CN114425285B - Microcapsule phase change energy storage material and preparation method and application thereof - Google Patents
Microcapsule phase change energy storage material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a microcapsule phase change energy storage material, a preparation method and application thereof. The microcapsule phase change energy storage material provided by the invention comprises a core material and a shell material; wherein the core material is a phase change material, and the shell material is a metal-based porous coordination polymer; the mass content of the core material is 70.5-80.5%, and the mass content of the shell material is 19.5-29.5%. The microcapsule phase change energy storage material integrates heat storage, temperature adjustment, humidity adjustment and harmful gas purification, and has the advantages of multifunction and industrial popularization.
Description
Technical Field
The invention belongs to the technical field of phase-change energy storage materials, and particularly relates to a microcapsule phase-change energy storage material and a preparation method thereof.
Background
The microcapsule phase change energy storage material is formed by continuously adsorbing a layer of uniform and stable film on the surface of a phase change material of single particles or liquid drops through a microcapsule technology, and the particle size of the microcapsule phase change energy storage material is between 1 and 1000 mu m. The microcapsule phase change energy storage material has a core-shell structure, can play a good role in protecting the core material, can isolate direct contact with the outside, prevents the core material from leaking in a long-term cyclic phase change process, and improves the working performance of the core material. Therefore, the microcapsule technology can break the limitation of the phase change material in application, so that the phase change material has wider application field.
Along with the gradual deep research work of the microcapsule phase change energy storage material, the microcapsule phase change energy storage material is changing from a single heat storage and temperature adjustment function to a plurality of functions of heat collection and storage, formaldehyde purification and bacteriostasis, humidity adjustment, harmful gas elimination and the like. The porous coordination polymer is a material which is connected with the organic ligand in a coordination mode to form a porous network structure, has higher specific surface area, porosity and abundant adjustable pore structure, and is representative of a new generation of hybrid porous materials. The microcapsule phase change energy storage material and the porous coordination polymer are organically combined, so that the technical advantages of the microcapsule phase change energy storage material and the porous coordination polymer can be fully exerted, and the novel multifunctional phase change energy storage material is formed.
CN106800917a discloses a preparation method of a phase change material of n-octadecane coated by ZIF-8 organic metal skeleton. Firstly, zinc nitrate is dissolved in proper deionized water, water bath heating is carried out, melted n-octadecane is slowly added under high-speed stirring for reaction for a period of time, then proper amount of dimethyl imidazole is added, the mixture is slowly stirred for dissolving, a phase-change material with a special material structure is formed through self-assembly, the mixture is oscillated overnight, and the mixture is taken out for suction filtration, washed for a plurality of times and freeze-dried to prepare the three-dimensional hexagonal petal-shaped phase-change material. In the preparation process of the material, the zinc ions are lack of connection with the n-octadecane in a molten state, namely, the zinc ions are gathered around the n-octadecane liquid drops simply by means of stirring, so that the zinc ions are easy to be scattered and unevenly distributed, and the physicochemical property of the n-octadecane phase change material coated by the subsequent ZIF-8 organic metal framework is influenced. Meanwhile, the phase-change core material is limited to n-octadecane, and the price of the n-alkane phase-change core material is generally high, so that the phase-change core material is not beneficial to subsequent industrial amplification and popularization.
CN103752239a discloses a method for preparing microcapsules of metal organic framework coated phase change material. Firstly, preparing a basic copper sulfate microsphere with a hollow structure or a yolk/shell structure, wherein a shell layer of the basic copper sulfate microsphere is assembled by nano sheets, a gap exists between the nano sheets, a phase change material can enter the microsphere through the gap of a shell layer of the basic copper sulfate microsphere, then the shell layer is converted into a metal organic framework material in situ to form a compact metal organic framework material shell layer, the phase change material is packaged, and the phase change material is dried to prepare the metal organic framework coated phase change material microcapsule. The phase change material microcapsule product coated by the metal-organic framework can be obtained in multiple steps, and the production process is complex; in addition, the phase change material enters the basic copper sulfate microsphere in a melting infiltration mode, and the storage capacity of the phase change material is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a microcapsule phase change energy storage material, and a preparation method and application thereof. The microcapsule phase change energy storage material integrates the functions of heat storage, temperature adjustment, humidity adjustment and harmful gas purification, and has the advantages of simple preparation method, multifunction and contribution to industrial popularization.
The first aspect of the invention provides a microcapsule phase change energy storage material, which comprises a core material and a shell material; wherein the core material is a phase change material, and the shell material is a metal-based porous coordination polymer; the mass content of the core material is 70.5-80.5%, and the mass content of the shell material is 19.5-29.5%.
In the above technical solution, the metal in the metal-based porous coordination polymer is one or more of aluminum, gallium and indium, preferably aluminum.
In the above technical scheme, the organic ligand in the metal-based porous coordination polymer is selected from one or more of pyromellitic acid, 2, 6-naphthalene dicarboxylic acid and terephthalic acid, and preferably pyromellitic acid.
In the above technical scheme, the mass ratio of the metal salt to the organic ligand in the metal-based porous coordination polymer is 1: (0.25 to 0.95), preferably 1: (0.4-0.7).
In the technical scheme, the phase change material is selected from one or more of normal alkane, paraffin and palmitic acid with the phase change temperature of 35-65 ℃, and paraffin is preferred.
In the technical scheme, the particle size of the microcapsule phase change energy storage material is 30-50 mu m.
In the technical scheme, the melting potential value of the microcapsule phase change energy storage material is 105-125J/g.
In the technical scheme, the coating rate of the microcapsule phase change energy storage material is 70.5% -80.5%.
In the technical proposal, the heat conductivity coefficient of the microcapsule phase change energy storage material is 0.5-1.23W m -1 ·k -1 Preferably 0.63 to 0.87W.m -1 ·k -1 。
In the technical proposal, the specific surface area of the microcapsule phase change energy storage material is 401 to 460 m 2 Per gram, pore volume of 0.31-0.42 cm 3 /g。
The invention provides a preparation method of a microcapsule phase change energy storage material, which comprises the following steps:
(1) Mixing a molten phase change material, an organic ligand, a neutral surfactant and a mixed solvent, and performing a shearing reaction to obtain a phase change microemulsion containing the organic ligand;
(2) Stirring and heating the phase-change microemulsion prepared in the step (1) for reaction, and simultaneously dropwise adding a metal salt solution;
(3) And (3) washing and drying the mixture after the reaction in the step (2) to obtain the microcapsule phase change energy storage material.
In the above technical scheme, the molten phase change material in the step (1) is selected from one or more of normal paraffin, paraffin wax and palmitic acid with a phase change temperature of 35-65 ℃, and paraffin wax is preferred.
In the above technical solution, the organic ligand in step (1) is selected from one or more of pyromellitic acid, 2, 6-naphthalene dicarboxylic acid and terephthalic acid, and preferably pyromellitic acid.
In the above technical scheme, the neutral surfactant in the step (1) is selected from one or more of span 40, tween 40 and octyl phenol polyoxyethylene ether-15, preferably octyl phenol polyoxyethylene ether-15.
In the above technical solution, the mixed solvent in step (1) is one or more selected from ethanol aqueous solution, methanol aqueous solution and acetone aqueous solution, preferably ethanol aqueous solution, wherein the mass ratio of ethanol to deionized water is 1: (10 to 50), preferably 1: (25-35).
In the above technical scheme, the mass ratio of the phase change material, the organic ligand, the neutral surfactant and the mixed solvent in the step (1) is 1: (0.05-0.35): (0.01-0.1): (3-10), preferably 1: (0.15-0.29): (0.03-0.08): (5-8).
In the technical scheme, the reaction temperature of the shearing reaction in the step (1) is 68-90 ℃, preferably 73-82 ℃; the shearing reaction time is 5-35 min, preferably 15-20 min; the shearing reaction speed is 7000rpm to 20000rpm, preferably 13000rpm to 16000rpm.
In the technical scheme, the stirring rotation speed in the step (2) is 350-850 rpm, preferably 500-600 rpm; the stirring reaction time is 1 h-5 h, preferably 1.5 h-2.5 h.
In the technical scheme, the reaction temperature of the heating reaction in the step (2) is 68-85 ℃, preferably 73-80 ℃.
In the above technical solution, the metal salt in step (2) is one or more selected from aluminum nitrate, gallium nitrate and indium nitrate, preferably aluminum nitrate.
In the technical scheme, the mass concentration of the metal salt aqueous solution in the step (2) is 5-15%, preferably 8-12%; the dropping rate of the metal salt aqueous solution is 1 g/min-10 g/min, preferably 3.5 g/min-6.5 g/min.
In the above technical scheme, the mass ratio of the metal salt in the step (2) to the organic ligand in the step (1) is 1: (0.25 to 0.95), preferably 1: (0.4-0.7).
In the technical scheme, the drying temperature in the step (3) is 50-90 ℃, preferably 65-75 ℃; the drying time is 12 to 24 hours, preferably 16 to 20 hours.
In the technical scheme, the washing in the step (3) can be repeatedly performed by absolute ethyl alcohol.
The third aspect of the invention provides a microcapsule phase change energy storage material prepared by the preparation method.
In a fourth aspect, the present invention provides a method for adsorbing the microcapsule phase change energy storage material according to the first aspect or the microcapsule phase change energy storage material according to the third aspect.
In the technical scheme, the flow rate of formaldehyde gas is 2-15mL/min at 20-30 ℃ and 0-100 kPa.
In the technical scheme, the flow rate of the carbon dioxide gas is 2-15mL/min at 20-30 ℃ and 0-100 kPa.
In the technical scheme, the flow rate of the water vapor is 10-30mL/min under the conditions of 20-30 ℃ and 0-100 kPa.
Compared with the prior art, the invention has the following advantages:
(1) The microcapsule phase change energy storage material containing the porous coordination polymer shell material is obtained by a one-step method through a complexation coordination technology by adopting a mode of synergistic emulsification of an organic ligand and a neutral surfactant. The aromatic ring structure in the organic ligand has lipophilicity, while the carboxyl structure has hydrophilicity, and is easy to uniformly distribute around the phase change core material in a molten state as a part of the synergistic emulsifier. The neutral surfactant has the capability of improving the stability of the phase-change microemulsion system, and effectively inhibits the probability that organic ligands with stronger polarity are easy to cause emulsion polymerization into macromolecules. The organic ligands are uniformly distributed around the molten phase-change core material, a certain targeting effect is provided for the complex coordination reaction of metal ions and the metal ions, the shape of the obtained microcapsule phase-change energy storage material is more regular, and the porous coordination polymer is more uniformly and compactly distributed on the surface.
(2) The synthesis method is simple, avoids tedious preparation process and operation conditions, and is suitable for large-scale preparation and use. The coating of the phase-change core material is completed by a one-step method, so that the microcapsule phase-change energy storage material with higher coating rate is obtained, and meanwhile, the phenomenon of liquid leakage of the melted phase-change core material is prevented.
(3) The microcapsule phase change energy storage material prepared by the invention takes the aluminum-based porous coordination polymer as a shell material, so that the microcapsule phase change energy storage material is endowed with more functionality, such as harmful gas absorption under normal temperature and normal pressure conditions, good humidity adjusting capability and the like. Can be used in a plurality of technical fields such as industrial waste heat recovery, solar heat storage, temperature and humidity adjustment, building heat preservation, indoor air purification and the like. For example, according to the embodiment of the invention, the formaldehyde gas adsorption amount is 80cm 3 /g～100 cm 3 Per gram, carbon dioxide gas adsorption capacity of 40cm 3 /g～60 cm 3 Per gram, the water vapor adsorption capacity is 140cm 3 /g～180 cm 3 /g。
(4) The porous coordination polymer is used as a wall material, and compared with the conventional inorganic porous materials (such as alumina, silica and active carbon), the porous coordination polymer has higher specific surface area and pore volume, particularly forms a certain amount of ultra-microporous structures in the complexing coordination reaction process, and is favorable for adsorbing small molecular gases such as formaldehyde and carbon dioxide; in addition, the central metal ion of the porous coordination polymer has certain hydrophilic property, and can form a coordination saturation structure with water molecules, so that the porous coordination polymer has high humidity adjusting performance.
Drawings
FIG. 1 is an infrared spectrum chart of a microcapsule phase change energy storage material of the embodiment 1;
FIG. 2 is a scanning electron microscope photograph of a microcapsule phase change energy storage material of example 1 of the present invention;
FIG. 3 is the formaldehyde adsorption amount of the microcapsule phase change energy storage materials of examples 1-2 and comparative examples 1-2;
FIG. 4 is the adsorption amount of carbon dioxide by the microcapsule phase change energy storage materials of examples 1-2 and comparative examples 1-2;
FIG. 5 shows the adsorption amounts of water vapor by the microcapsule phase change energy storage materials of examples 1-2 and comparative examples 1-2.
Detailed Description
The preparation method and effect of the phase-change temperature-regulating gypsum board of the present invention are further described below by way of examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
The preparation method and effect of the microcapsule phase change energy storage material of the invention are further described below by examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
The invention adopts a Differential Scanning Calorimeter (DSC) to test the phase-change latent heat value of the microcapsule phase-change energy storage material in the melting process, and the model of the instrument is DSC-60 Plus of Shimadzu corporation. The temperature test range is 25-80 ℃ under the nitrogen atmosphere, the temperature rising rate is 10 ℃/min, and the weight of the sample is about 3.5mg.
The invention adopts a Japanese Hitachi S-4700 type field emission Scanning Electron Microscope (SEM) to observe the morphology, microstructure and particle size of the synthesized microcapsule phase change energy storage material.
The invention adopts Bei Shide instrument technology (Beijing) limited company 3H-2000PM type high-performance specific surface and micropore analyzer to carry out N 2 Adsorption-desorption analysis, vacuum degassing at 180deg.C for 12 hr, weighing, transferring to analysis station, and N-treating at 77K 2 Adsorption-desorption isotherm measurements, BET method calculated specific surface area and pore volume.
The invention adopts a DRL-III-P type thermal conductivity coefficient tester of Hunan instrument limited company to measure the thermal conductivity coefficient of microcapsule samples. The coating rate of the microcapsule phase change energy storage material is calculated as follows:
coating rate/% = microcapsule melting potential value/phase change material melting potential value
The invention adopts an HPVA-100 type high-pressure gas adsorber of Micromeritics company in the United states to test the adsorption performance of a sample on formaldehyde and carbon dioxide. The adsorption performance of the sample on water vapor was tested using a self-built fixed bed microreactor.
Example 1
10g of paraffin wax with a melting phase transition temperature of 57 ℃, 2.5g of benzene tetracarboxylic acid, 0.5g of octyl phenol polyoxyethylene ether-15 and 75g of ethanol aqueous solution are taken and mixed, wherein the mass ratio of ethanol to deionized water is 1:30. and (3) carrying out high-speed shearing reaction for 17min at 75 ℃ and 15000rpm to obtain the phase-change microemulsion containing the organic ligand. The phase-change microemulsion is filled in a four-neck flask, transferred into an electric heating sleeve containing a mechanical stirrer, stirred and reacted for 2 hours at the temperature of 75 ℃ and the rpm of 550rpm, and simultaneously 50g of aluminum nitrate nonahydrate aqueous solution with the mass concentration of 10 percent is dropwise added at the speed of 5g/min. And (3) carrying out suction filtration treatment on the mixture after the reaction is finished, repeatedly flushing with absolute ethyl alcohol, and carrying out forced air drying treatment on the obtained filtrate at 70 ℃ for 18 hours to obtain the microcapsule phase-change energy storage material, wherein the mass content of the core material is 78.3%, and the mass content of the shell material is 21.7%.
Example 2
10g of paraffin wax with a melting phase transition temperature of 57 ℃, 1.5g of benzene tetracarboxylic acid, 0.3g of octyl phenol polyoxyethylene ether-15 and 50g of ethanol aqueous solution are taken and mixed, wherein the mass ratio of ethanol to deionized water is 1:25. and (3) carrying out high-speed shearing reaction for 15min at 73 ℃ and 13000rpm to obtain the phase-change microemulsion containing the organic ligand. The phase-change microemulsion is contained in a four-neck flask, transferred into an electric heating sleeve containing a mechanical stirrer, stirred and reacted for 1.5 hours at the temperature of 73 ℃ and the speed of 500rpm, and meanwhile 46.9g of aluminum nitrate nonahydrate aqueous solution is dropwise added at the speed of 3.5g/min, and the mass concentration of the aluminum nitrate nonahydrate aqueous solution is 8%. And (3) carrying out suction filtration treatment on the mixture after the reaction is finished, repeatedly flushing with absolute ethyl alcohol, and carrying out forced air drying treatment on the obtained filtrate at 65 ℃ for 16 hours to obtain the microcapsule phase-change energy storage material, wherein the mass content of the core material is 73.6%, and the mass content of the shell material is 26.4%.
Example 3
10g of paraffin wax with a melting phase transition temperature of 57 ℃, 2.9g of benzene tetracarboxylic acid, 0.8g of octyl phenol polyoxyethylene ether-15 and 80g of ethanol aqueous solution are taken and mixed, wherein the mass ratio of ethanol to deionized water is 1:35. and (3) carrying out high-speed shearing reaction for 20min at 82 ℃ and 16000rpm to obtain the phase-change microemulsion containing the organic ligand. The phase-change microemulsion is contained in a four-neck flask, transferred into an electric heating sleeve containing a mechanical stirrer, stirred and reacted for 2.5 hours at the temperature of 80 ℃ and the speed of 600rpm, and simultaneously 34.5g of aluminum nitrate nonahydrate aqueous solution with the mass concentration of 12 percent is dropwise added at the speed of 6.5g/min. And (3) carrying out suction filtration treatment on the mixture after the reaction is finished, repeatedly flushing with absolute ethyl alcohol, and carrying out forced air drying treatment on the obtained filtrate at 75 ℃ for 20 hours to obtain the microcapsule phase-change energy storage material, wherein the mass content of the core material is 74.8%, and the mass content of the shell material is 25.2%.
Example 4
The difference from example 1 is that n-hexacosane is used instead of paraffin, and other reaction conditions and material composition are unchanged, so as to obtain the microcapsule phase change energy storage material, wherein the mass content of the core material is 72.1%, and the mass content of the shell material is 27.9%.
Example 5
The difference from example 1 is that palmitic acid is used instead of paraffin, other reaction conditions and material composition are unchanged, and the microcapsule phase change energy storage material is obtained, wherein the mass content of the core material is 73%, and the mass content of the shell material is 27%.
Example 6
The difference from example 1 is that naphthalene dicarboxylic acid is used instead of benzene tetracarboxylic acid, and other reaction conditions and material compositions are unchanged, so that the microcapsule phase change energy storage material is obtained, wherein the mass content of the core material is 71.8%, and the mass content of the shell material is 28.2%.
Example 7
The difference from example 1 is that benzene diacetic acid is used to replace benzene tetracarboxylic acid, other reaction conditions and material composition are unchanged, and the microcapsule phase change energy storage material is obtained, wherein the mass content of the core material is 72.6%, and the mass content of the shell material is 27.4%.
Example 8
The difference from example 1 is that span 40 is adopted to replace octyl phenol polyoxyethylene ether-15, other reaction conditions and material composition are unchanged, and the microcapsule phase change energy storage material is obtained, wherein the mass content of the core material is 70.8%, and the mass content of the shell material is 29.2%.
Example 9
The difference with example 1 is that tween 40 is used to replace octyl phenol polyoxyethylene ether-15, other reaction conditions and material composition are unchanged, and the microcapsule phase change energy storage material is obtained, wherein the mass content of the core material is 71.3%, and the mass content of the shell material is 28.7%.
Example 10
The difference from example 1 is that the aqueous methanol solution is used instead of the aqueous ethanol solution, and other reaction conditions and material compositions are unchanged, so as to obtain the microcapsule phase change energy storage material, wherein the mass content of the core material is 74.5%, and the mass content of the shell material is 25.5%.
Example 11
The same as in example 1 was different in that an aqueous acetone solution was used instead of an aqueous ethanol solution, and other reaction conditions and material compositions were unchanged, to obtain a microcapsule phase-change energy storage material, wherein the mass content of the core material was 73.7%, and the mass content of the shell material was 26.3%.
Example 12
The difference from example 1 is that in the high-speed shear reaction process, the reaction temperature is increased to 90 ℃, the reaction time is shortened to 5min, the reaction speed is increased to 20000rpm, other reaction conditions and material composition are unchanged, and the microcapsule phase-change energy storage material is obtained, wherein the mass content of the core material is 70.6%, and the mass content of the shell material is 29.4%.
Example 13
The same as in example 1, except that the reaction temperature was reduced to 68 ℃ and the reaction speed was increased to 850rpm during the mechanical stirring reaction, the reaction time was prolonged to 5 hours, and other reaction conditions and material composition were unchanged, to obtain a microcapsule phase-change energy storage material, wherein the mass content of the core material was 71.7% and the mass content of the shell material was 28.3%.
Example 14
The difference from example 1 is that gallium nitrate nonahydrate is used to replace aluminum nitrate nonahydrate, other reaction conditions and material composition are unchanged, and the microcapsule phase change energy storage material is obtained, wherein the mass content of the core material is 73.6%, and the mass content of the shell material is 26.4%.
Example 15
The same as in example 1 was different in that indium nitrate tetrahydrate was used instead of aluminum nitrate nonahydrate, and other reaction conditions and material compositions were unchanged, to obtain a microcapsule phase change energy storage material, wherein the mass content of the core material was 75%, and the mass content of the shell material was 25%.
Example 16
The difference from example 1 was that the mass concentration of the aluminum nitrate nonahydrate aqueous solution was reduced to 5%, and other reaction conditions and material composition were unchanged, to obtain a microcapsule phase change energy storage material, wherein the mass content of the core material was 75.6%, and the mass content of the shell material was 24.4%.
Example 17
The difference from example 1 is that in the process of dropping the aqueous solution of the metal salt, the dropping rate is increased to 10g/min, other reaction conditions and material composition are unchanged, and the microcapsule phase change energy storage material is obtained, wherein the mass content of the core material is 73.2%, and the mass content of the shell material is 26.8%.
Example 18
The difference from example 1 is that in the forced air drying process, the drying temperature is raised to 90 ℃, the drying time is shortened to 12 hours, other reaction conditions and material compositions are unchanged, and the microcapsule phase change energy storage material is obtained, wherein the mass content of the core material is 76.2%, and the mass content of the shell material is 23.8%.
Comparative example 1
The difference from example 1 is that in the phase-change core emulsion preparation process, octyl phenol polyoxyethylene ether-15 is omitted, other reaction conditions and material composition are unchanged, and the microcapsule phase-change energy storage material is obtained, wherein the mass content of the core is 47.8%, and the mass content of the shell is 52.2%.
Comparative example 2
The difference from example 1 is that in the phase-change core emulsion preparation process, the ethanol aqueous solution is replaced by deionized water, other reaction conditions and material composition are unchanged, and the microcapsule phase-change energy storage material is obtained, wherein the mass content of the core material is 40.9%, and the mass content of the shell material is 59.1%.
Comparative example 3
The difference from example 1 is that in the process of dropwise adding the metal salt aqueous solution, the prepared metal salt aqueous solution is directly poured into the phase-change microemulsion to react without adopting a dropwise adding mode, and other reaction conditions and material compositions are unchanged, so that the microcapsule phase-change energy storage material is obtained, wherein the mass content of the core material is 45%, and the mass content of the shell material is 55%.
Comparative example 4
According to the method described in CN106800917A, 0.2424g of zinc nitrate is dissolved in 4mL of deionized water, and the solution is fully dissolved by magnetic stirring for 10 min-15 min in water bath at 500rpm at 40-60 ℃; melting 0.3mL of n-octadecane at 50 ℃, dropwise adding into a zinc nitrate aqueous solution which is stirred at 1000rpm and high speed, and stirring for 30-60 min at the water bath temperature of 50 ℃ to form the Zn-containing zinc alloy 2+ N-octadecane droplets of (2); adding 0.6623g of dimethyl imidazole into the mixed solution dropwise, stirring for 60min, shaking at 150rpm, and mixing dimethyl imidazole with Zn 2+ Forming a metal organic framework, coating n-octadecane, taking out, rapidly cooling, and suction filteringWashing with deionized water at 0 ℃ for several times, and freeze-drying to obtain the three-dimensional hexagonal petal-shaped phase change material.
Comparative example 5
According to the method described in CN103752239A, 4mL of copper sulfate solution with the concentration of 0.75mol/L is prepared at normal temperature, 0.04mol/L of 1, 3-propanediamine solution is added, then the mixture is kept stand for 2 hours at room temperature, filtered and washed, and dried for 12 hours at 60 ℃ to obtain the basic copper sulfate microsphere with a yolk/shell structure. Dispersing 0.003mol of basic copper sulfate microspheres with a core-shell structure in 4mL of mixed solution of ethanol and water (the mol ratio of ethanol to water is 1:1), adding 2mL of 0.2mol/L polyethylene glycol 2000 aqueous solution, stirring for 2h, adding 3mL of ethanol aqueous solution with the concentration of 0.05mol/L trimesic acid under stirring, reacting for 1h at room temperature, filtering and washing, and drying at 40 ℃ for 12h to obtain the metal-organic framework coated phase-change material microcapsule.
Test example 1
Physical and chemical properties of the shaped phase change energy storage materials in examples 1-18, comparative examples 1-3 and commercially available paraffin samples were measured, and specific results are shown in table 1. Wherein paraffin wax, which was tested alone, was not subjected to any treatment.
Table 1 properties of the microcapsule phase change energy storage materials prepared in examples and comparative examples
| Sample of | Particle size/. Mu. m | Melting potential value/J.g -1 | Continuous useMelting potential value/J.after 20 cycles g -1 | Coating Rate/% | Thermal conductivity/W.m -1 ·K -1 | Specific surface area/(m) 2 ·g -1 ) | Pore volume/(cm) 3 ·g -1 ) |
| Paraffin wax | — | 157.5 | — | — | 0.12 | — | — |
| Example 1 | 40 | 123.3 | 120.5 | 78.3 | 0.87 | 450 | 0.39 |
| Example 2 | 30 | 115.9 | 111.2 | 73.6 | 0.65 | 410 | 0.30 |
| Example 3 | 50 | 117.8 | 112.3 | 74.8 | 0.76 | 430 | 0.33 |
| Example 4 | 35 | 113.5 | 109.8 | 72.1 | 0.77 | 420 | 0.32 |
| Example 5 | 37 | 114.9 | 110.2 | 73.0 | 0.75 | 425 | 0.34 |
| Example 6 | 46 | 113.0 | 107.6 | 71.8 | 0.68 | 407 | 0.31 |
| Example 7 | 45 | 114.3 | 108.9 | 72.6 | 0.70 | 410 | 0.32 |
| Example 8 | 33 | 111.5 | 106.7 | 70.8 | 0.63 | 402 | 0.31 |
| Example 9 | 35 | 112.3 | 107.8 | 71.3 | 0.64 | 405 | 0.31 |
| Examples 10 | 42 | 117.3 | 112.6 | 74.5 | 0.69 | 420 | 0.35 |
| Examples 11 | 46 | 116.0 | 110.9 | 73.7 | 0.64 | 415 | 0.33 |
| Examples 12 | 48 | 111.2 | 105.8 | 70.6 | 0.65 | 410 | 0.34 |
| Examples 13 | 37 | 112.9 | 106.0 | 71.7 | 0.65 | 407 | 0.34 |
| Examples 14 | 42 | 115.9 | 110.2 | 73.6 | 0.78 | 435 | 0.36 |
| Examples 15 | 43 | 118.1 | 112.4 | 75.0 | 0.80 | 430 | 0.36 |
| Examples 16 | 39 | 119.0 | 112.7 | 75.6 | 0.78 | 420 | 0.34 |
| Examples 17 | 45 | 115.2 | 110.1 | 73.2 | 0.67 | 415 | 0.34 |
| Examples 18 | 41 | 120.0 | 114.9 | 76.2 | 0.81 | 435 | 0.37 |
| Comparative example 1 | 70 | 75.2 | 65.3 | 47.8 | 0.46 | 270 | 0.25 |
| Comparative example 2 | 10 | 64.4 | 50.3 | 40.9 | 0.41 | 230 | 0.21 |
| Comparative example 3 | 90 | 70.8 | 62.4 | 45 | 0.43 | 240 | 0.25 |
As can be seen from table 1, fig. 1 and fig. 2, the microcapsule phase change energy storage material prepared by the invention has good physicochemical properties and regular morphology structure. In the infrared spectrum of the sample of example 1, the infrared characteristic peaks of the porous coordination polymer and the paraffin wax appear at the same time, which indicates that the coating of the phase change core material paraffin wax by the porous coordination polymer is successfully completed. In the scanning electron microscope photograph of the sample of example 1, the surface of the phase-change core material is covered with the granular porous coordination polymer shell material, and the distribution is more uniform. The sample of example 1 had a melting potential value and a coating ratio of 123.3 J.g, respectively -1 And 78.3%, the latent heat of fusion value is still maintained at 120.5 J.g after 20 continuous use cycles -1 The thermal conductivity, specific surface area and pore volume were 0.87 W.m, respectively -1 ·k -1 、450m 2 Per g and 0.39cm 3 And/g. The melting potential value of the comparative sample is generally lower than 80 J.g -1 Its specific surface area and pore volume are lower than 300m 2 /g and 0.3cm 3 According to the preparation method disclosed by the invention, a mode of synergistic emulsification of an organic ligand and a neutral surfactant is adopted, a complex coordination technology is adopted, and the microcapsule phase change energy storage material containing the porous coordination polymer shell material is obtained by a one-step method, so that the coating rate of the microcapsule is improved, and the porous coordination polymer is distributed more uniformly and compactly on the surface.
Test example 2
The adsorption properties of the microcapsule phase change energy storage materials of examples 1-2 and comparative examples 1-2 on formaldehyde, carbon dioxide and water vapor were measured, and the specific results are shown in Table 2. Before testing the adsorption performance of formaldehyde and carbon dioxide, vacuum degassing a sample in a device at 180 ℃ for 12 hours, wherein the adsorption conditions are 25 ℃ and 100kPa, the flow rates of formaldehyde and carbon dioxide gas are respectively 10mL/min, and the mass of the microcapsule phase-change energy storage material is 5g. The sample is vacuum deaerated for 12 hours at 180 ℃ before testing the adsorption performance of the water vapor, the adsorption condition is 25 ℃ and 100kPa, the water vapor flow rate is 20mL/min, and the mass of the microcapsule phase change energy storage material is 8g.
TABLE 2 adsorption Properties of microcapsule phase-change energy storage Material on different gases
| Sample of | Formaldehyde adsorption quantity/(cm) 3 ·g -1 ) | Carbon dioxide adsorption quantity/(cm) 3 ·g -1 ) | Water vapor adsorption capacity/(cm) 3 ·g -1 ) |
| Example 1 | 100 | 60 | 180 |
| Example 2 | 83 | 43 | 148 |
| Comparative example 1 | 52 | 30 | 95 |
| Comparative example 2 | 42 | 27 | 80 |
As can be seen from Table 2, FIG. 3, FIG. 4 and FIG. 5, the adsorption amount of the samples of the examples on formaldehyde, carbon dioxide and water vapor is obviously higher than that of the samples of the comparative examples, which is consistent with the test results of specific surface area and pore volume in Table 1, and it is demonstrated that the microcapsule phase change energy storage material prepared by the invention uses the porous coordination polymer as the shell material, so that the microcapsule phase change energy storage material has more functions, such as adsorbing harmful gas under normal temperature and normal pressure, better humidity adjusting capability and the like.
Claims (19)
1. A microcapsule phase change energy storage material comprises a core material and a shell material; wherein the core material is a phase change material, and the shell material is a metal-based porous coordination polymer; the mass content of the core material is 70.5-80.5%, and the mass content of the shell material is 19.5-29.5%;
the phase change material is selected from one or more of normal alkane, paraffin and palmitic acid with the phase change temperature of 35-65 ℃;
the organic ligand in the metal-based porous coordination polymer is selected from one or more of pyromellitic acid, 2, 6-naphthalene dicarboxylic acid and terephthalic acid;
the coating rate of the microcapsule phase change energy storage material is 70.5% -80.5%;
the preparation method of the microcapsule phase change energy storage material comprises the following steps:
(1) Mixing a molten phase change material, an organic ligand, a neutral surfactant and a mixed solvent, and performing a shearing reaction to obtain a phase change microemulsion containing the organic ligand;
(2) Stirring and heating the phase-change microemulsion prepared in the step (1) for reaction, and simultaneously dropwise adding a metal salt solution;
(3) Washing and drying the mixture after the reaction in the step (2) to obtain a microcapsule phase change energy storage material;
wherein the metal salt in the step (2) is one or more selected from aluminum nitrate, gallium nitrate and indium nitrate.
2. The microcapsule phase change energy storage material of claim 1, wherein the metal in the metal-based porous coordination polymer is aluminum.
3. The microcapsule phase change energy storage material of claim 1, wherein the organic ligand in the metal-based porous coordination polymer is pyromellitic acid.
4. The microcapsule phase change energy storage material of claim 1, wherein the phase change material is selected from paraffin wax.
5. The microcapsule phase change energy storage material according to claim 1, wherein the particle size of the microcapsule phase change energy storage material is 30 μm to 50 μm.
6. The microcapsule phase change energy storage material according to claim 1, wherein the microcapsule phase change energy storage material has a melting potential value of 105-125J/g.
7. The microcapsule phase-change energy storage material according to claim 1, wherein the microcapsule phase-change energy storage material has a thermal conductivity of 0.5-1.23W m -1 ·k -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific surface area of the microcapsule phase change energy storage material is 401-460 m 2 Per gram, pore volume of 0.31-0.42 cm 3 /g。
8. The microcapsule phase-change energy storage material according to claim 1, wherein the microcapsule phase-change energy storage material has a thermal conductivity of 0.63-0.87W m -1 ·k -1 。
9. A preparation method of a microcapsule phase change energy storage material comprises the following steps:
(1) Mixing a molten phase change material, an organic ligand, a neutral surfactant and a mixed solvent, and performing a shearing reaction to obtain a phase change microemulsion containing the organic ligand;
(2) Stirring and heating the phase-change microemulsion prepared in the step (1) for reaction, and simultaneously dropwise adding a metal salt solution;
(3) Washing and drying the mixture after the reaction in the step (2) to obtain a microcapsule phase change energy storage material;
wherein the molten phase change material in the step (1) is selected from one or more of normal alkane, paraffin and palmitic acid with the phase change temperature of 35-65 ℃; the organic ligand in the step (1) is selected from one or more of pyromellitic acid, 2, 6-naphthalene dicarboxylic acid and terephthalic acid; the neutral surfactant in the step (1) is one or more selected from span 40, tween 40 and octyl phenol polyoxyethylene ether-15;
the metal salt in the step (2) is one or more selected from aluminum nitrate, gallium nitrate and indium nitrate.
10. The method of claim 9, wherein the molten phase change material of step (1) is paraffin; the organic ligand in the step (1) is pyromellitic acid; the neutral surfactant in the step (1) is octyl phenol polyoxyethylene ether-15.
11. The preparation method according to claim 9, wherein the mass ratio of the phase change material, the organic ligand, the neutral surfactant and the mixed solvent in the step (1) is 1: (0.05-0.35): (0.01-0.1): (3-10).
12. The preparation method according to claim 9, wherein the mass ratio of the phase change material, the organic ligand, the neutral surfactant and the mixed solvent in the step (1) is 1: (0.15-0.29): (0.03-0.08): (5-8).
13. The method of claim 9, wherein the metal salt in step (2) is aluminum nitrate.
14. The method according to claim 9, wherein the reaction temperature of the heating reaction in the step (2) is 68 to 85 ℃; the drying temperature of the step (3) is 50-90 ℃; the drying time is 12-24 hours.
15. The method according to claim 9, wherein the reaction temperature of the heating reaction in the step (2) is 73 ℃ to 80 ℃; the drying temperature of the step (3) is 65-75 ℃; the drying time is 16-20 h.
16. A method of using a microcapsule phase change energy storage material according to any of claims 1-8 or a microcapsule phase change energy storage material prepared by a method of any of claims 9-15 for adsorption.
17. The method according to claim 16, wherein the formaldehyde gas flow rate is 2 to 15mL/min at 20 to 30 ℃ and 0 to 100 kPa.
18. The method according to claim 16, wherein the flow rate of the carbon dioxide gas is 2 to 15mL/min at 20 to 30 ℃ and 0 to 100 kPa.
19. The method of claim 16, wherein the steam flow rate is 10 to 30mL/min at 20 ℃ to 30 ℃ and 0kPa to 100 kPa.
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