CN110270283B - Preparation method of photo-thermal conversion phase change energy storage microcapsule - Google Patents
Preparation method of photo-thermal conversion phase change energy storage microcapsule Download PDFInfo
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- CN110270283B CN110270283B CN201910632598.9A CN201910632598A CN110270283B CN 110270283 B CN110270283 B CN 110270283B CN 201910632598 A CN201910632598 A CN 201910632598A CN 110270283 B CN110270283 B CN 110270283B
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/12—Making microcapsules or microballoons by phase separation removing solvent from the wall-forming material solution
- B01J13/125—Making microcapsules or microballoons by phase separation removing solvent from the wall-forming material solution by evaporation of the solvent
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Abstract
The invention relates to a photo-thermal conversion phase-change energy storage microcapsule which is prepared by taking a two-dimensional material as a base material, constructing an oil phase dispersed two-dimensional material-gold photo-thermal conversion material by a one-step method, mixing the photo-thermal conversion material with paraffin as a core material and adopting a solvent volatilization method. Meanwhile, the method has strong universality, controllable preparation process and higher industrial application value.
Description
Technical Field
The invention relates to the field of microcapsule material preparation, in particular to a preparation method of a photo-thermal conversion phase change energy storage microcapsule.
Background
The phase-change microcapsule is a micro container containing phase-change materials, and the encapsulation technology of the phase-change microcapsule has wide application prospects in the fields of aerospace, buildings, automobiles, environmental protection, textile and clothing, medical sanitation, electronic device cooling, military camouflage and the like. At present, common phase-change microcapsules are applied by utilizing the change of temperature to realize the performance of the microcapsules. In recent years, with the development of technology, a variety of novel phase change microcapsules have been developed. As is well known, light is a naturally occurring substance that can generate heat. If the photo-thermal conversion and the phase change microcapsules can be combined, the comprehensive performance of the microcapsules can be further improved, and the application range of the microcapsules is widened. Chinese patent document CN201710716648.2 discloses a preparation method of a copper/cuprous oxide-coated paraffin microcapsule photo-thermal conversion phase-change energy-storage composite material, which is to wrap paraffin by using copper with high thermal conductivity and cuprous oxide with high light absorption so as to form a photo-thermal conversion phase-change energy-storage microcapsule. The coating is incomplete due to the existence of crystal grains and is easy to damage, and meanwhile, as the coating is used as a shell material, the heat conductivity of the core material is low, so that the heat converted by the shell material cannot be effectively transferred to the core material and is transferred to surrounding media, and energy dissipation is caused.
Few layers of two-dimensional materials and precious metal nanoparticles are known photo-thermal conversion materials, the absorption spectrum range of the two-dimensional materials can cover an ultraviolet-visible-near infrared region, but the two-dimensional materials cannot be dispersed in an oil phase generally, the two-dimensional materials are difficult to be used as core material fillers, the precious metal nanoparticles are generally used as shell material adding materials, the thermal conductivity of the precious metal nanoparticles is high, but the spectral absorption of the precious metal nanoparticles only covers a short-wavelength visible light region, and therefore the mode that a single material and the photo-thermal materials are shell materials has limited utilization of the energy of sunlight.
The document of the publication of the Fabrication of Graphene/TiO2/Paraffin Composite Phase Change Materials for Enhancement of Solar Energy Efficiency in Photocatalysis and tension Heat Storage constructs a Phase Change Energy Storage microcapsule material with Graphene/titanium dioxide as a shell material, and Graphene cannot be coated in the microcapsule, and only can play a role in integrally improving the thermal conductivity. Similarly, the document "Novel stearic acid/graphene core-shell composite microcapsular as a phase change material exhibiting high viscosity state and performance" merely adsorbs graphene on the surface of the phase change material through electrostatic action, and the structure is easy to leak in the repeated phase change process. Therefore, the development of the photo-thermal energy storage material which is complete in coating, not easy to damage and high in efficiency is significant.
Disclosure of Invention
The invention aims to solve the technical problem of developing a preparation method of a photo-thermal conversion phase change energy storage microcapsule. Specifically, the invention relates to a preparation method of a photo-thermal conversion phase-change energy storage microcapsule.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a photo-thermal conversion phase-change energy storage microcapsule is characterized in that an oil phase is dispersed in a two-dimensional material, namely a gold photo-thermal conversion material, is dispersed in a core material, and the phase-change energy storage microcapsule with the photo-thermal conversion characteristic is constructed.
The method comprises the following specific steps:
(1) preparing an oil-phase dispersed photothermal conversion material by a one-step method and dispersing the material in an oil-phase solvent;
(2) then dissolving the phase change material and the shell material in the oil phase solvent to form an oil phase;
(3) preparing a polyvinyl alcohol (PVA) aqueous solution to construct a water phase;
(4) slowly injecting the oil phase into the water phase at room temperature, stirring and emulsifying;
(5) stirring and volatilizing at room temperature after emulsification, washing and drying to obtain the photo-thermal conversion phase change energy storage microcapsule.
The oil phase dispersed photo-thermal conversion material is a PMMA-modified two-dimensional material-gold nanoparticle material.
The concentration of the two-dimensional material organic dispersion liquid is 1 mg/mL-20 mg/mL, the two-dimensional material is graphene oxide, black phosphorus, molybdenum disulfide, bismuth selenide and the like, and the organic solvent is NMP or DMF.
The specific method for preparing the oil-phase photothermal conversion material by the one-step method comprises the following steps: adding a certain amount of chloroauric acid aqueous solution and PMMA organic dispersion liquid into the organic dispersion liquid of the two-dimensional material, and obtaining the PMMA modified two-dimensional material-gold nanoparticle material capable of dispersing oil phase through ultrasound for a certain time.
The concentration of the chloroauric acid aqueous solution is 25mmol/L, and the volume ratio of the added volume to the two-dimensional material dispersion liquid is 0.005-0.05. The concentration of the PMMA organic dispersion liquid is 0.1g/mL, the organic solvent is one or more of toluene, xylene, dichloromethane, chloroform and ethyl acetate, and the volume ratio of the added volume to the two-dimensional material dispersion liquid is 0.005-0.025. The ultrasonic time is 2-10 min.
The oil phase solvent is one or more of toluene, xylene, dichloromethane, chloroform and ethyl acetate. .
The shell material is PMMA, the core material is paraffin, and the mass ratio of the shell material to the core material is 0.25-1.
The molecular weight of the PVA is 2W-10W, and the mass concentration is 2 mg/mL-10 mg/L. The emulsifying and stirring speed is 1000rpm to 3000rpm, and the emulsifying time is 10min to 30 min.
The room-temperature volatilization stirring speed is 300-500 rpm, and the volatilization time is 6-12 h. The invention relates to a photo-thermal conversion phase-change energy storage microcapsule which is prepared by taking a two-dimensional material as a base material, constructing an oil phase dispersed two-dimensional material-gold photo-thermal conversion material through a one-step method, mixing the photo-thermal conversion material with paraffin as a core material and adopting a solvent volatilization method. When the oil phase dispersed two-dimensional material-gold photo-thermal conversion material is prepared by a one-step method, chloroauric acid ions are adsorbed on the surface of the two-dimensional material and are reduced into gold atoms and grow up to form gold nanoparticles under the action of ultrasonic energy, and meanwhile, oxygen in an ester group of PMMA is grafted and modified with the two-dimensional material through covalent action under the action of the ultrasonic energy. In the solvent volatilization process, the shell material PMMA is polymerized again at an oil-water interface along with the volatilization of the solvent to form a shell structure, and the PMMA-modified photo-thermal conversion material cannot move to the oil-water interface along with the PMMA due to large mass and is uniformly dispersed in the core material paraffin, so that the photo-thermal conversion phase-change energy storage microcapsule taking the PMMA as the shell material and the paraffin dispersed with the two-dimensional material-gold photo-thermal conversion material as the core material is finally formed.
Has the advantages that:
compared with the prior art, the technical method is novel, unique, simple and efficient, and the invention not only provides a preparation method of the photo-thermal conversion phase change energy storage microcapsule, but also provides a preparation method of an oil phase dispersed two-dimensional material-gold photo-thermal conversion material. The PMMA modified two-dimensional material-gold photo-thermal conversion material prepared by the invention can be effectively dispersed in an oil phase without aggregation, so that the PMMA modified two-dimensional material can be completely coated in a core material instead of being adsorbed on the surface of a shell material. According to the invention, the high-light-transmittance PMMA is used as a shell material, the oil phase dispersed two-dimensional material-gold photo-thermal conversion material is dispersed in paraffin, gold nanoparticles can enhance the light absorption, and the heat converted by the material can be effectively transferred to the paraffin for storage, and the whole energy storage process is carried out in the phase change material, so that no energy is dissipated.
The microcapsule material according to the present invention has no limitation on its application, and can be applied to currently known fields such as energy chemical industry, phase change thermal conduction, electronics and electrics, and the like. And those skilled in the art will readily appreciate that they may be applied to other possible fields depending on their physical and chemical properties.
Drawings
FIG. 1 is a diagram of the dispersion of an oil phase dispersed two-dimensional material-gold material prepared in example 1 in methylene chloride and toluene;
FIG. 2 is a TEM photograph of the two-dimensional material-gold material prepared in example 1;
FIG. 3 is a microscope picture of the microcapsule prepared in example 2;
FIG. 4 is a thermal performance diagram of the microcapsules prepared in example 3;
FIG. 5 is a photo-thermal energy storage diagram of the microcapsule prepared in example 3;
FIG. 6 is a graph showing the dispersion of the material prepared in comparative example 1 in methylene chloride and toluene.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
Taking 20mL of a 1mg/mL NMP solution of molybdenum disulfide, adding 100 microliters of a 25mmol/L chloroauric acid aqueous solution and 100 microliters of a 0.1g/mL PMMA dichloromethane solution, performing ultrasonic treatment for 2min, centrifuging to obtain an oil-phase dispersed molybdenum disulfide-gold material, and dispersing the material into dichloromethane and toluene respectively, wherein the material is good in dispersibility as shown in figure 1. As shown in fig. 2, gold nanomaterials were grown on the two-dimensional material. Taking 20mL of a DMF (dimethyl formamide) solution of 10mg/mL of graphene oxide, adding 500 microliters of a 25mmol/L chloroauric acid aqueous solution and 200 microliters of a 0.1g/mL PMMA dichloromethane solution, performing ultrasonic treatment for 10min, centrifuging to obtain an oil-phase dispersed graphene oxide-gold material, and dispersing the material into 10mL dichloromethane. 0.5g of PMMA and 2g of paraffin were dissolved in the above solvent to form an oil phase. 0.1g of PVA (molecular weight: 2W) was dissolved in 50mL of water to prepare an aqueous phase. Slowly injecting the oil phase into the water phase, emulsifying for 30min at the rotating speed of 1000rpm, stirring and volatilizing for 6h at the room temperature at the rotating speed of 300rpm after the emulsification is finished, and washing and drying to obtain the photo-thermal conversion phase change microcapsule. As shown in fig. 3, the microcapsule size is 20 microns.
Example 2
Taking 20mL of a 1mg/mL NMP solution of molybdenum disulfide, adding 100 microliters of a 25mmol/L chloroauric acid aqueous solution and 100 microliters of a 0.1g/mL PMMA dichloromethane solution, performing ultrasonic treatment for 2min, centrifuging to obtain an oil-phase dispersed molybdenum disulfide-gold material, and dispersing the material into dichloromethane and toluene respectively, wherein the material is good in dispersibility as shown in figure 1. As shown in fig. 2, gold nanomaterials were grown on the two-dimensional material. Taking 20mL of an NMP solution containing 5mg/mL of bismuth selenide, adding 200 microliters of a 25mmol/L chloroauric acid aqueous solution and 500 microliters of a 0.1g/mL PMMA dichloromethane solution, performing ultrasonic treatment for 5min, centrifuging to obtain an oil-phase bismuth selenide-gold material, and dispersing the material into 20mL dichloromethane. 1g of PMMA and 2g of paraffin were dissolved in the above solvent to form an oil phase. 0.5g of PVA (molecular weight: 10W) was dissolved in 50mL of water to prepare an aqueous phase. Slowly injecting the oil phase into the water phase, emulsifying at 3000rpm for 20min, stirring at 500rpm for volatilization at room temperature for 12h after emulsification, and washing and drying to obtain the photothermal conversion phase change microcapsule. As shown in FIG. 4, the microcapsule has excellent phase change energy storage performance, and as shown in FIG. 5, the temperature rise is obvious in sunlight.
Comparative example 1
Taking 20mL of a 1mg/mL NMP solution of molybdenum disulfide, adding 100 microliters of a 25mmol/L chloroauric acid aqueous solution, performing ultrasonic treatment for 2min, centrifuging, and dispersing the material into dichloromethane and toluene respectively, wherein the material which is not modified by PMMA is completely aggregated as shown in figure 6. Therefore, the photothermal conversion microcapsule material cannot be further prepared.
Claims (10)
1. A preparation method of a photo-thermal conversion phase-change energy-storage microcapsule is characterized in that an oil phase is dispersed in a two-dimensional material-gold photo-thermal conversion material to be dispersed in a core material, and the phase-change energy-storage microcapsule with photo-thermal conversion characteristic is constructed,
the method comprises the following specific steps:
(1) preparing a PMMA modified two-dimensional material, namely a gold nanoparticle material, by a one-step method, and dispersing the gold nanoparticle material in an oil phase solvent;
(2) then dissolving the phase change material and the shell material in the oil phase solvent to form an oil phase;
(3) preparing a polyvinyl alcohol (PVA) aqueous solution to construct a water phase;
(4) slowly injecting the oil phase into the water phase at room temperature, stirring and emulsifying;
(5) stirring and volatilizing at room temperature after emulsification, washing and drying to obtain the photo-thermal conversion phase change energy storage microcapsule.
2. The preparation method of the photo-thermal conversion phase change energy storage microcapsule according to claim 1, wherein: the two-dimensional material is graphene oxide, black phosphorus, molybdenum disulfide and bismuth selenide.
3. The preparation method of the photo-thermal conversion phase change energy storage microcapsule according to claim 1, wherein: the specific method for preparing the oil-phase photothermal conversion material by the one-step method comprises the following steps: adding a certain amount of chloroauric acid aqueous solution and PMMA organic dispersion liquid into the organic dispersion liquid of the two-dimensional material, and obtaining the PMMA modified two-dimensional material-gold nanoparticle material capable of dispersing oil phase through ultrasound for a certain time.
4. The preparation method of the photo-thermal conversion phase change energy storage microcapsule according to claim 3, wherein the preparation method comprises the following steps: the concentration of the two-dimensional material organic dispersion liquid is 1 mg/mL-20 mg/mL, and the organic solvent for dispersing the two-dimensional material is NMP or DMF.
5. The preparation method of the photo-thermal conversion phase change energy storage microcapsule according to claim 3, wherein the preparation method comprises the following steps: the concentration of the chloroauric acid aqueous solution is 25mmol/L, the volume ratio of the added volume to the two-dimensional material dispersion liquid is 0.005-0.05, the concentration of the PMMA organic dispersion liquid is 0.1g/mL, the volume ratio of the added volume to the two-dimensional material dispersion liquid is 0.005-0.025, the organic solvent for dispersing PMMA is one or more of toluene, xylene, dichloromethane, chloroform and ethyl acetate, and the ultrasonic time is 2-10 min.
6. The preparation method of the photo-thermal conversion phase change energy storage microcapsule according to claim 1, wherein: the oil phase solvent is one or more of toluene, xylene, dichloromethane, chloroform and ethyl acetate.
7. The preparation method of the photo-thermal conversion phase change energy storage microcapsule according to claim 1, wherein: the shell material is PMMA, the core material is paraffin, and the mass ratio of the shell material to the core material is 0.25-1.
8. The preparation method of the photo-thermal conversion phase change energy storage microcapsule according to claim 1, wherein: the molecular weight of the PVA is 20000-100000, and the mass concentration of the PVA is 2-10 mg/L.
9. The preparation method of the photo-thermal conversion phase change energy storage microcapsule according to claim 1, wherein: the emulsifying and stirring speed is 1000-3000 rpm, and the emulsifying time is 10-30 min.
10. The preparation method of the photo-thermal conversion phase change energy storage microcapsule according to claim 1, wherein: the room-temperature volatilization stirring speed is 300-500 rpm, and the volatilization time is 6-12 h.
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| CN109536137A (en) * | 2018-11-13 | 2019-03-29 | 中国矿业大学 | Phase-change microcapsule and preparation method thereof a kind of while that there is magnetism and photothermal conversion characteristic |
| CN109609100A (en) * | 2018-12-26 | 2019-04-12 | 上海驰纺材料科技有限公司 | A kind of photothermal composite material and preparation method thereof being provided simultaneously with extinction fever heat storage function |
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| CN107603570A (en) * | 2017-09-15 | 2018-01-19 | 中国科学院过程工程研究所 | Phase-changing energy storage material with photothermal deformation performance and preparation method thereof |
| CN109536137A (en) * | 2018-11-13 | 2019-03-29 | 中国矿业大学 | Phase-change microcapsule and preparation method thereof a kind of while that there is magnetism and photothermal conversion characteristic |
| CN109609100A (en) * | 2018-12-26 | 2019-04-12 | 上海驰纺材料科技有限公司 | A kind of photothermal composite material and preparation method thereof being provided simultaneously with extinction fever heat storage function |
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