CN112724935A - Sound-heat energy conversion type composite phase change energy storage material and preparation method and application thereof - Google Patents
Sound-heat energy conversion type composite phase change energy storage material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a sound-heat energy conversion type composite phase change energy storage material and a preparation method and application thereof, belonging to the field of composite materials. The phase change energy storage material consists of three-dimensional network frameworks and an organic solid-liquid phase change material filled between the three-dimensional network frameworks, wherein the three-dimensional network frameworks are of a three-dimensional network structure formed by mutually connecting graphene oxide nanosheets loaded with metal oxide nanoparticles on the surfaces. According to the invention, a three-dimensional network in-situ loaded phase-change material is constructed by adopting a one-pot method through coordination and complexation of metal ions and carboxyl functional groups on the surfaces of graphene oxide nanosheets, and then a part of metal ions are subjected to alkalization reduction to generate metal oxide nanoparticles, so that the construction of an acoustic-thermal converter and the compounding of the acoustic-thermal converter and the phase-change material are realized. Has the advantages of simple synthesis process and low energy consumption, and can effectively reduce the production cost.
Description
Technical Field
The invention relates to a sound-heat energy conversion type composite phase change energy storage material and a preparation method and application thereof, belonging to the field of composite materials.
Background
With the development of modern industry, environmental pollution is generated, and noise pollution is one kind of environmental pollution and is a great harm to human beings. The medium is propagated in the form of sound waves in the medium, and when the medium is propagated in the solid medium, internal friction among particles is caused due to viscosity of the medium, so that a part of sound energy is converted into heat energy; meanwhile, due to heat conduction of the medium, heat exchange is carried out between the dense part and the sparse part of the medium, and therefore sound wave attenuation and heat energy generation are achieved. So far, the related research and development of the acoustic-thermal energy conversion material is less, and therefore, the development and preparation of an effective acoustic-thermal energy conversion storage technology is of great significance.
Thermal energy storage is a key factor in improving energy utilization efficiency. Phase Change Materials (PCM), a substance that provides latent heat by changing the state of existence (from liquid to solid, solid to liquid), are the best green and environmentally friendly carriers for energy conservation and environmental protection. The use of PCMs enables the storage and release of large amounts of Energy, and they are therefore widely used in the field of thermal Energy management and storage (m.m.farid, a.m.khudair, s.a.k.razack and s.al-halaj, Energy conversion and management,2004,45,1597-
Disclosure of Invention
Aiming at the key problems of preventing and controlling noise pollution, effectively storing and utilizing heat energy and the like, the invention aims to combine the sound wave attenuation heat generation phenomenon with the phase-change heat collection characteristic of a phase-change material to construct a composite material integrating sound absorption, heat generation and heat storage, and realize the intelligent temperature regulation effect while reducing noise and noise. The construction of the phase-change material with the functions of sound wave absorption and thermal energy storage is an effective way for realizing the acoustic-thermal energy conversion and storage. The graphene oxide is a sound absorption material with great potential due to the inherent corrugated structure on the surface and easy grafting modification, and meanwhile, the graphene oxide is also an ideal phase change component support carrier due to good heat conduction performance. Therefore, the three-dimensional graphene oxide support network is constructed by a sol-gel method, the organic solid-liquid phase change component is coated in situ, and the phase change energy storage material with the graphene network structure is designed and prepared, so that the problem of liquid leakage of the phase change material can be solved, and the material is endowed with the acousto-thermal conversion capability. In addition, the porosity of the three-dimensional graphene oxide network is regulated and controlled to realize directional reduction of sound waves with different frequencies, the method can be used for manufacturing a noise elimination and sound insulation coating, and has important application value in the fields of building sound insulation, external wall heat insulation, noise reduction and energy conservation and the like.
The invention aims to provide a composite phase change energy storage material with the sound-heat energy conversion effect and the heat energy storage utilization. The material integrates sound-heat energy conversion and heat energy storage and utilization, has good heat management capability and simple synthesis process, and has wide application prospect.
The phase change energy storage material consists of three-dimensional network frameworks and an organic solid-liquid phase change material filled between the three-dimensional network frameworks, wherein the three-dimensional network frameworks are of a three-dimensional network structure formed by mutually connecting graphene oxide nanosheets loaded with metal oxide nanoparticles on the surfaces.
The acoustic-thermal energy conversion type composite phase change energy storage material takes a three-dimensional graphene oxide nanosheet network as a sound absorption main body, and realizes the attenuation of sound waves and the conversion of acoustic-thermal energy by cooperating with the thermal vibration effect of metal oxide nanoparticles.
Furthermore, the three-dimensional network framework is formed by bridging graphene oxide nano sheets loaded with metal oxide nano particles, and the graphene oxide nano sheets are connected and built in a random mode to form a three-dimensional network and simultaneously load phase change components in situ.
Preferably, the mass ratio of the three-dimensional network framework to the phase-change material is 1: 5-1: 24.
Preferably, the mass ratio of the graphene oxide nanosheets to the metal oxide nanoparticles in the three-dimensional network framework is 1: 0.5-1: 5.
Preferably, the organic solid-liquid phase change material is at least one of n-dodecanol, n-tetradecanol, n-hexadecanol, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, butyl stearate, methyl palmitate, methyl stearate, octadecyl thioglycolate, acetamide, phorone, polyethylene glycol and polyvinyl alcohol.
Preferably, the metal oxide nanoparticlesIs CaO, MgO, FeO, Fe2O3、Fe3O4、MgO、Al2O3、CuO、BaO、Cr2O3And AgO nanoparticles.
Preferably, the metal oxide nanoparticles are monodisperse nanoparticles having a particle size of 50nm to 100nm and nanoparticle clusters having a particle size of 100nm to 300 nm.
The metal oxide nanoparticles of the present invention are composed of monodisperse nanoparticles and clusters, and particles having a small particle diameter (particle diameter of 50nm to 100nm) are monodisperse nanoparticles, and particles having a large particle diameter (particle diameter of 100nm to 300nm) are nanoparticle clusters.
Preferably, the metal ion is at least one of calcium ion, magnesium ion, ferrous ion, ferric ion, zinc ion, aluminum ion, cupric ion, barium ion, trivalent chromium ion, cobalt ion or silver ion.
The invention also aims to provide a preparation method of the acoustic-thermal energy conversion and thermal energy storage shape-stabilized phase change composite material.
A preparation method of a sound-heat energy conversion and heat energy storage shape-stabilized phase change composite material comprises the following process steps:
firstly, preparing a mixed system of graphene oxide nanosheets and an organic solid-liquid phase change material;
secondly, metal ions are used as a cross-linking agent, and the mixed system obtained in the first step is prepared into the composite phase-change hydrogel by a sol-gel method;
and thirdly, carrying out alkalization reduction on the composite phase-change hydrogel obtained in the second step, standing, and freeze-drying to obtain the acoustic-thermal energy conversion type composite phase-change energy storage material.
The acoustic-thermal conversion phase-change heat storage material realizes the construction of an acoustic-thermal energy conversion type composite phase-change energy storage material and the compounding of the acoustic-thermal energy conversion type composite phase-change energy storage material and the phase-change heat storage material through a one-pot method.
In the technical scheme, the method comprises the steps of mixing an organic solid-liquid phase-change material with 5-10mg/ml of graphene oxide nanosheet dispersion liquid, and uniformly mixing the organic solid-liquid phase-change material and the graphene oxide nanosheet through magnetic stirring, wherein the mass ratio of the organic solid-liquid phase-change material to the graphene oxide nanosheet is 8.5: 1-9.6: 1.
Further, the magnetic stirring time is 1-3 h, and the rotation speed is preferably 2000 r/min.
In the above technical scheme, the metal ions used as the cross-linking agent in the step (II) are added to the mixed system obtained in the step (I) in the form of a metal ion inorganic salt solution.
Further, the metal ion inorganic salt is at least one of chloride, sulfate, nitrate and phosphate of metal ions.
Further, the molar concentration of the metal ion inorganic salt solution is 0.05-1 mol/L.
In the above technical scheme, in the step (c), the reducing agent used in the alkalization reduction is one of ammonia water, hydrazine hydrate, and sodium borohydride.
Further, the mass ratio of the reducing agent to the metal ion crosslinking agent is 5-10: 10-50.
Further, the standing temperature is room temperature, and the standing time is 2-12 hours.
It is a further object of the present invention to provide the use of the above-described acousto-thermal energy conversion and thermal energy storage shape-stabilized phase change composite as an acousto-thermal converter.
Furthermore, the sound-heat energy conversion and heat energy storage shape-stabilized phase change composite material has important application value in the fields of building sound insulation, external wall heat preservation, noise reduction, energy conservation and the like.
The invention has the beneficial effects that: according to the invention, a three-dimensional network in-situ loaded phase-change material is constructed by adopting a one-pot method through coordination and complexation of metal ions and carboxyl functional groups on the surfaces of graphene oxide nanosheets, and then a part of metal ions are subjected to alkalization reduction to generate metal oxide nanoparticles, so that the construction of an acoustic-thermal converter and the compounding of the acoustic-thermal converter and the phase-change material are realized. Has the advantages of simple synthesis process and low energy consumption, and can effectively reduce the production cost.
The composite phase-change material with the sound-heat energy conversion and heat energy storage effects has the characteristics of high energy storage efficiency and stable shape. The effective absorption of the material to sound waves and the heat energy conversion are realized through the dual functions of the graphene three-dimensional network and the metal oxide nanoparticles. In addition, the generation of the metal oxide nano particles further improves the heat conducting property of the composite material and reduces the phase change latent heat loss.
The phase-change material with the sound-heat conversion function is formed by compounding a sound-heat converter and a phase-change material. The three-dimensional graphene network morphology and porosity are effectively regulated and controlled through selection of the type and concentration of the cross-linking agent, and finally directional reduction of sound waves with different frequencies is achieved. In addition, the intelligent regulation and control of the phase-change temperature range can be realized by directionally selecting the organic phase-change energy storage material, and the method has wide application prospect in the fields of building sound insulation, external wall heat preservation, noise reduction, energy conservation and the like.
Drawings
FIG. 1 shows GO and Fe in example 13O4-GO、PEG/Fe3O4-Scanning Electron Microscopy (SEM) images of GO.
FIG. 2 shows Fe in example 12+,3+-GO、Fe3O4Transmission Electron Microscopy (TEM) in GO.
FIG. 3 shows PEG/Fe in example 12+,3+-GO、PEG/Fe3O4Sweep rheology profile of GO hydrogel.
FIG. 4 shows Fe in example 13O4-GO and PEG/Fe3O4GO nitrogen adsorption test.
FIG. 5 shows PEG and PEG/Fe described in example 13O4-digital photo of shape stability of GO composite phase change energy storage material.
FIG. 6 shows PEG and PEG/Fe described in example 13O4-DSC profile of GO composite phase change energy storage material.
FIG. 7 shows PEG and PEG/Fe as described in example 12+,3+-GO、PEG/Fe3O4And testing the thermal conductivity performance of the GO composite phase change energy storage material.
FIG. 8 shows PEG/Fe in example 13O4-sound absorption coefficient (a) and acoustic-thermal conversion curve (b) of GO composite phase change energy storage material.
Fig. 9 is a schematic diagram of the acoustic-thermal energy conversion type composite phase change energy storage material mechanism of the present invention. The composite phase change energy storage material prepared by the invention has a structure shown in the figure, graphene oxide nanosheets are mutually connected through the bridging action of metal ions to form a three-dimensional sound wave absorption network, metal oxide nanoparticles are loaded on the graphene oxide nanosheets, the sound absorption effect of the graphene nanosheets is cooperated with the network structure and the enhancement effect of functional nanoparticles on sound wave reflection and scattering, and the effective conversion from sound waves to heat energy is realized. Meanwhile, the phase change component is uniformly filled between the graphene nanosheet layer and the three-dimensional network, and the continuous graphene heat conduction network can immediately transmit the generated heat to the phase change component, so that the effective storage of the heat energy is realized.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
1. And adding 5.0g of PEG-6000 and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring for 2 hours at the rotating speed of 2000r/min to uniformly mix the mixture to obtain a mixed system of the PEG-6000 phase-change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at 2000r/min, dripping 1ml of Fe into the mixed system obtained in the step (1)2+With Fe3+FeCl with total concentration of 0.5mol/L2And FeCl3(the molar ratio is 1:2) mixing a solution crosslinking agent, and carrying out coordination crosslinking reaction on metal ions and carboxyl of graphene oxide nanosheets to form gel so as to obtain a graphene oxide composite phase-change gel system;
3. 150ul of substances are dripped into the graphene oxide composite phase-change gel systemNH in an amount fraction of 40%3H2O, so that partial metal ions are converted into Fe with the particle size of 50-100nm through alkalization3O4Nanoparticles and Fe with particle size of 100-300nm3O4Nano particle clusters are generated in situ in a graphene oxide composite phase change gel system, and the PEG/Fe phase change composite material for sound-heat energy conversion and heat energy storage shaping is obtained after standing for 4h and freeze drying3O4-GO。
The composite phase change energy storage material is subjected to morphology characterization by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM). The natural stacking of graphene oxide nanoplatelets into a film is shown in fig. 1 a. After the metal ions are crosslinked, as shown in fig. 1b and fig. 2a, the graphene oxide nanosheets are connected with each other to form a network. While the pore size and the number of the composite phase change energy storage material finally obtained in fig. 1c are obviously reduced, proving the effective load of the phase change material. The combination of the spherical nanoparticles formed in the transmission electron microscope results in FIG. 2 demonstrates Fe3O4In situ generation of nanoparticles. .
Under the condition of room temperature, the obtained PEG/Fe is subjected to rheometer rotation2+,3+-GO、PEG/Fe3O4The GO hydrogel system was subjected to rheological characterization, as shown in FIG. 3, the storage modulus (G ') of both gel systems was consistently higher than the loss modulus (G'), indicating Fe2+、Fe3+Ion and graphene oxide are subjected to coordination crosslinking to obtain PEG/Fe2+,3+-formation of GO gel and PEG/Fe after reduction with ammonia3O4-retention of GO gel system.
For Fe at room temperature3O4-GO and PEG/Fe3O4The GO system was tested for nitrogen adsorption. The results are shown in FIG. 4, PEG/Fe3O4The adsorption amount of GO is obviously reduced, which indicates that the phase change component PEG-6000 is effectively filled.
The shaping effect of the composite phase change material is tested at 60 ℃, and figure 5 shows that PEG/Fe3O4the-GO composite phase change energy storage material has excellent shape stability, and does not leak at 60 ℃.
Using differential scanning calorimetry technique to perform doublingDSC test is carried out on the phase-change material, and the result is shown in figure 6, wherein PEG/Fe3O4The phase change enthalpy value of the-GO composite phase change energy storage material is 150-170J/g, so that the practical application of the phase change energy storage coating is guaranteed.
The thermal conductivity of the composite phase change material is measured under the room temperature condition, and compared with pure PEG (2.5), the thermal conductivity of the composite phase change energy storage material can reach 3.8W/(m.K). Indicates Fe3O4The generation of the nano particles effectively improves the heat conducting property of the material.
The sound absorption coefficient test (figure 8a) and the sound-heat conversion performance test (figure 8b) show that the PEG/Fe is subjected to room temperature3O4-GO composite phase change energy storage material in graphene oxide network and Fe3O4The sound-heat energy conversion capability of the nano particles under the double action is further improved.
Example 2
1. And adding 5.0g of PEG-4000 and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring for 2 hours at the rotating speed of 2000r/min to uniformly mix the mixture to obtain a mixed system of the PEG-4000 phase change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at 2000r/min, dripping 1ml of Fe into the mixed system obtained in the step (1)2+With Fe3+FeCl with total concentration of 0.5mol/L2And FeCl3(the molar ratio is 1:2) mixing a solution crosslinking agent, and carrying out coordination crosslinking reaction on metal ions and carboxyl of graphene oxide nanosheets to form gel so as to obtain a graphene oxide composite phase-change gel system;
3. 150ul of NH with the mass fraction of 40 percent is dripped into the graphene oxide composite phase-change gel system3H2O, so that partial metal ions are converted into Fe with the particle size of 50-100nm through alkalization3O4Nanoparticles and Fe with particle size of 100-300nm3O4Generating nano particle clusters in situ in a graphene oxide composite phase change gel system, standing for 4h, and freeze-drying to obtain the PEG-4000/Fe phase change composite material with the functions of sound-heat energy conversion and heat energy storage and shaping3O4-GO。
Example 3
1. And adding 5.0g of PEG-8000 and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring for 2 hours at the rotating speed of 2000r/min to uniformly mix the mixture to obtain a mixed system of the PEG-8000 phase change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at 2000r/min, dripping 1ml of Fe into the mixed system obtained in the step (1)2+With Fe3+FeCl with total concentration of 0.5mol/L2And FeCl3(the molar ratio is 1:2) mixing a solution crosslinking agent, and carrying out coordination crosslinking reaction on metal ions and carboxyl of graphene oxide to form gel so as to obtain a graphene oxide composite phase-change gel system;
3. 150ul of NH with the mass fraction of 40 percent is dripped into the graphene oxide composite phase-change gel system3H2O, so that partial metal ions are converted into Fe with the particle size of 50-100nm through alkalization3O4Nanoparticles and Fe with particle size of 100-300nm3O4Generating nano particle clusters in situ in a graphene oxide composite phase change gel system, standing for 4h, and freeze-drying to obtain the PEG-8000/Fe phase change composite material with the functions of sound-heat energy conversion and heat energy storage and shaping3O4-GO。
Example 4
1. And adding 5.0g of PEG-6000 and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring for 2 hours at the rotating speed of 2000r/min to uniformly mix the mixture to obtain a mixed system of the PEG-6000 phase change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at 2000r/min, 1ml of AlCl with the concentration of 0.5mol/L is dripped into the mixed system obtained in the step (1)3The metal ions and the carboxyl of the graphene oxide are subjected to coordination crosslinking reaction to form gel, so that a graphene oxide composite phase change gel system is obtained;
3. 150ul of NH with the mass fraction of 40 percent is dripped into the graphene oxide composite phase-change gel system3H2O, so that part of metal ions are converted into Al with the particle size of 50-100nm through alkalization2O3Nano meterThe particles are generated in situ in a graphene oxide composite phase change gel system, and the PEG/Al composite material for sound-heat energy conversion and heat energy storage shaping phase change is obtained after standing for 4 hours at room temperature and freeze drying2O3-GO。
Example 5
1. And adding 5.0g of PEG-8000 and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring for 2 hours at the rotating speed of 2000r/min to uniformly mix the mixture to obtain a mixed system of the PEG-8000 phase change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at the rotating speed of 2000r/min, FeCl with the volume of 1ml and the concentration of 0.5mol/L is dripped into the mixed system obtained in the step (1)2The metal ions and the carboxyl of the graphene oxide are subjected to coordination crosslinking reaction to form gel, so that a graphene oxide composite phase change gel system is obtained;
3. 150ul of NH with the mass fraction of 40 percent is dripped into the graphene oxide composite phase-change gel system3H2And O, alkalizing partial metal ions to convert the metal ions into FeO nanoparticles with the particle size of 50-100nm and FeO nanoparticle clusters with the particle size of 100-300nm respectively, generating the FeO nanoparticles in situ in a graphene oxide composite phase change gel system, standing for 4 hours at room temperature, and performing a freeze drying step to obtain the sound-heat energy conversion and heat energy storage shape-stabilized phase change composite material PEG/FeO-GO.
Example 6
1. And adding 5.0g of paraffin and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring for 2 hours at the rotating speed of 2000r/min to uniformly mix the paraffin and the graphene oxide nanosheet dispersion liquid to obtain a mixed system of the paraffin phase-change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at the rotating speed of 2000r/min, 1ml of CuCl with the concentration of 0.5mol/L is dripped into the mixed system obtained in the step (1)2The metal ions and the carboxyl of the graphene oxide are subjected to coordination crosslinking reaction to form gel, so that a graphene oxide composite phase change gel system is obtained;
3. 150ul of NH with the mass fraction of 40 percent is dripped into the graphene oxide composite phase-change gel system3H2And O, converting partial metal ions into CuO nano particles and clusters with the particle sizes of 50-100nm and 100-200nm respectively through alkalization, generating the CuO nano particles and the clusters in situ in a graphene oxide composite phase change gel system, standing for 4 hours at room temperature, and performing freeze drying to obtain the sound-heat energy conversion and heat energy storage shape-stabilized phase change composite material.
Example 7
1. And adding 5.0g of paraffin and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring for 2 hours at the rotating speed of 2000r/min to uniformly mix the paraffin and the graphene oxide nanosheet dispersion liquid to obtain a mixed system of the paraffin phase-change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at the rotating speed of 2000r/min, FeCl with the volume of 1ml and the concentration of 0.5mol/L is dripped into the mixed system obtained in the step (1)3The metal ions and the carboxyl of the graphene oxide are subjected to coordination crosslinking reaction to form gel, so that a graphene oxide composite phase change gel system is obtained;
3. 150ul of hydrazine hydrate reducing agent with the mass fraction of 40% is dripped into the graphene oxide composite phase-change gel system, so that part of metal ions are converted into Fe with the particle sizes of 50-100nm respectively through alkalization2O3Nanoparticles and Fe with particle size of 100-300nm2O3And (3) generating nano particle clusters in situ in a graphene oxide composite phase change gel system, standing for 4 hours at room temperature, and freeze-drying to obtain the acoustic-thermal energy conversion and thermal energy storage shape-stabilized phase change composite material.
Example 8
1. And adding 5.0g of dodecanol and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring at the rotating speed of 2000r/min for 2 hours to uniformly mix the dodecanol and the graphene oxide nanosheet dispersion liquid to obtain a mixed system of the dodecanol phase-change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at the rotating speed of 2000r/min, FeCl with the volume of 1ml and the concentration of 0.5mol/L is dripped into the mixed system obtained in the step (1)3The metal ions and the carboxyl of the graphene oxide are subjected to coordination crosslinking reaction to form gel, so that a graphene oxide composite phase change gel system is obtained;
3. 150ul of NH with the mass fraction of 40 percent is dripped into the graphene oxide composite phase-change gel system3H2O, so that part of metal ions are converted into Fe with the particle sizes of 50-100nm respectively through alkalization2O3Nanoparticles and Fe with particle size of 100-300nm2O3And (3) generating nano particle clusters in situ in a graphene oxide composite phase change gel system, standing for 4 hours at room temperature, and freeze-drying to obtain the acoustic-thermal energy conversion and thermal energy storage shape-stabilized phase change composite material.
Example 9
1. Adding 5.0g of tetradecanol and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring for 2 hours at the rotating speed of 2000r/min to uniformly mix the tetradecanol phase-change material and the graphene oxide nanosheet dispersion liquid to obtain a mixed system of the tetradecanol phase-change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at the rotating speed of 2000r/min, 1ml of CuCl with the concentration of 0.5mol/L is dripped into the mixed system obtained in the step (1)2The metal ions and the carboxyl of the graphene oxide are subjected to coordination crosslinking reaction to form gel, so that a graphene oxide composite phase change gel system is obtained;
3. and (2) dropwise adding 150ul of hydrazine hydrate reducing agent with the mass fraction of 40% into the graphene oxide composite phase-change gel system, so that part of metal ions are converted into CuO nanoparticles with the particle size of 50-100nm and CuO nanoparticle clusters with the particle size of 100-300nm through alkalization, the CuO nanoparticles are generated in situ in the graphene oxide composite phase-change gel system, standing for 4 hours at room temperature, and performing freeze drying to obtain the sound-heat energy conversion and heat energy storage shape-stabilized phase-change composite material.
Example 10
1. And adding 5.0g of hexadecanol and 5.0ml of graphene oxide nanosheet dispersion liquid with the concentration of 5.0mg/ml into a 20ml beaker, and magnetically stirring for 2 hours at 2000r/min to uniformly mix the mixture to obtain a mixed system of the hexadecanol phase-change material and the graphene oxide nanosheet dispersion liquid.
2. Under the condition of magnetic stirring at the rotating speed of 2000r/min, 1ml of TiCl with the concentration of 0.5mol/L is added into the mixed system obtained by the step (1)3Crosslinking agents, metal ions and oxidized stonesCarrying out coordination crosslinking reaction on carboxyl of graphene to form gel, and obtaining a graphene oxide composite phase change gel system;
3. 150ul of hydrazine hydrate reducing agent with the mass fraction of 40 percent is dripped into the graphene oxide composite phase-change gel system, so that part of metal ions are converted into Ti with the particle sizes of 50-100nm respectively through alkalization2O3Nanoparticles and Ti with particle size of 100-300nm2O3And (3) generating nano particle clusters in situ in a graphene oxide composite phase change gel system, standing for 4 hours at room temperature, and freeze-drying to obtain the acoustic-thermal energy conversion and thermal energy storage shape-stabilized phase change composite material.
Claims (9)
1. An acoustic-thermal energy conversion type composite phase change energy storage material is characterized in that: the phase change energy storage material is composed of three-dimensional network frameworks and organic solid-liquid phase change materials filled among the three-dimensional network frameworks, and the three-dimensional network frameworks are three-dimensional network structures formed by mutually connecting and building oxidized graphene nanosheets loaded with metal oxide nanoparticles on the surfaces.
2. The material of claim 1, wherein: the graphene oxide nanosheets with the metal oxide nanoparticles loaded on the surfaces thereof are connected with each other through the bridging effect of metal ions.
3. The material of claim 1, wherein: the mass ratio of the three-dimensional network framework to the phase-change material is 1: 5-1: 24; the mass ratio of the graphene oxide nanosheets to the metal oxide nanoparticles in the three-dimensional network framework is 1: 0.5-1: 5.
4. The material of claim 1, wherein: the organic solid-liquid phase change material is at least one of n-dodecanol, n-tetradecanol, n-hexadecanol, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, butyl stearate, methyl palmitate, methyl stearate, octadecyl thioglycolate, acetamide, phorone, polyethylene glycol and polyvinyl alcohol.
5. The material of claim 1, wherein: the metal oxide nano particles are CaO, MgO, FeO and Fe2O3、Fe3O4、MgO、Al2O3、CuO、BaO、Cr2O3And AgO nanoparticles.
6. The material according to claim 1 or 5, characterized in that: the metal oxide nanoparticles are monodisperse nanoparticles with the particle size of 50 nm-100 nm and nanoparticle clusters with the particle size of 100 nm-300 nm.
7. The material according to claim 2 or 5, characterized in that: the metal ions are at least one of calcium ions, magnesium ions, ferrous ions, ferric ions, zinc ions, aluminum ions, cupric ions, barium ions, trivalent chromium ions, cobalt ions or silver ions.
8. A preparation method of the acoustic-thermal energy conversion type composite phase change energy storage material as claimed in any one of claims 1 to 7, wherein the preparation method comprises the following steps: the method comprises the following process steps:
preparing a mixed system of graphene oxide nanosheets and an organic solid-liquid phase change material;
secondly, metal ions are used as a cross-linking agent, and the mixed system obtained in the first step is prepared into the composite phase-change hydrogel by a sol-gel method;
and thirdly, carrying out alkalization reduction on the composite phase-change hydrogel obtained in the second step, standing, and freeze-drying to obtain the acoustic-thermal energy conversion type composite phase-change energy storage material.
9. Use of the acousto-thermal energy conversion type composite phase change energy storage material according to any one of claims 1 to 7 as an acousto-thermal converter.
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