CN114395375A - Metal organic framework based photo-thermal composite phase change material and application thereof - Google Patents
Metal organic framework based photo-thermal composite phase change material and application thereof Download PDFInfo
- Publication number
- CN114395375A CN114395375A CN202111676137.5A CN202111676137A CN114395375A CN 114395375 A CN114395375 A CN 114395375A CN 202111676137 A CN202111676137 A CN 202111676137A CN 114395375 A CN114395375 A CN 114395375A
- Authority
- CN
- China
- Prior art keywords
- change material
- organic framework
- phase change
- metal
- optionally
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012782 phase change material Substances 0.000 title claims abstract description 146
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 106
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 230000008859 change Effects 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 100
- 238000003756 stirring Methods 0.000 claims description 23
- 239000011159 matrix material Substances 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 229920000128 polypyrrole Polymers 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- 239000013178 MIL-101(Cr) Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000547 conjugated polymer Polymers 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000013144 Fe-MIL-100 Substances 0.000 claims description 3
- 239000013132 MOF-5 Substances 0.000 claims description 3
- -1 ZIF-67 Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000013118 MOF-74-type framework Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- MOFVSTNWEDAEEK-UHFFFAOYSA-M indocyanine green Chemical compound [Na+].[O-]S(=O)(=O)CCCCN1C2=CC=C3C=CC=CC3=C2C(C)(C)C1=CC=CC=CC=CC1=[N+](CCCCS([O-])(=O)=O)C2=CC=C(C=CC=C3)C3=C2C1(C)C MOFVSTNWEDAEEK-UHFFFAOYSA-M 0.000 claims description 2
- 229960004657 indocyanine green Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000004032 porphyrins Chemical class 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000005338 heat storage Methods 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011232 storage material Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004146 energy storage Methods 0.000 description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000004776 molecular orbital Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012924 metal-organic framework composite Substances 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 230000010399 physical interaction Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/002—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches with controlled internal environment
- A41D13/005—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches with controlled internal environment with controlled temperature
- A41D13/0051—Heated garments
Abstract
The embodiment of the invention relates to the field of phase-change materials, in particular to a metal organic framework based photo-thermal composite phase-change material and application thereof. The phase-change material comprises a metal organic framework based composite phase-change material and a photosensitizer coated on the metal organic framework based composite phase-change material, wherein the metal organic framework based composite phase-change material comprises a porous metal organic framework base body and a phase-change material adsorbed on the surface or in a pore channel of the metal organic framework base body. The photosensitizer adopted by the invention has high-efficiency light absorption performance, and the photosensitive particles realize polymerization growth and uniform coating on the surface and/or in pores of the metal organic framework based composite phase change material, thereby being beneficial to shortening a heat transfer path so as to promote high-efficiency transfer of photo-induced heat to the outside, endowing the composite material with high-efficiency photo-thermal conversion performance, widening the utilization range of a single material to a spectrum, and solving the problem of single functionality of the traditional metal organic framework based phase change heat storage material.
Description
Technical Field
The invention relates to the field of phase-change materials, in particular to a metal organic framework based photo-thermal composite phase-change material and application thereof.
Background
In recent years, as unrecoverable fossil fuels easily cause environmental pollution and energy crisis, renewable, abundant and clean solar energy is expected to replace the fossil fuels, and the energy crisis is relieved. Therefore, the application of solar energy storage has received a wide attention. However, it is difficult to directly and effectively utilize solar energy due to the intermittency and instability of solar radiation. Phase change materials have been used to collect and store solar energy due to the latent heat of the phase change material during phase change. Therefore, the development of phase change material based energy management systems with solar thermal conversion performance is considered to be one of the most promising technologies to overcome solar radiation discontinuities and improve solar energy utilization efficiency.
Currently, various organic compounds (such as polyethylene glycol, esters, and paraffin wax) and inorganic compounds (such as hydroxides, alloys, and salts) have been studied for energy storage. Among the various phase change materials, organic alcohols are one of the most attractive and studied candidates due to their high latent heat, good chemical stability and ideal phase transition temperature. However, leakage of organic alcohol in the molten state limits its large-scale application in the field of thermal energy storage. Currently, most research is focused on the use of microencapsulation to solve the leakage problem of phase change materials. However, the core-shell structure and the preparation process of the microcapsules are complicated. Furthermore, since the shell material hardly contributes to the heat storage properties of the composite phase change material, a high proportion of the shell material in the microcapsules will significantly reduce the enthalpy of phase change of the composite material. As the three-dimensional metal organic framework has high specific surface area and high porosity, the three-dimensional metal organic framework can be used as a porous carrier to realize the encapsulation of the organic alcohol phase-change material, and the leakage problem is effectively solved. However, the organic alcohol has low photothermal conversion efficiency, which limits practical application thereof in the field of solar energy utilization. Therefore, there is a need to develop a metal-organic framework-based photothermal composite phase change material having a high energy storage density and excellent solar thermal conversion performance.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Object of the Invention
In order to solve the technical problems, the invention aims to provide a metal organic framework based photo-thermal composite phase-change material and an application thereof, which solve the problem of function simplification of the metal organic framework based phase-change material in the prior art, solve the problem of easy agglomeration of a photosensitizer used for modifying the phase-change composite material, and overcome the defect of low photo-thermal conversion efficiency of the photo-thermal conversion type phase-change composite material.
Solution scheme
In order to achieve the purpose of the present invention, an embodiment of the present invention provides a metal-organic framework-based photothermal composite phase change material, including a metal-organic framework-based composite phase change material and a photosensitizer coated on the metal-organic framework-based composite phase change material, where the metal-organic framework-based composite phase change material includes a porous metal-organic framework substrate and a phase change material adsorbed on the surface of the metal-organic framework substrate or in a pore channel.
The phase-change material is packaged by the high capillary adsorption force of the metal organic framework matrix, and provides sites for the growth and coating of the photosensitizer, so that the aggregation of photosensitizer particles is avoided, and the functionalization of the structure is realized. The phase-change material of the invention preferentially adopts a solid-liquid phase-change material, can generate solid-liquid phase change under the drive of external temperature to realize the release/absorption of heat energy, and can cooperate with a photosensitizer to play the roles of photo-thermal conversion and heat energy storage.
Furthermore, the pore channels of the metal organic framework based composite phase change material also contain a photosensitizer. The photosensitizer can be uniformly dispersed in pores of the metal organic framework based composite phase change material, and is beneficial to shortening a heat transfer path, so that the high-efficiency transfer of light-induced heat to the outside is promoted.
The photosensitizer is an organic photosensitizer, and is formed by polymerizing a photosensitizer monomer on the surface or pores of the metal-organic framework based composite phase change material under the action of an oxidant. Namely, the photosensitizer monomer is polymerized on the surface of the metal organic framework based composite phase change material, and can be uniformly dispersed and polymerized in the pores of the metal organic framework based composite phase change material, which is beneficial to shortening a heat transfer path, thereby promoting the high-efficiency transfer of photo-initiated heat to the outside.
Further, the photosensitizer is an organic conjugated polymer.
Optionally, the organic conjugated polymer is selected from one or more of organic dye-based polymers and nanoparticle-based polymers.
Further, the organic dye polymer comprises one or more of porphyrin, indocyanine green and heptane.
Further, the nanoparticle polymer comprises one or more of polypyrrole, polydopamine and polyaniline.
Further, the photosensitizer accounts for 2-10% of the weight of the metal organic framework based composite phase change material, optionally 4% -6%, preferably 4%, 5%, 6%.
Further, the metal-organic framework matrix is of a three-dimensional structure; optionally one or more selected from MIL-101(Cr), MIL-100(Fe), ZIF-8, ZIF-67, MOF-5, MOF-74.
Further, the metal organic framework substrate encapsulates the phase change material through capillary adsorption force.
Further, the phase change material is a solid-liquid phase change material, optionally selected from one or more of fatty alcohol, fatty acid, n-alkane and paraffin; optionally, the fatty alcohol comprises stearyl alcohol. Wherein, the weight percentage of each phase-change material is adjustable.
Further, the phase change material accounts for 60-80%, optionally 65-80%, optionally 70% of the total weight of the metal-organic framework based composite phase change material.
Further, the preparation method comprises the following steps: immersing the metal organic framework-based composite phase-change material into an oxidant solution, adding a photosensitizer monomer according to the amount to realize polymerization reaction, stirring for 1-20 h, centrifuging, and drying to obtain the organic photosensitizer-coated photo-thermal composite phase-change material;
optionally, the weight ratio of the metal-organic framework-based composite phase change material to the photosensitizer monomer is 100: 4-6, optionally 100:4, 100:5, 100: 6.
Optionally, in the polymerization reaction, the stirring time is 5-10 h, optionally 8 h.
Alternatively, in the polymerization reaction, the stirring condition is vigorous stirring, alternatively, the stirring speed is 800r/min, and a magnetic stirrer can be used for stirring.
Alternatively, in the polymerization reaction, stirring is carried out at room temperature.
Optionally, the oxidant is selected from one or more of ferric chloride, hydrogen peroxide, ammonium persulfate and potassium permanganate.
Further, the concentration of the oxidizing agent is 0.5% to 2%, optionally 1%.
Optionally, the preparation method of the metal-organic framework matrix powder comprises the following steps: adding a hydrated metal salt solution into a solution of an organic ligand and an alkali, mixing, transferring into a reaction kettle, treating at 160-180 ℃ for 5-20 h, and drying; optionally, the hydrated metal salt and the organic ligand are in a molar ratio of 1:0.5 to 1.5, optionally in a molar ratio of 1: 1.
Further, the metal organic framework based composite phase change material is prepared by the following steps: drying metal organic framework matrix powder, immersing the dried metal organic framework matrix powder into the phase change material mixed solution, stirring for 1-10 h, and drying the reaction solution to obtain a metal organic framework matrix composite phase change material containing the phase change material;
optionally, before the metal-organic framework matrix powder is immersed in the phase-change material mixed solution, vacuum drying is performed, and optionally the vacuum drying method is as follows: vacuum drying at 60-100 ℃ for 20-28 h to fully activate and open pores;
optionally, the reaction solution is dried by the following method: vacuum drying at 60-100 ℃ for 20-28 h;
optionally, the stirring conditions for immersing the metal-organic framework matrix powder into the phase-change material mixed solution are as follows: vigorously stirring for 1-5 h at 60-80 ℃, optionally vigorously stirring for 2h at 70 ℃;
optionally, the preparation method of the phase-change material mixed solution comprises: completely dissolving the phase change material in a solvent at a temperature above the phase change point; optionally, the solvent is absolute ethanol.
In another aspect, an application of the metal-organic framework-based photothermal composite phase change material is provided, wherein the metal-organic framework-based photothermal composite phase change material is used as a photothermal conversion material, optionally used in the field of solar heat storage, and optionally used in self-heating clothing.
Advantageous effects
(1) According to the embodiment of the invention, the metal organic framework based photo-thermal composite phase-change material is used as an excellent carrier of the phase-change material by taking the metal organic framework with high specific surface area and adjustable pore diameter as well as is packaged by high capillary adsorption force of the metal organic framework, so that the heat storage performance and the cycle stability of the phase-change composite material are obviously enhanced, and meanwhile, the metal organic framework based composite phase-change material is used as a growth and coating site of a photosensitizer, so that the aggregation of photosensitizer particles is avoided, and the particle size, the dispersion degree and the position of the photosensitizer are effectively controlled; the photosensitizer adopted by the invention has high-efficiency light absorption performance, and the photosensitive particles realize polymerization growth and uniform coating on the surface and/or in pores of the metal organic framework based composite phase change material, thereby being beneficial to shortening a heat transfer path so as to promote high-efficiency transfer of photo-induced heat to the outside, endowing the composite material with high-efficiency photo-thermal conversion performance, widening the utilization range of a single material to a spectrum, and solving the problem of single functionality of the traditional metal organic framework based phase change heat storage material.
(2) According to the metal organic framework based photo-thermal composite phase change material provided by the embodiment of the invention, the adsorbed solid-liquid phase change material reaches 70% without leakage, the phase change enthalpy value can reach 129.50J/g, and the photo-thermal composite phase change material has stable phase change performance and thermal performance.
(3) According to the metal organic framework based photo-thermal composite phase change material provided by the embodiment of the invention, the phase change material is packaged through the high capillary adsorption force of the metal organic framework matrix, and a site is provided for the growth and coating of the photosensitizer, so that the aggregation of photosensitizer particles is avoided, and the functionalization of the structure is realized. The phase-change material of the invention preferentially adopts a solid-liquid phase-change material, can generate solid-liquid phase change under the drive of external temperature to realize the release/absorption of heat energy, and can cooperate with a photosensitizer to play the roles of photo-thermal conversion and heat energy storage.
(4) The metal organic framework based photothermal composite phase change material provided by the embodiment of the invention adopts an organic conjugated polymer as a photosensitizer, and C-C and C ═ C in the organic conjugated polymer are alternately arranged. The pi electrons in the conjugated double bonds are not fixed to a carbon atom and they can be transferred from one carbon atom to another, i.e. the pi electrons have a tendency to cross the entire molecular chain. When exposed to external light, the organic photosensitizer can absorb light energy by utilizing transition of electrons in molecular orbitals, and then convert the absorbed light energy into heat energy, thereby showing a solar thermal effect. That is, under the induction of light, pi electrons on the pi-bonded molecular orbital of the organic photosensitizer absorb light energy and then jump to pi-x anti-bonded molecular orbital. During the return of the excited electrons to the ground state, part of the energy is released in the form of heat, thereby generating a solar heating effect. According to the invention, the metal-organic framework based composite phase-change material is used for providing a growth site for a monomer of an organic conjugated polymer, and the photosensitizer is grown and coated on the surface of the metal-organic framework based composite phase-change material, so that excellent light absorption can be provided, and the prepared photo-thermal composite phase-change material has high-efficiency solar heat conversion capability.
Drawings
One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
FIG. 1 is an SEM picture of an MOF and photothermal composite material ODA @ MOF/PPy-6 in example 3 of the present invention, wherein ODA is an abbreviation for octadecanol, PPy is an abbreviation for polypyrrole, MOF is an abbreviation for metal organic framework MIL-101(Cr) prepared in example 3, and PPy-6 is an abbreviation for ODA @ MOF/PPy-6 in example 3.
Fig. 2 is a DSC cold-heat cycle curve of the photothermal composite phase change material ODA @ MOF/PPy-6 of example 3 of the present invention after 50 times of cold-heat alternation experiments.
FIG. 3 is a structural representation diagram of the MOF and photothermal composite phase change material in examples 1-3 and comparative examples 1-3 of the present invention, wherein (a) is FTIR spectrum, and (b) is XRD spectrum. MOF is the metal organic framework MIL-101(Cr) prepared in example 3, ODA @ MOF is the phase change material of the metal organic framework composite ODA prepared in example 3, PPy-4 is the abbreviation of ODA @ MOF/PPy-4 of example 1, PPy-5 is the abbreviation of ODA @ MOF/PPy-5 of example 2, and PPy-6 is the abbreviation of ODA MOF @ PPy-6 of example 3.
FIG. 4 is a graph showing latent heat storage properties of photothermal composite phase change materials of examples 1 to 3 of the present invention and comparative example 1, wherein (a) is a DSC heating curve and (b) is a DSC cooling curve; ODA is short for octadecanol, ODA @ MOF is the phase change material of the metal organic framework composite ODA prepared in example 3, PPy-4 is short for ODA @ MOF/PPy-4 in example 1, PPy-5 is short for ODA @ MOF/PPy-5 in example 2, and PPy-6 is short for ODA @ MOF/PPy-6 in example 3.
FIG. 5 shows the photo-thermal composite phase change material of the embodiment and the comparative example at 150mW/cm2And (3) a photothermal curve under illumination, wherein ODA @ MOF is an abbreviation for ODA @ MOF composite phase change material of comparative example 1, PPy-4 is an abbreviation for ODA @ MOF/PPy-4 of example 1, PPy-5 is an abbreviation for ODA @ MOF/PPy-5 of example 2, and PPy-6 is an abbreviation for ODA @ MOF/PPy-6 of example 3.
FIG. 6 is a photograph of a leakage test of the photothermal composite phase change material of the present invention at 80 ℃ for various times under continuous heating; wherein ODA is short for octadecanol, ODA @ MOF is short for ODA @ MOF composite phase change material of comparative example 1, and PPy-6 is short for ODA @ MOF/PPy-6 of example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
In the following examples, all the raw materials used were commercially available materials. The metal-organic framework matrix MIL-101(Cr) can be a commercially available product or synthesized by the method of the embodiment.
In the following examples, the metal-organic framework matrix is MIL-101(Cr) for illustration, and in practical application, different metal-organic framework matrices, such as MIL-100(Fe), ZIF-8, ZIF-67, MOF-5, etc., can be selected according to different requirements.
In the following embodiments, Octadecanol (ODA) is selected as the phase change material, and in practical applications, different phase change materials can be selected according to different requirements.
In the following examples, the specific detection method of the photothermal curve is as follows: placing the prepared 200mg photo-thermal phase change energy storage material at the intensity of 150mW/cm2Is carried out under a xenon lamp, a heat sensor is utilized to record the temperature change of a sample, and finally a formula is utilized
(wherein m is the mass of the photothermal phase change energy storage material, Δ H represents latent heat of fusion, P is the irradiation intensity of simulated sunlight, S is the area of the photothermal phase change energy storage material exposed to light, and t is the irradiation time.) the photothermal conversion efficiency (η) of the photothermal phase change energy storage material in the absorption process is calculated.
In the following embodiments, the method for detecting latent heat storage performance is as follows: first, a solid sample is prepared, and the latent heat value of the photothermal composite phase change material is measured by differential scanning calorimetry (DSC, MettlerDSC822e, Japan).
In the following examples, polypyrrole (corresponding to the used pyrrole monomer) is selected as the photosensitizer for illustration, and in actual application, different photosensitizers can be selected according to different requirements.
ODA @ MOF/PPy-x is given as an example below, where "x" represents the relative percentage of photosensitizer added during the preparation of the phase change composite. The metal-organic framework-based photothermal composite phase change material with photothermal conversion performance, which can be applied to the field of solar heat storage, and the preparation method thereof are further described by specific embodiments and the accompanying drawings.
Example 1
A preparation method of a metal organic framework-based photothermal composite phase change material with a photothermal conversion function comprises the following steps:
(1) MIL-101(Cr) is synthesized by adopting a one-step hydrothermal method: first, 1.44g (8.0mmol) of 2-aminoterephthalic acid (H)2BDC-NH2)、3.20g(8.0mmol)Cr(NO3)3·9H2Dissolving O and 0.80g (20.0mmol) of NaOH in 60mL of deionized water, and stirring at room temperature for 30 min; the mixed solution was then transferred to a teflon-lined autoclave and reacted at 180 ℃ for 12 h. Finally, the solid product was purified several times using N-N dimethylformamide, methanol and deionized water, respectively. And drying the solid product after centrifugation in a vacuum oven at 100 ℃ for 24h to obtain MOF powder.
(2) The metal organic framework substrate MIL-101(Cr) adsorbs phase change materials: drying the MOF powder in step (1) in a vacuum oven at 80 ℃ for 24h to sufficiently activate and open the pores; 1.0g of the MOF powder after vacuum drying was taken up in the ODA mixture from step A) and stirred vigorously at 70 ℃ for 2 h. And finally, putting the mixed solution into a vacuum oven, and drying at 80 ℃ for 24h to obtain the ODA @ MOF composite phase change material, wherein the maximum load capacity of ODA is 70%.
Wherein, the preparation of ODA mixed solution is as follows: completely dissolving 2.3g of ODA in 25mL of absolute ethyl alcohol at 70 ℃, and stirring for 0.5h to obtain a phase change material mixed solution;
(3) preparation of ODA @ MOF/PPy-4: first, 100mg of oda @ MOF composite phase change material of step (2) was immersed in a 1 wt% ferric chloride solution. Then, 4mL of pyrrole monomer was added to the mixture to effect polymerization, and stirred vigorously at 25 ℃ for 8h until the solution became black. Finally, ODA @ MOF/PPy-4 was obtained by centrifuging and drying the above mixture.
The enthalpy value of the MOF-based photothermal composite phase change material ODA @ MOF/PPy-4 prepared in the embodiment is 127.93J/g, and the highest photothermal conversion efficiency can reach 79.8%; the leakage-proof test results show that the phase change composite material hardly generates any leakage when being processed in an oven at 80 ℃ for 1 h.
Example 2
The difference from the preparation method of example 1 is that the amount of pyrrole monomer added was 5mL, and ODA @ MOF/PPy-5 was obtained.
The enthalpy value of the MOF-based photothermal composite phase change material ODA @ MOF/PPy-5 prepared in the embodiment is 130.85J/g, and the highest photothermal conversion efficiency can reach 85.6%; the leakage-proof test results show that the phase change composite material hardly generates any leakage when being processed in an oven at 80 ℃ for 1 h.
Example 3
The difference from the preparation method of example 1 is that the amount of pyrrole monomer added was 6mL, and ODA @ MOF/PPy-6 was obtained.
The enthalpy value of the MOF-based photothermal composite phase change material ODA @ MOF/PPy-6 prepared in the embodiment is 129.58J/g, and the highest photothermal conversion efficiency can reach 88.3%; the leakage-proof test results show that the phase change composite material hardly generates any leakage when being processed in an oven at 80 ℃ for 1 h.
SEM images of the MOF and composite materials of this example 3, ODA @ MOF/PPy-6, are shown in FIG. 1, and the morphologies of MOF and ODA @ MOF/PPy-6 are shown at the same magnification. ODA @ MOF/PPy-6 exhibits a larger size than the original MOF due to the coating effect of the PPy particle polymer on the surface of ODA @ MOF.
The DSC cycle curve of ODA @ MOF/PPy-6 of example 3 through ODA @ MOF/PPy-6 is shown in FIG. 2, and the results show that the melting points, crystallization points, latent heats of fusion and enthalpy of crystallization of the three curves of ODA @ MOF/PPy-6 prepared in this example are almost unchanged before and after 50 thermal cycles, so that the ODA @ MOF/PPy-6 prepared in this example has good stability.
The ODA @ MOF/PPy-6 photothermal composite phase change material in example 3 was subjected to a leakage test, and heating was continued at 80 ℃ which is far higher than the transformation point of Octadecanol (ODA), and as a result, as shown in fig. 6, ODA liquefies with the lapse of time, and the phase change material in the ODA @ MOF-PPy photothermal composite phase change material does not flow out, which indicates that the photothermal composite phase change material in this example has good encapsulation property.
Comparative example 1
The difference from example 2 is that step (3) was not performed, i.e., this comparative example produced only ODA @ MOF composite phase change material.
The enthalpy value of the MOF-based photo-thermal composite phase change material ODA @ MOF prepared in the comparative example is 131.45J/g, and the leakage prevention test result shows that the phase change composite material hardly leaks when being treated in an oven at 80 ℃ for 1h (figure 5).
The results of the characterization and analysis of the chemical structures of the photothermal composite phase change materials of the embodiments 1 to 3 and the comparative example 1 are shown in fig. 2, and the results show that all characteristic peaks of ODA, MOF and PPy are observed in the ODA @ MOF/PPy composite phase change material, and no obvious new peak is observed, which indicates that no new chemical bond is formed. FTIR spectra show that ODA, PPy and MOF are physical interactions, not chemical interactions. The XRD patterns of ODA and ODA @ MOF-PPy were characterized to explore the crystallization behavior of ODA in the MOF pores, and the diffraction peaks of ODA, MOF and PPy were all observed in the composite ODA @ MOF-PPy without significant shift, confirming the physical interaction between the components.
The results of the latent heat storage performance of the photothermal composite phase change materials of examples 1 to 3 and comparative example 1 are shown in fig. 3 and fig. 4, and show that the enthalpy value of the composite obtained when the photosensitizer is added in an amount of 4mL, 5mL and 6mL is not greatly different, the enthalpy value of the composite obtained when the photosensitizer is added in an amount of 5mL is relatively good, and the photothermal efficiency of the composite obtained when the photosensitizer is added in an amount of 6mL is relatively good, which indicates that the enthalpy value and the photothermal efficiency are not completely corresponding.
The photothermal conversion test was performed on the photothermal composite phase change materials of examples 1 to 3 and comparative example 1, and the results are shown in fig. 5, which shows that the concentration of the photothermal composite phase change material is 150mW/cm2Under the light intensity drive, ODA @ MOF composite material can not reach the phase transition point, means nearly no photothermal conversion ability, and is showing after introducing PPy and has improved photothermal conversion efficiency of photothermal composite phase transition material, makes composite material become the material that has excellent solar thermal conversion performance and high energy storage density, and along with the increase of PPy content, photothermal conversion efficiency has also obtained the promotion.
Comparative example 2
(1) The MOF powder (MIL-101(Cr)) was prepared according to the method of step (1) of example 1.
(2) The metal-organic framework substrate MIL-101(Cr) was immersed in a 1 wt% ferric chloride solution. Then, 5mL of pyrrole monomer was added to the mixture to effect polymerization, and stirred vigorously at 25 ℃ for 8h until the solution became black. Finally, MOF/PPy-5 was obtained by centrifuging and drying the above mixture.
(3) Drying the MOF/PPy-5 powder in a vacuum oven at 80 ℃ for 24h to fully activate and open the pores; 1g of vacuum dried MOF/PPy-5 powder was taken up in the ODA mixture and stirred vigorously at 70 ℃ for 2 h. And finally, putting the mixed solution into a vacuum oven, and drying at 80 ℃ for 24h to obtain ODA @ MOF/PPy-5-2.
The preparation method of the ODA mixed solution comprises the following steps: 2.3g of ODA is completely dissolved in 25mL of absolute ethyl alcohol at 70 ℃ and stirred for 0.5h to obtain a phase change material mixed solution.
In the comparative example, the photosensitizer is loaded firstly, so that the photosensitizer occupies the pore channels of the MOF, the efficient adsorption of the phase-change material cannot be realized, and the encapsulation effect on the phase-change material is poor.
The inventor of the invention finds that the photothermal conversion efficiency of the photothermal composite phase change material is firstly increased and then reduced along with the increase of the concentration of the oxidant, and the concentration of the oxidant is suitably 0.5-2%.
The inventor of the invention finds that the photothermal conversion efficiency of the photothermal composite phase change material is firstly increased and then reduced along with the increase of the content of the phase change material, and in the metal organic framework based composite phase change material, the weight ratio of the phase change material is 60-80%, and is optionally 65-80%.
Application example 1 photothermal energy storage application of composite material
The MOF-based photo-thermal composite phase change material has good phase change energy storage performance, the enthalpy value is 130.85J/g, the polypyrrole can be used as a light energy catcher to convert light energy into heat energy, the heat energy is further utilized by the phase change material to store and release the energy, and the enthalpy value is 150mW/cm2The photo-thermal conversion efficiency can reach 88.3 percent under the driving of light intensity.
For example, the MOF-based photothermal composite phase change material is encapsulated in fabric fibers, and further prepared into human body wearable thermal energy management equipment, and the equipment can perform photothermal conversion under the condition of sufficient sunlight in daytime to drive the phase change material to melt and store heat; during night, the phase-change material is solidified, and the heat energy stored in the phase-change material is released, so that the function of adjusting the temperature of a human body is achieved.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The metal organic framework based photo-thermal composite phase change material is characterized by comprising a metal organic framework based composite phase change material and a photosensitizer coated on the metal organic framework based composite phase change material, wherein the metal organic framework based composite phase change material comprises a porous metal organic framework matrix and a phase change material adsorbed on the surface of the metal organic framework matrix or in a pore channel.
2. The metal-organic framework-based photothermal composite phase change material according to claim 1, wherein the pores of the metal-organic framework-based composite phase change material also contain a photosensitizer;
and/or, it has photothermal conversion properties.
3. The metal-organic framework based photothermal composite phase change material according to claim 1 or 2, wherein the photosensitizer is an organic photosensitizer, and optionally, the photosensitizer is formed by polymerizing a photosensitizer monomer on the surface or pores of the metal-organic framework based composite phase change material through the action of an oxidizing agent.
4. The metal-organic framework-based photothermal composite phase change material according to any of claims 1 to 3, wherein the photosensitizer is an organic conjugated polymer; optionally, the organic conjugated polymer is selected from one or more of organic dye polymers and nanoparticle polymers;
optionally, the organic dye polymer comprises one or more of porphyrin, indocyanine green and heptane;
optionally, the nanoparticle-based polymer comprises one or more of polypyrrole, polydopamine and polyaniline.
5. The metal-organic framework based photothermal composite phase change material according to any one of claims 1 to 4, wherein the photosensitizer is 2-10% by weight of the metal-organic framework based composite phase change material, optionally 4-6%, preferably 4%, 5%, 6%.
6. The metal-organic framework-based photothermal composite phase change material according to any of claims 1 to 5, wherein the metal-organic framework matrix is a three-dimensional structure; optionally one or more selected from MIL-101(Cr), MIL-100(Fe), ZIF-8, ZIF-67, MOF-5, MOF-74.
7. The metal-organic framework-based photothermal composite phase change material according to any one of claims 1 to 6, wherein the metal-organic framework matrix encapsulates the phase change material by capillary adsorption force;
and/or the phase change material is a solid-liquid phase change material, optionally selected from one or more of fatty alcohol, fatty acid, n-alkane and paraffin; alternatively, the fatty alcohol comprises stearyl alcohol;
and/or the phase-change material accounts for 60-80%, optionally 65-80%, optionally 70% of the total weight of the metal-organic framework-based composite phase-change material.
8. The metal-organic framework-based photothermal composite phase change material according to any one of claims 1 to 7, wherein the preparation step comprises: immersing the metal organic framework-based composite phase-change material into an oxidant solution, adding a photosensitizer monomer according to the amount to realize polymerization reaction, stirring for 1-20 h, centrifuging, and drying to obtain the organic photosensitizer-coated photo-thermal composite phase-change material;
optionally, the weight ratio of the metal-organic framework-based composite phase change material to the photosensitizer monomer is 100: 4-6, optionally 100:4, 100:5, 100: 6;
optionally, in the polymerization reaction, the stirring time is 5-10 hours, optionally 8 hours;
optionally, in the polymerization reaction, the stirring condition is vigorous stirring, and optionally, the stirring speed is 800 r/min;
alternatively, in the polymerization reaction, stirring is carried out at room temperature;
optionally, the oxidant is selected from one or more of ferric chloride, hydrogen peroxide, ammonium persulfate and potassium permanganate; optionally, the concentration of the oxidizing agent is 0.5% to 2%, optionally 1%.
9. The metal-organic framework-based photothermal composite phase change material according to claim 8, wherein the metal-organic framework-based composite phase change material is prepared by the following steps: immersing metal organic framework matrix powder into the phase change material mixed solution, stirring for 1-10 h, and drying the reaction solution to obtain a metal organic framework matrix composite phase change material containing the phase change material;
optionally, before the metal-organic framework matrix powder is immersed in the phase-change material mixed solution, vacuum drying is performed, and optionally the vacuum drying method is as follows: vacuum drying at 60-100 ℃ for 20-28 h to fully activate and open pores;
optionally, the reaction solution is dried by the following method: vacuum drying at 60-100 ℃ for 20-28 h;
optionally, the stirring conditions for immersing the metal-organic framework matrix powder into the phase-change material mixed solution are as follows: vigorously stirring for 1-5 h at 60-80 ℃, optionally vigorously stirring for 2h at 70 ℃;
optionally, the preparation method of the phase-change material mixed solution comprises: completely dissolving the phase change material in a solvent at a temperature above the phase change point; optionally, the solvent is absolute ethanol;
optionally, the preparation method of the metal-organic framework matrix powder comprises the following steps: adding a hydrated metal salt solution into a solution of an organic ligand and an alkali, mixing, transferring into a reaction kettle, treating at 160-180 ℃ for 5-20 h, and drying; optionally, the hydrated metal salt and the organic ligand are in a molar ratio of 1:0.5 to 1.5, optionally in a molar ratio of 1: 1.
10. Use of the metal-organic framework-based photothermal composite phase change material according to any of claims 1 to 9 as a photothermal conversion material, optionally in the field of solar thermal storage, optionally in self-heating apparel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111676137.5A CN114395375A (en) | 2021-12-31 | 2021-12-31 | Metal organic framework based photo-thermal composite phase change material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111676137.5A CN114395375A (en) | 2021-12-31 | 2021-12-31 | Metal organic framework based photo-thermal composite phase change material and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114395375A true CN114395375A (en) | 2022-04-26 |
Family
ID=81229271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111676137.5A Pending CN114395375A (en) | 2021-12-31 | 2021-12-31 | Metal organic framework based photo-thermal composite phase change material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114395375A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479770B (en) * | 2021-12-31 | 2024-05-03 | 苏州荣格君新材料有限公司 | Photo-thermal phase-change energy storage material and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628218A (en) * | 2009-05-15 | 2010-01-20 | 清华大学深圳研究生院 | Method for quickly preparing phase change energy storage microcapsule by ultraviolet light irradiation and polymerization |
| CN103756646A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework based composite phase-change material |
| CN106860864A (en) * | 2017-01-10 | 2017-06-20 | 中国人民解放军南京军区南京总医院 | A kind of mesoporous organosilicon gold nano triangular plate composite for loading sensitising agent and preparation method thereof, application |
| KR20170114265A (en) * | 2017-07-24 | 2017-10-13 | 가톨릭대학교 산학협력단 | Drug delivery system containing phase change material and crystalline carbon nanoparticles and method of making the same |
| CN110157385A (en) * | 2019-06-10 | 2019-08-23 | 常州港华燃气有限公司 | It is a kind of using modified resin as the phase-transition heat-storage particle and its preparation process of shell material |
| US20200408471A1 (en) * | 2017-06-13 | 2020-12-31 | South China University Of Technology | Phase-change energy-storage structure for building insulation |
| CN113403039A (en) * | 2021-07-01 | 2021-09-17 | 四川大学 | Multifunctional phase change energy storage composite material and preparation method thereof |
| WO2021253286A1 (en) * | 2020-06-17 | 2021-12-23 | 苏州科技大学 | Preparation method for flexible optical/electrical-thermal dual-response phase-change cloth |
-
2021
- 2021-12-31 CN CN202111676137.5A patent/CN114395375A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628218A (en) * | 2009-05-15 | 2010-01-20 | 清华大学深圳研究生院 | Method for quickly preparing phase change energy storage microcapsule by ultraviolet light irradiation and polymerization |
| CN103756646A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework based composite phase-change material |
| CN106860864A (en) * | 2017-01-10 | 2017-06-20 | 中国人民解放军南京军区南京总医院 | A kind of mesoporous organosilicon gold nano triangular plate composite for loading sensitising agent and preparation method thereof, application |
| US20200408471A1 (en) * | 2017-06-13 | 2020-12-31 | South China University Of Technology | Phase-change energy-storage structure for building insulation |
| KR20170114265A (en) * | 2017-07-24 | 2017-10-13 | 가톨릭대학교 산학협력단 | Drug delivery system containing phase change material and crystalline carbon nanoparticles and method of making the same |
| CN110157385A (en) * | 2019-06-10 | 2019-08-23 | 常州港华燃气有限公司 | It is a kind of using modified resin as the phase-transition heat-storage particle and its preparation process of shell material |
| WO2021253286A1 (en) * | 2020-06-17 | 2021-12-23 | 苏州科技大学 | Preparation method for flexible optical/electrical-thermal dual-response phase-change cloth |
| CN113403039A (en) * | 2021-07-01 | 2021-09-17 | 四川大学 | Multifunctional phase change energy storage composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 谭帼馨;阮雄杰;宁成云;霍延平;陈荣;廖景文;: "PEGDA/NIPAM共聚物水凝胶的溶胀性能及体积相变研究", 广东工业大学学报, no. 03, pages 5 - 8 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479770B (en) * | 2021-12-31 | 2024-05-03 | 苏州荣格君新材料有限公司 | Photo-thermal phase-change energy storage material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Solvothermal synthesis of porphyrin-ferrocenyl conjugated microporous polymer nanospheres for shape-stable phase change materials with improved latent heat and cyclability | |
| CN110484214B (en) | Shaped MOF-based composite phase change material and preparation method and application thereof | |
| CN109096998B (en) | Preparation method of photo-thermal conversion phase-change energy storage composite material | |
| CN113663615A (en) | High-latent-heat-value phase-change microcapsule with photo-thermal conversion effect and preparation method thereof | |
| JP7226834B2 (en) | Method for producing flexible photovoltaic and photothermal dual reactive phase change fabric | |
| Yang et al. | Polyethylene glycol-based phase change materials with high photothermal conversion efficiency and shape stability in an aqueous environment for solar water heater | |
| CN114395375A (en) | Metal organic framework based photo-thermal composite phase change material and application thereof | |
| CN114479770B (en) | Photo-thermal phase-change energy storage material and preparation method and application thereof | |
| Hou et al. | N-eicosane@ TiO2/TiN composite phase change microcapsules: Efficient visible light-driven reversible solid-liquid phase transition | |
| Zhao et al. | Cuprous oxide modified nanoencapsulated phase change materials fabricated by RAFT miniemulsion polymerization for thermal energy storage and photothermal conversion | |
| Feng et al. | Effects of in-situ acid dopants on the latent heat storage properties and morphology of palmitic acid@ polyaniline microencapsulated phase change materials | |
| CN105702938A (en) | Iron-based oxide lithium ion battery negative electrode material and preparation method and application thereof | |
| CN113231081A (en) | Flower-shaped CDs-ZnIn2S4Composite photocatalyst and preparation method and application thereof | |
| Li et al. | Ultrafast and continuous synthesis of phase change nanocapsules using salt-accelerated microwave-assisted polymerization | |
| Shahmoradi et al. | Effect of SiO2 nanoparticles on thermal properties of polyaniline/palmitic acid composite as an energy storage system | |
| CN116093283A (en) | Phthalocyanine-based covalent organic framework coated nano silicon composite material and preparation method thereof | |
| CN114316919B (en) | Polymer/graphene oxide composite microcapsule for phase-change energy storage material encapsulation and preparation method thereof | |
| CN114479771A (en) | Metal organic framework derivative-based photothermal phase change material and application thereof | |
| CN113896610B (en) | Photothermal conversion eutectic material containing pyrene and preparation method thereof | |
| CN110129010B (en) | Preparation method of high-thermal-conductivity composite phase-change material | |
| CN112375545B (en) | Manganese dioxide-melamine formaldehyde resin double-shell composite phase change material and preparation method thereof | |
| CN111187599B (en) | Three-dimensional basic manganese oxide nanorod foam composite phase change material and preparation method and application thereof | |
| CN113559927A (en) | g-C3N4CuS quantum dot modified COFs composite material and preparation method thereof | |
| CN114231256B (en) | Magnetic high graphitization carbon-based photo-thermal composite phase change material and application thereof | |
| CN114806510B (en) | Composite phase-change energy storage material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240410 Address after: No.6, Anmin Road, Huangdai Town, Xiangcheng District, Suzhou City, Jiangsu Province Applicant after: Suzhou ronggejun New Material Co.,Ltd. Country or region after: China Address before: 215152 Room 401, no.6, Anmin Road, Dongqiao, Huangdai Town, Xiangcheng District, Suzhou City, Jiangsu Province Applicant before: SUZHOU ADEWANGSI NEW MATERIALS Co.,Ltd. Country or region before: China |
|
| TA01 | Transfer of patent application right |