CN103923620A - Preparation method of heat storage composite material based on nanoparticle electromagnetic wave absorption - Google Patents
Preparation method of heat storage composite material based on nanoparticle electromagnetic wave absorption Download PDFInfo
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- 239000002131 composite material Substances 0.000 title abstract 2
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of a heat storage composite material based on nanoparticle electromagnetic wave absorption. The method comprises the steps of uniformly dispersing nanoparticles with plasma resonance absorption characteristics to a heat storage material matrix through the steps of performing surface modification on the nanoparticles and performing controllable dispersion on the nanoparticles in the heat storage material matrix to prepare a nano composite heat storage material. Compared with the prior art, the method has the characteristics that electromagnetic waves can be directly converted into heat energy, and the heat storage material can be quickly, uniformly and efficiently heated on the premise of unchanging excellent thermophysical property of the heat storage material.
Description
Technical field
The invention belongs to preparation and the applied technical field of functional nano matrix material, especially relate to a kind of preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave.
Background technology
Thermal energy storage is the important component part of energy science and technology.Energy storage technology can solve energy supply and demand unmatched contradiction on time and space, thereby it is the effective means that improves energy utilization rate.Thermal energy storage industry and civilian in of many uses, occupy extremely important status in energy storage technology field.Sun power has the feature of huge energy, distribution on global and spatter property, makes full use of sun power and has also become current development focus.Thermmal storage material is to exploitation and effectively utilize renewable energy solar energy most important.
Traditional affects and has limited its thermmal storage speed and efficiency because there is the shortcoming that thermal conductivity is little based on thermal conduction mechanism heat accumulating.In existing energy storage material and technology, people select, to adding in heat accumulating metallic substance that thermal conductivity is higher or graphite, carbon nanotube etc. to improve material monolithic thermal conductivity, to use to improve and fill thermal velocity and heating uniformity thereof.The thermal conductivity that effectively improves heat accumulating needs a large amount of additives, and this tends to sacrifice the ability premium properties of matrix heat accumulating, has also greatly increased cost simultaneously.Simultaneously, the current thermmal storage material that fills heat engine system based on thermal conduction, generally all cannot directly absorb sun power and be translated into heat energy, but first solar energy converting is become to heat energy, by thermal conduction, heat accumulating is filled to heat again, cause final photo-thermal conversion efficiency low, and fill thermal velocity and homogeneity is all undesirable.
Summary of the invention
Object of the present invention is exactly to provide a kind of light and heat energy transformation efficiency high in order to overcome the defect that above-mentioned prior art exists, the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave of thermmal storage excellent in efficiency.
Object of the present invention can be achieved through the following technical solutions:
The preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave, the nano particle with plasma resonance absorption characteristic is evenly spread to and in heat accumulating matrix, prepares nano combined heat accumulating, specifically by nanoparticle surface modified, in thermmal storage material matrix, controlled dispersion prepares, adopt following steps:
(1) finishing technique: to solvent, then add surface modified active agent to above-mentioned mixing solutions by dispersed the nano particle with electromaganic wave absorbing property, with solvent washing, be finally re-dispersed in solvent after centrifugal being precipitated;
(2) dispersing technology: heat accumulating matrix heat fused is extremely liquid, or to the solution that adds step (1) to prepare in liquid stored material matrix, continuous heating stirs until solvent evaporates is complete, then cool to room temperature, obtains the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave.
The described nano particle with electromaganic wave absorbing property is to have the metal of electromaganic wave absorbing property or the nano particle of its alloy or nonmetal inorganics, comprises gold and silver, platinum or its alloy, graphite, carbon nanotube, Graphene or lead selenide.Nanoparticle size is nano material in broad sense, and particle morphology can be spherical, bar-shaped, trilateral, tubulose, sheet etc., and morphology of particles comprises single chemical composition and nucleocapsid structure etc.
Described heat accumulating matrix is little to electromagnetic scattering, is transparent organic thermmal storage material or inorganic salts thermmal storage material.As preferred embodiment, transparent organic thermmal storage material is transparent paraffin, organic silicone oil or vegetables oil, and inorganic salts thermmal storage material is sodium-chlor and the calcium chloride of SODIUMNITRATE, sodium sulfate or mixing.
Solvent described in step (1) is water, ethanol, Virahol, toluene, chloroform, tetrahydrofuran (THF) or normal hexane.Described surface modified active agent, for different because of thermmal storage body material character, is the mercaptan with water-soluble ionization carboxylate radical, oil soluble aliphatics mercaptan part or molecule or the polymer close with structure with heat accumulating matrix chemical composition.
As preferred embodiment, the described mercaptan with water-soluble ionization carboxylate radical is that 11-dredges base undecanoic acid or sulfydryl-polyoxyethylene glycol, described oil soluble aliphatics mercaptan part is the alkanethiol taking positive Dodecyl Mercaptan as representative, the described molecule close with structure with heat accumulating matrix chemical composition or polymer be with the akin oleic acid of transparent paraffin or oleyl amine or with polydimethyl silane polymer or the Polymethylphenylsilane polymer of the akin end of organic silicone oil with carboxyl or sulfydryl.Absorption or bonding action between this type of coating materials its end group of one side and nanoparticle surface are strong, simultaneously similar to heat accumulating matrix chemical composition again, effectively reduce the adelphotaxy between nano particle, ensured dispersed in matrix of nano particle.The photo-thermal conversion of the nano particle that the thermmal storage matrix material utilization preparing contains is carried out Quick uniform and is filled heat: in the time that electromagnetic wave irradiation arrives nano combined heat accumulating, equally distributed nano particle electromagnetic wave absorption, and be converted into heat energy, the heat producing around conducts in heat-storage medium to it, heat accumulating is carried out to Quick uniform and fill heat.
Described hertzian wave is laser wave, visible light wave, sunlight, infrared waves or microwave.
Compared with prior art, the present invention has the following advantages:
(1) adopting the absorption of electromagnetic wave effect of nano particle is heat energy by light energy conversion, and transformation efficiency is high, can approach 100%, thereby the thermmal storage efficiency of prepared nano composite material is high.
(2) present method is because absorption of electromagnetic wave nano particle is uniformly distributed, therefore heating uniformity is better.
(3) the compound thermal stored material to absorption of electromagnetic wave based on nanoparticle, can realize direct absorption and storage to renewable energy solar energy.
(4), because of the small-size effect of nano material with to electromagnetic effective absorption, therefore a small amount of even nanoparticle of trace can significantly improve thermal storage performance, there is low-cost advantage.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of plasma nano gold grain;
Fig. 2 is nano combined heat accumulating average surface temperature graph of a relation over time under laser and solar light irradiation:
Fig. 3 is the heat accumulating average surface temperature over time graph of a relation of tradition based on thermodiffusion under laser and solar light irradiation.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
(1) preparation of gold nano grain
Require HAuCl according to formula
4ultrasonic dissolution is in toluene, add part oleyl amine, heat and stir, pass to nitrogen atmosphere and cold-water reflux, after reacting completely, to adding in mixing solutions, methyl alcohol normal hexane mixing solutions two-forty are centrifugal again, remove supernatant liquor, gained nano particle is dispersed in toluene again, and nano particle diameter is about 8 ± 1nm, and its transmission electron microscope photo as shown in Figure 1.
(2) preparation of nano combined heat accumulating
(3) by transparent paraffin heat accumulating heating and melting, add a certain amount of gold solution and follow stirring, and continuous heating for some time, so that toluene fully volatilizees.After cooling, obtain the equally distributed nano combined heat accumulating of gold nano grain.
(4) utilize the photo-thermal of nm gold particles to change heat accumulating is carried out to Quick uniform and fill heat
(5) nano combined heat accumulating being added in glass cuvette, is 1000w/m by green laser and the normal intensity of wavelength 532nm respectively
2the nano combined heat accumulating of simulated solar rayed, its average surface temperature changes and is shown in Fig. 2.At laser prolonged exposure, after 200 seconds, nano combined heat accumulating surface temperature rises to rapidly approximately 35 DEG C, has realized heat accumulating to fill fast heat.After 10 minutes, stop laser radiation, nano combined thermmal storage material temperature reduces rapidly, has realized the quick heat release of heat accumulation.Under the irradiation of simulated solar irradiation, the surface temperature of nano combined thermmal storage material rose to 70 DEG C from 16 DEG C in 1 minute, had realized quick conversion and storage to renewable sun power.
Comparative example 1
For the advantage of outstanding this technology, nano composite material is replaced by Aluminium Foil Package and overlays on heat accumulating front end, be 1000w/m by green laser and the normal intensity of wavelength 532nm respectively
2the nano combined heat accumulating of simulated solar rayed, its average surface temperature changes and is shown in Fig. 3.Under same laser and solar light irradiation condition, the surface temperature of the coated thermmal storage material of black aluminium foil based on traditional thermodiffusion mechanism rises to respectively 25 DEG C and 42 DEG C, has shown lower temperature rise rate, photo-thermal conversion and efficiency of storage.As we know from the figure, adopt its rate of heating of gold nano grain thermal energy storage material of this technology and heating uniformity to be all significantly better than the aluminium foil coated heat accumulating of tradition based on thermal conduction mechanism.
Embodiment 2
(1) preparation of gold nano grain
Require HAuCl according to formula
4ultrasonic dissolution is in toluene, add part oleyl amine, heat and stir, pass to again nitrogen atmosphere and cold-water reflux, after reacting completely, to adding in mixing solutions, methyl alcohol normal hexane mixing solutions two-forty are centrifugal, remove supernatant liquor, gained nano particle is dispersed in toluene again, and nano particle diameter is about 10 ± 2nm.
(2) finishing of gold nano grain
In the gold nano grain dispersion soln of aforementioned acquisition, add the polydimethyl silane polymer of a certain amount of end with sulfydryl, heat and stir, and pass into nitrogen and reflux 12 hours, by adding methyl alcohol by the gold nano grain precipitation of modifying in reacted solution, after high speed centrifugation, be again dispersed in toluene solvant.
(3) preparation of nano combined heat accumulating
Gold nano grain after modifying and transparent organic silicone oil heat accumulating are uniformly mixed, heating for some time, toluene are fully volatilized.After cooling, obtain the equally distributed nano combined heat accumulating of gold nano grain.
(4) utilize the photo-thermal of nm gold particles to change heat accumulating is carried out to Quick uniform and fill heat
Nano combined heat accumulating is added in glass cuvette, is 1000w/m by green laser and the normal intensity of wavelength 532nm respectively
2the nano combined heat accumulating of simulated solar rayed, take means identical with similar with embodiment 1 to characterize the Modified bitumen of matrix material.
Embodiment 3
The preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave, the nano particle with plasma resonance absorption characteristic is evenly spread to and in heat accumulating matrix, prepares nano combined heat accumulating, specifically by nanoparticle surface modified, in thermmal storage material matrix, controlled dispersion prepares, adopt following steps:
(1) finishing technique: the even carbon nanotube with electromaganic wave absorbing property is dispersed in alcohol solvent, again above-mentioned mixing solutions is added in carboxyl-polyoxyethylene glycol surface modified active agent solution, be precipitated, after centrifugal, with solvent washing, be finally re-dispersed in solvent;
(2) dispersing technology: the carbon nano-tube solution of the finishing of acquisition is mixed with organic silicone oil, and continuous heating stirs until solvent evaporates is complete, and then cool to room temperature obtains the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave.
The photo-thermal conversion of the nano particle that the thermmal storage matrix material utilization preparing contains is carried out Quick uniform and is filled heat: work as hertzian wave, for example laser wave, visible light wave, sunlight, when infrared waves or microwave irradiation arrive nano combined heat accumulating, equally distributed nano particle electromagnetic wave absorption, and be converted into heat energy, the heat producing around conducts in heat-storage medium to it, heat accumulating is carried out to Quick uniform and fill heat.
Embodiment 4
The preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave, the nano particle with plasma resonance absorption characteristic is evenly spread to and in heat accumulating matrix, prepares nano combined heat accumulating, specifically by nanoparticle surface modified, in thermmal storage material matrix, controlled dispersion prepares, adopt following steps:
(1) finishing technique: will there is the nano particle of electromaganic wave absorbing property, for example lead selenide nano particle is dispersed to chloroform solvent, again above-mentioned mixing solutions is added in surface modified active agent oleic acid solutions, absorption or bonding action between this type of coating materials its end group of one side and nanoparticle surface are strong, simultaneously similar to heat accumulating matrix chemical composition again, effectively reduce the adelphotaxy between nano particle, ensure dispersed in matrix of nano particle, the precipitation obtaining is used solvent washing after centrifugal, finally be re-dispersed in solvent,
(2) dispersing technology: by transparent heat accumulating matrix heating paraffin fusing, the solution that adds wherein step (1) to prepare, continuous heating stirs until solvent evaporates is complete, and then cool to room temperature obtains the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave.
The photo-thermal conversion of the nano particle that the thermmal storage matrix material utilization preparing contains is carried out Quick uniform and is filled heat: work as hertzian wave, for example laser wave, visible light wave, sunlight, when infrared waves or microwave irradiation arrive nano combined heat accumulating, equally distributed nano particle electromagnetic wave absorption, and be converted into heat energy, the heat producing around conducts in heat-storage medium to it, heat accumulating is carried out to Quick uniform and fill heat.
Embodiment 5
The preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave, the nano particle with plasma resonance absorption characteristic is evenly spread to and in heat accumulating matrix, prepares nano combined heat accumulating, specifically by nanoparticle surface modified, in thermmal storage material matrix, controlled dispersion prepares, adopt following steps:
(1) finishing technique: by dispersed the graphite nanoparticles with electromaganic wave absorbing property to tetrahydrofuran solvent, again above-mentioned mixing solutions is added in the polydimethyl silane macromolecular surface modification activator solution of end with carboxyl or sulfydryl, be precipitated, after centrifugal, with solvent washing, be finally re-dispersed in solvent;
(2) dispersing technology: to the solution that adds step (1) to prepare in transparent organic silicon oil base body, continuous heating stirs until solvent evaporates is complete, then cool to room temperature, obtains the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave.
The photo-thermal conversion of the nano particle that the thermmal storage matrix material utilization preparing contains is carried out Quick uniform and is filled heat: work as hertzian wave, for example laser wave, visible light wave, sunlight, when infrared waves or microwave irradiation arrive nano combined heat accumulating, equally distributed nano particle electromagnetic wave absorption, and be converted into heat energy, the heat producing around conducts in heat-storage medium to it, heat accumulating is carried out to Quick uniform and fill heat.
Embodiment 6
The preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave, the nano particle with plasma resonance absorption characteristic is evenly spread to and in heat accumulating matrix, prepares nano combined heat accumulating, specifically by nanoparticle surface modified, in thermmal storage material matrix, controlled dispersion prepares, adopt following steps:
(1) finishing technique: by dispersed the nano-platinum particle with electromaganic wave absorbing property to normal hexane solvent, again above-mentioned mixing solutions is added 11-to dredge in base undecanoic acid surface modified active agent solution, be precipitated, after centrifugal, with solvent washing, be finally re-dispersed in solvent;
(2) dispersing technology: by heat accumulating matrix SODIUMNITRATE heat fused, the solution that adds wherein step (1) to prepare, continuous heating stirs until solvent evaporates is complete, and then cool to room temperature obtains the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave.
The photo-thermal conversion of the nano particle that the thermmal storage matrix material utilization preparing contains is carried out Quick uniform and is filled heat: work as hertzian wave, for example laser wave, visible light wave, sunlight, when infrared waves or microwave irradiation arrive nano combined heat accumulating, equally distributed nano particle electromagnetic wave absorption, and be converted into heat energy, the heat producing around conducts in heat-storage medium to it, heat accumulating is carried out to Quick uniform and fill heat.
Claims (10)
1. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave, is characterized in that, the method is that the nano particle with plasma resonance absorption characteristic is evenly spread to and in heat accumulating matrix, prepares nano combined heat accumulating.
2. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave according to claim 1, it is characterized in that, the method by nanoparticle surface modified, in thermmal storage material matrix, controlled dispersion prepares, and specifically adopts following steps:
(1) finishing technique: to solvent, then add surface modified active agent to above-mentioned mixing solutions by dispersed the nano particle with electromaganic wave absorbing property, with solvent washing, be finally re-dispersed in solvent after centrifugal being precipitated;
(2) dispersing technology: heat accumulating matrix heat fused is extremely liquid, or to the solution that adds step (1) to prepare in liquid stored material matrix, continuous heating stirs until solvent evaporates is complete, then cool to room temperature, obtains the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave.
3. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave according to claim 1 and 2, it is characterized in that, the described nano particle with electromaganic wave absorbing property is to have the metal of electromaganic wave absorbing property or the nano particle of its alloy or nonmetal inorganics, comprise gold and silver, platinum or its alloy, graphite, carbon nanotube, Graphene or lead selenide.
4. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave according to claim 1 and 2, it is characterized in that, described heat accumulating matrix is little to electromagnetic scattering, is transparent organic thermmal storage material or inorganic salts thermmal storage material.
5. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave according to claim 4, it is characterized in that, described transparent organic thermmal storage material is transparent paraffin, organic silicone oil, polyoxyethylene glycol or vegetables oil, and described inorganic salts thermmal storage material is sodium-chlor and the calcium chloride of SODIUMNITRATE, sodium sulfate or mixing.
6. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave according to claim 2, is characterized in that, the solvent described in step (1) is water, ethanol, Virahol, toluene, chloroform, tetrahydrofuran (THF) or normal hexane.
7. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave according to claim 2, it is characterized in that, surface modified active agent described in step (1), for different because of thermmal storage body material character, is the mercaptan with water-soluble ionization carboxylate radical, oil soluble aliphatics mercaptan part or molecule or the polymer close with structure with heat accumulating matrix chemical composition.
8. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave according to claim 7, it is characterized in that, the described mercaptan with water-soluble ionization carboxylate radical is that 11-dredges base undecanoic acid or sulfydryl-polyoxyethylene glycol, described oil soluble aliphatics mercaptan part is the alkanethiol taking positive Dodecyl Mercaptan as representative, the described molecule close with structure with heat accumulating matrix chemical composition or polymer are and the akin oleic acid of transparent paraffin or oleyl amine, or with the akin end of organic silicone oil with the polydimethyl of carboxyl or Polymethylphenylsilane polymer or end polydimethyl or the Polymethylphenylsilane polymer with sulfydryl.
9. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave according to claim 1 and 2, it is characterized in that, the photo-thermal conversion of the nano particle that the thermmal storage matrix material utilization preparing contains is carried out Quick uniform and is filled heat: in the time that electromagnetic wave irradiation arrives nano combined heat accumulating, equally distributed nano particle electromagnetic wave absorption, and be converted into heat energy, the heat producing around conducts in heat-storage medium to it, heat accumulating is carried out to Quick uniform and fill heat.
10. the preparation method of the thermmal storage matrix material based on nanoparticle absorption of electromagnetic wave according to claim 9, is characterized in that, described hertzian wave is laser wave, visible light wave, sunlight, infrared waves or microwave.
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