aerogel disclosed by the invention is excellent in performance, the required preparation equipment is simple to operate, continuous automatic production can be realized, the preparation period and the cost are greatly shortened, and the boron nitride aerogel has a huge application prospect.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A preparation method of a boron nitride aerogel phase-change film is characterized by comprising the following steps:
providing a melamine borate based material comprising a host material comprising boric acid and melamine and an additive;
applying pressure to the melamine borate-based material, and carrying out pressure-induced assembly to obtain a melamine borate-based film;
carrying out high-temperature pyrolysis treatment on the melamine borate-based film to obtain a boron nitride aerogel film;
and filling the boron nitride aerogel film with a phase-change material in a melting filling mode to obtain the boron nitride aerogel phase-change film.
2. The method of claim 1, wherein: the additive comprises any one or the combination of more than two of cyanuric acid, biuret, dimethylguanidine and triethylamine; and/or the mass ratio of the boric acid to the melamine is 1: 10-10: 1; and/or the additive content in the melamine borate based material is 0-50 wt%.
3. The production method according to claim 1, characterized by comprising: cutting the melamine borate based material in bulk form into pieces to obtain light and thin melamine borate based sheets; preferably, the melamine borate based sheet has a thickness of 100 μm to 3 mm.
4. The production method according to claim 3, characterized by comprising: compressing the melamine borate based sheet at a pressure of 0.01MPa to 10MPa, and performing the pressure induced assembly to produce the melamine borate based film; preferably, the melamine borate based film has a thickness of 50 to 500. mu.m.
5. The method of claim 1, wherein: the temperature of the high-temperature pyrolysis treatment is 600-1500 ℃, the preferred temperature is 1000-1400 ℃, and the time of the high-temperature pyrolysis treatment is 1-24 hours, and the preferred time is 3-12 hours; and/or, the preparation method comprises the following steps: carrying out the high-temperature pyrolysis treatment under a protective atmosphere; preferably, the protective atmosphere comprises any one or a combination of two or more of nitrogen, argon, ammonia, hydrogen and air.
6. The production method according to claim 1, characterized by comprising: dipping the boron nitride aerogel film in a molten phase change material for 1 min-6 h to obtain a boron nitride aerogel phase change film; and/or the phase-change material is an organic solid-liquid phase-change material, and the organic solid-liquid phase-change material comprises any one or combination of more than two of polyethylene glycol, paraffin, stearic acid, fatty amine, alkane, polyalcohol and fatty alcohol.
7. A boron nitride aerogel thin film produced by the method of any of claims 1-6, having a three-dimensional porous network formed by intertwining, overlapping boron nitride nanoribbons; preferably, the boron nitride nanobelt mainly consists of boron and nitrogen elements, and the total content of the nitrogen elements and the boron elements in the boron nitride nanobelt is higher than 80 wt%; preferably, the boron nitride nanoribbon contains elements of boron, nitrogen, carbon and oxygen; preferably, the thermal conductivity of the boron nitride aerogel film is 0.015-0.5W/mK; preferably, the thickness of the boron nitride aerogel film is 10-3 mm, preferably 50-500 μm, the boron nitride aerogel film has mechanical flexibility without temperature dependence and can be bent, folded or twisted, and the density of the boron nitride aerogel film is 15-750 mg/mL.
8. The boron nitride aerogel phase change film produced by the method of any of claims 1-6, comprising: the boron nitride aerogel film and the phase-change material of claim 7, wherein the boron nitride aerogel film has a three-dimensional porous network formed by winding and overlapping boron nitride nanobelts, and the phase-change material is filled and embedded in the three-dimensional porous network.
9. The boron nitride aerogel phase change film of claim 8, wherein: the shape of the boron nitride aerogel phase-change film comprises a rectangle, a triangle, a circle, a square, a star or an irregular shape; and/or the thickness of the boron nitride aerogel phase-change film is 10-3 mm, preferably 50-500 μm, and/or the boron nitride aerogel phase-change film is electrically insulated, the thermal conductivity of the boron nitride aerogel phase-change film is 0.05-5.0W/mK, and/or the phase-change temperature of the boron nitride aerogel phase-change film is 10-150 ℃, and the enthalpy value of the boron nitride aerogel phase-change film is 10-200J/g;
and/or the content of the boron nitride aerogel film in the boron nitride aerogel phase-change film is 1-90 wt%, and the content of the phase-change material is 10-99 wt%;
and/or the boron nitride aerogel phase-change film has the function of reversible absorption and release of heat energy.
10. Use of the boron nitride aerogel film of claim 7 or the boron nitride aerogel phase change film of claim 8 or 9 in the field of thermal insulation, thermal energy storage and release, portable electronics, or thermal management of wearable electronic systems under 5G technology;
preferably, the application comprises: and embedding the boron nitride aerogel film or the boron nitride aerogel phase-change film into an electronic device to realize heat management.
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