CN113549429A - Phase change microcapsule with controllable supercooling degree and preparation method and application thereof - Google Patents

Phase change microcapsule with controllable supercooling degree and preparation method and application thereof Download PDF

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CN113549429A
CN113549429A CN202110955960.3A CN202110955960A CN113549429A CN 113549429 A CN113549429 A CN 113549429A CN 202110955960 A CN202110955960 A CN 202110955960A CN 113549429 A CN113549429 A CN 113549429A
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phase
phase fluid
supercooling degree
shell
nucleating agent
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CN113549429B (en
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贾莉斯
钟凯
陈颖
莫松平
王慧昌
李俊
覃光军
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Guangdong University of Technology
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/06Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/06Making microcapsules or microballoons by phase separation
    • B01J13/14Polymerisation; cross-linking

Abstract

The invention belongs to the technical field of functional material preparation, and discloses a phase change microcapsule with controllable supercooling degree, and a preparation method and application thereof. After the liquid nucleating agent and the organic phase-change material are uniformly mixed, the phase-change microcapsule with uniform and controllable shell thickness and grain diameter is obtained by adopting microfluidic double emulsification and ultraviolet curing, the liquid nucleating agent is uniformly dispersed in the phase-change microcapsule, and the phase-change microcapsule has good dispersibility and thermal cycle stability, so that the supercooling degree of the capsule is remarkably reduced along with the increase of the concentration of the nucleating agent. The particle size and the shell thickness are strictly controlled by using a microfluidic technology, the influence of the particle size and the shell thickness on the supercooling degree is eliminated, and the accurate regulation and control of the supercooling degree is realized. The invention uses 1, 6-hexanediol diacrylate as the shell material, the monomer is irradiated by ultraviolet lamp to generate cross-linking reaction and polymerize into solid to form the shell, the method is simple, and the surface of the formed shell is smooth and firm. Is suitable for scientific research and industrial production of multifunctional phase change microcapsules.

Description

Phase change microcapsule with controllable supercooling degree and preparation method and application thereof
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a phase change microcapsule with controllable supercooling degree, and a preparation method and application thereof.
Background
The phase-change material has the characteristic of absorbing and releasing a large amount of latent heat in the liquid-solid phase conversion process, is a good heat storage material, and has wide application in the fields of latent heat storage of buildings, heat control of electronic modules and the like. Paraffin is the most widely used organic phase change material, and has the advantages of good economy, high enthalpy value and wide application temperature range. However, the paraffin often causes leakage due to the fluidity and the deformability during the use, which is not favorable for the recycling. And by using a microcapsule encapsulation technology, the paraffin phase-change material can be encapsulated in an organic or inorganic shell layer to form a phase-change microcapsule, so that the phase change is carried out in a closed space, and the leakage is prevented. Meanwhile, the heat conduction area after paraffin microencapsulation is increased, and the effect of heat exchange enhancement can also be achieved.
However, a new problem occurs after the phase change microencapsulation of paraffin, and in practical application, the supercooling phenomenon does not exist in large-volume paraffin, but the severe supercooling phenomenon occurs after the phase change material of paraffin is microencapsulated. Phase-change microcapsules formed by coating n-dodecane with Melamine Formaldehyde (MF) have exhibited significant supercooling, and the smaller the particle size, the more serious the supercooling problem. The supercooling problem of the energy storage working medium can reduce the efficiency of the heat storage system and increase the energy consumption.
In order to solve the supercooling problem of the paraffin phase-change microcapsule, researchers try to add a nucleating agent in a microcapsule core material to promote heterogeneous nucleation. Nucleating agents used include SiO2、TiO2And the like solid nucleating agents and liquid nucleating agents such as octadecanol, tetradecanol and the like. The Chinese patent (CN106753261A) reduces the supercooling degree of the microcapsule by adding the composite aluminum and the graphite nano particles, and really achieves a certain supercooling degree reduction effect, but when solid particles are used as the nucleating agent, because the dispersibility of the particles is poor, the agglomeration and delamination phenomena are easy to occur, and the recycling of the phase-change microcapsule is not facilitated. And using a liquid which is mutually soluble with the core material as a nucleating agent to ensure thatThe obtained nucleating agent can be uniformly dispersed in the phase-change material, and the liquid nucleating agent firstly generates phase transition by utilizing different melting points of the two, serves as a seed crystal for the phase change of a core material at the back, can effectively promote heterogeneous nucleation, and achieves the purpose of inhibiting supercooling. When the temperature is increased, the nucleating agent is uniformly dissolved in the core material again, so that the cyclic utilization rate of the capsule is greatly enhanced.
The supercooling degree of the phase-change microcapsule is related to the type and concentration of the nucleating agent and is also influenced by various factors such as the particle size of the capsule, the thickness of a shell layer, the material of the shell layer and the like. Therefore, even if the same type of nucleating agent is used for acting on the phase-change microcapsules made of the same material, the amplitude of the supercooling degree of the microcapsules is different under the same nucleating agent concentration. The main reason for this problem is that the capsule preparation methods commonly used today have no way to precisely control the size of the capsule particle size and the thickness of the capsule wall, and the amount of the nucleating agent encapsulated in the capsule is also inconsistent, so the concentration of the nucleating agent required for each elimination of supercooling degree is always not referenced. And the microfluidic technology can form single-weight O/W (W/O) or double-weight O/W/O (W/O/W) template liquid drops even higher-order template liquid drops by shearing of various immiscible fluids, and provides an excellent template for synthesizing nano-microcapsules with uniform size, shape and functionality.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention mainly aims to provide a preparation method of a phase-change microcapsule with controllable supercooling degree; the method adopts mutual dissolution of a liquid nucleating agent and a phase-change material, adopts a microfluidic double emulsification combined ultraviolet curing method, injects core materials after mutual dissolution into a capsule shell, strictly controls the particle size and the shell thickness of the capsule, and ensures that the nucleating agents in each capsule are almost the same in quantity and are uniformly distributed. Thereby realizing the accurate control of the supercooling degree of the phase change microcapsule.
The invention further aims to provide the phase change microcapsule with the controllable supercooling degree, which is prepared by the preparation method.
The invention also aims to provide application of the phase change microcapsule with the controllable supercooling degree.
The purpose of the invention is realized by the following technical scheme:
a phase change microcapsule with controllable supercooling degree comprises a capsule core and a shell of a doped liquid nucleating agent, wherein the particle size of the capsule is accurately regulated and controlled to be 50-1500 mu m and the shell thickness of the shell is 20-500 mu m by utilizing a microfluidic technology, and the mass percentage content ratio of the capsule core to the shell is (5% -95%): (5% -95%); the mass percentage concentration of the liquid nucleating agent in the capsule core is 0-20%.
The capsule core consists of an organic phase-change material and a liquid nucleating agent, wherein the organic phase-change material is at least one of a straight-chain alkane compound and a straight-chain alkane halide; the liquid nucleating agent is at least one of an alcohol compound and a fatty acid compound.
The shell is made of the following raw materials: 97 percent of 1, 6-hexanediol diacrylate (HDDA), 2 percent of photoinitiator 2-hydroxy-2-methyl propiophenone and 1 percent of surfactant span 80.
The organic phase change material is more than one of tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane and composite paraffin phase change material; the liquid nucleating agent is more than one of tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid.
The preparation method of the phase change microcapsule with the controllable supercooling degree comprises the following steps:
(1) adding polyvinyl alcohol (PVA) into deionized water, and stirring at 70 ℃ to obtain an aqueous phase fluid with the mass fraction of 2%; mixing 97% by mass of 1, 6-hexanediol diacrylate (HDDA), 2% by mass of 2-hydroxy-2-methyl propiophenone and 1% by mass of surfactant span80, and uniformly stirring at normal temperature to obtain an intermediate phase fluid; adding 0-20% of liquid nucleating agent by mass percent into the organic phase-change material, and uniformly stirring the mixture to be used as oil phase fluid under the condition that the melting point temperature of the organic phase-change material and the melting point temperature of the organic phase-change material are higher than the melting point temperature of the organic phase-change material;
(2) the microcapsule is prepared by utilizing the microfluidic chip, and the specific operation steps are as follows: respectively pushing an aqueous phase fluid, an intermediate phase fluid and an oil phase fluid into a Teflon guide tube from an injection pump of the microfluidic chip and then leading the aqueous phase fluid, the intermediate phase fluid and the oil phase fluid into the microfluidic chip, wherein the oil phase fluid is led into the microfluidic chip from a small-tip glass capillary tube, the intermediate phase fluid is led into the microfluidic chip from a first closed liquid storage tank, and the aqueous phase fluid is led into the microfluidic chip from a second closed liquid storage tank; the oil phase fluid flows out of the small sharp nozzle glass capillary, is cut by the intermediate phase fluid to form jet flow, is cut by the water phase fluid to form liquid drops with uniform and controllable sizes, the liquid drops are irradiated by an ultraviolet lamp to serve as energy sources to initiate when passing through the small glass capillary, 1, 6-hexanediol diacrylate is subjected to cross-linking reaction and polymerization to form a shell, an organic phase change material containing a nucleating agent serves as a core material and is completely wrapped in the shell, and the phase change microcapsule with the controllable supercooling degree is obtained.
And replacing the oil phase fluid containing the nucleating agents with different concentrations to obtain capsules of the nucleating agents with different concentrations under the strict uniform inner and outer diameters, thereby realizing the accurate regulation and control of the supercooling degree.
The micro-fluidic chip is a double-emulsified glass capillary micro-fluidic chip in the Chinese invention patent with the application number of 201811008829.0.
The application of the phase change microcapsule with the controllable supercooling degree in the field of phase change energy storage.
The relationship between the injection pump flow rate and the droplet size is as follows: the flow velocity of the aqueous phase fluid is increased, so that the aqueous phase cutting force can be enhanced, and the outer diameter of the capsule is reduced; the flow of the core material in the same time can be increased by increasing the flow speed of the oil phase fluid, and the inner diameter of the capsule is increased; increasing the flow rate of the intermediate phase fluid can simultaneously increase the outer diameter and decrease the inner diameter to achieve the effect of increasing the wall thickness.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention breaks through the means that the grain diameter of the capsule is not uniform and the thickness of the shell layer is uncontrollable in the traditional capsule preparation means, realizes the strict control of the grain diameter of the microcapsule and the thickness of the shell layer by means of the three-phase coaxial flow type micro-fluidic chip, eliminates the influence of other factors on the supercooling degree, ensures that the supercooling degree change is only hooked with the concentration of the nucleating agent, and realizes the accurate regulation and control of the supercooling degree.
(2) The invention breaks through the limitation that most of the traditional phase-change microcapsules use solid nucleating agents, uses the liquid nucleating agents to be mutually dissolved with the phase-change materials and then injects the solution into the shell layer in equal quantity by using the microfluidic technology, thereby ensuring that the nucleating agents are uniformly distributed in the phase-change materials and keeping the number of nucleation points in each capsule consistent; the repeatability of the experiment is improved, the liquid nucleating agent cannot agglomerate or sink, and the cyclic utilization rate of the capsule is greatly enhanced.
(3) 1, 6-hexanediol diacrylate (HDDA) is used as a shell layer, and the surface formed by ultraviolet light curing of the shell layer material is highly compact and smooth, so that the capsule leakage can be greatly prevented; and meanwhile, the shell is hard and the thickness can be regulated and controlled, so that the capsule can normally work in some high-pressure environments.
Drawings
FIG. 1 is a microscopic view of phase-change microcapsules with different particle sizes.
FIG. 2 is a scanning electron microscope image of phase change microcapsules.
FIG. 3 is a differential scanning calorimetry spectrum of microcapsules at different concentrations of nucleating agent at an internal diameter of 220 μm.
FIG. 4 is a graph showing the degree of supercooling according to the concentration of the nucleating agent at each grain size.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
preparing raw materials: 10g of polyvinyl alcohol (PVA) is added into 500mL of deionized water, and the mixture is continuously stirred for 40min at 70 ℃ and 1000r/min to obtain PVA aqueous solution as an aqueous phase fluid. 9.7g of 1, 6-hexanediol diacrylate (HDDA) was weighed out, 0.1g of surfactant (span80) and 0.2g of photoinitiator (2-hydroxy-2-methylpropiophenone) were added, and the mixture was stirred on a magnetic stirrer at 25 ℃ and 1000r/min for 20min to obtain an intermediate phase fluid. Eleven groups of octadecane phase change materials with the mass of 10g are weighed, octadecanol with the mass of 0g, 0.1g, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g, 0.7g, 0.8g, 0.9g and 1g is respectively added into the octadecanol, and the mixture is placed on a magnetic stirrer to be continuously stirred for 30min at the temperature of 70 ℃ and the speed of 1000r/min to be used as oil phase fluid.
The microcapsule is prepared by using a double-emulsified glass capillary microfluidic chip in the Chinese invention patent with the application number of 201811008829.0 as a microfluidic chip: respectively pushing an aqueous phase fluid, an intermediate phase fluid and an oil phase fluid into a Teflon guide tube from an injection pump of the microfluidic chip and then leading the aqueous phase fluid, the intermediate phase fluid and the oil phase fluid into the microfluidic chip, wherein the oil phase fluid is led into the microfluidic chip from a small-tip glass capillary tube, the intermediate phase fluid is led into the microfluidic chip from a first closed liquid storage tank, and the aqueous phase fluid is led into the microfluidic chip from a second closed liquid storage tank; the three phase fluid flow rate through the syringe pump regulation, and the use of optical microscope and computer to microchip internal reaction visualization, in the microscope we can see: the oil phase fluid flows out of the small sharp nozzle glass capillary, is cut by the intermediate phase fluid to form jet flow, is cut by the water phase fluid to form liquid drops with uniform and controllable sizes, the liquid drops are irradiated by an ultraviolet lamp to be used as energy to initiate when passing through the small glass capillary, 1, 6-hexanediol diacrylate is subjected to cross-linking reaction and polymerization to form a shell, an organic phase change material containing a nucleating agent is used as a core material and is completely wrapped in the shell, and the phase change microcapsule is obtained. And changing the flow rate of the water phase to 850 mu L/min, regulating the flow rate of the intermediate phase to 35 mu L/min, regulating the flow rate of the oil phase to 10 mu L/min, adding 4ml of water phase solution into a 5ml collection bottle after the flow rate is stable, and collecting the water phase solution, wherein the microcapsules with the inner diameter of 150 microns, the shell thickness of 75 mu m and the specified nucleating agent concentration are obtained after 3-4 minutes. Then keeping the three-phase flow velocity unchanged, replacing the octadecane oil phase with different octadecanol concentrations, ensuring that the old oil phase completely flows out, and then collecting by using a new collecting bottle, repeating the steps to finally obtain six groups of microcapsules with the inner and outer diameters of 150 mu m/300 mu m and the nucleating agent concentration of 0-10%. And after the collection is finished, continuously adjusting the flow rate of the water phase to 700 mu L/min, the flow rate of the intermediate phase to 35 mu L/min and the flow rate of the oil phase to 15 mu L/min to obtain microcapsules with the inner diameter of 220 mu m and the shell thickness of 75 mu m, and replacing different oil phases to obtain six groups of microcapsules with the inner diameter of 220 mu m/370 mu m and the nucleating agent concentration of 0% -8%. Regulating the flow rate of the water phase to 550 mu L/min, regulating the flow rate of the intermediate phase to 35 mu L/min, regulating the flow rate of the oil phase to 20 mu L/min to obtain microcapsules with the inner diameter of 300 mu m and the shell thickness of 75 mu m, and replacing different oil phases to obtain six groups of microcapsules with the inner diameter of 300 mu m/450 mu m and the nucleating agent concentration of 0-6%. And finally washing the obtained product with deionized water for 4-5 times, filtering, and drying for 24 hours at 40 ℃ by using a vacuum drying oven. And obtaining the phase change microcapsule.
An optical micrograph of the phase-change microcapsule prepared as described above is shown in fig. 1. The capsules are regular in morphology, the polydispersity indexes PDI are all less than 3%, the particle size meets the high monodispersion standard, the phase change microcapsules can be considered to be uniform in particle size, and meanwhile, the shell layer thickness is controlled to be about 75 microns. The influence of supercooling degree caused by the size of the grain diameter and the thickness of the shell layer is eliminated.
The scanning electron micrograph of the phase-change microcapsules prepared above is shown in fig. 2. It can be clearly seen from the SEM image that each phase-change microcapsule is in a regular spherical shape and has a compact and smooth surface without leakage.
The differential scanning calorimetry curve of the 220 μm phase-change microcapsule prepared above is shown in fig. 3, and octadecanol is added, a new solidification phase-change peak appears in the high-temperature direction, and the higher the octadecanol concentration is, the area ratio of the high-temperature peak gradually increases, and the phase-change temperature gradually moves towards the high-temperature direction. The supercooling degree had decreased to 0 when the octadecanol concentration reached 4%.
The variation curve of the supercooling degree of the phase-change microcapsules with the grain sizes along with the concentration of the nucleating agent is shown in fig. 4. From the figure, the fact that the addition of the octadecanol can effectively promote heterogeneous nucleation and solve the problem of supercooling of the capsule can be obtained, and the supercooling degree of the capsule is gradually reduced to zero along with the increase of the concentration of the octadecanol. When the concentration of octadecanol in 150 μm octadecane capsule is 0%, 2%, 4%, 6%, the supercooling degree is 4 deg.C, 1.7 deg.C, 0.75 deg.C, 0 deg.C; when the concentration of octadecanol in octadecane capsules with the inner diameter of 220 mu m is 0%, 2%, 3% and 4% respectively, the supercooling degree is 3.8 ℃, 1.3 ℃, 0.5 ℃ and 0 ℃; when the concentration of octadecanol in 300 μm diameter octadecane capsule is 0%, 1%, 2%, 3%, the supercooling degree is 3.5 deg.C, 1.9 deg.C, 0.75 deg.C, 0 deg.C, respectively. According to the comparison of curves of different grain sizes, the difference between different grain sizes is large no matter the amplitude of supercooling degree reduced along with the concentration of the nucleating agent or the minimum concentration of the nucleating agent required for reducing the supercooling degree to zero. Therefore, the important precondition for researching the nucleation supercooling phenomenon is to ensure the uniform particle size distribution of the phase-change microcapsules. And the accurate regulation and control of the supercooling degree can be realized only by controlling the particle size of the capsule and the thickness of the shell layer and ensuring that the nucleating agent is uniformly dispersed in the core material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (6)

1. A phase change microcapsule with controllable supercooling degree is characterized in that: the microcapsule comprises a capsule core doped with a liquid nucleating agent and a shell, the particle size of the capsule is accurately regulated and controlled to be 50-1500 mu m and the shell thickness of the shell is controlled to be 20-500 mu m by utilizing a microfluidic technology, and the mass percentage of the capsule core to the shell is (5% -95%): (5% -95%); the mass percentage concentration of the liquid nucleating agent in the capsule core is 0-20%.
The capsule core consists of an organic phase-change material and a liquid nucleating agent, wherein the organic phase-change material is at least one of a straight-chain alkane compound and a straight-chain alkane halide; the liquid nucleating agent is at least one of an alcohol compound and a fatty acid compound.
The shell is made of the following raw materials: 97 percent of 1, 6-hexanediol diacrylate, 2 percent of photoinitiator 2-hydroxy-2-methyl propiophenone and 1 percent of surfactant span 80.
2. A phase change microcapsule with controllable supercooling degree as claimed in claim 1, wherein: the organic phase change material is more than one of tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane and composite paraffin phase change material; the liquid nucleating agent is more than one of tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid.
3. The method for preparing the phase-change microcapsule with the controllable supercooling degree of the claim 1, which is characterized by comprising the following steps:
(1) adding polyvinyl alcohol into deionized water, and stirring at 70 ℃ to obtain an aqueous phase fluid with the mass fraction of 2%; mixing 97% by mass of 1, 6-hexanediol diacrylate, 2% by mass of 2-hydroxy-2-methyl propiophenone and 1% by mass of surfactant span80, and uniformly stirring at normal temperature to obtain an intermediate phase fluid; adding 0-20% of liquid nucleating agent by mass percent into the organic phase-change material, and uniformly stirring the mixture to be used as oil phase fluid under the condition that the melting point temperature of the organic phase-change material and the melting point temperature of the organic phase-change material are higher than the melting point temperature of the organic phase-change material;
(2) the microcapsule is prepared by utilizing the microfluidic chip, and the specific operation steps are as follows: respectively pushing an aqueous phase fluid, an intermediate phase fluid and an oil phase fluid into a Teflon guide tube from an injection pump of the microfluidic chip and then leading the aqueous phase fluid, the intermediate phase fluid and the oil phase fluid into the microfluidic chip, wherein the oil phase fluid is led into the microfluidic chip from a small-tip glass capillary tube, the intermediate phase fluid is led into the microfluidic chip from a first closed liquid storage tank, and the aqueous phase fluid is led into the microfluidic chip from a second closed liquid storage tank; the oil phase fluid flows out of the small sharp nozzle glass capillary, is cut by the intermediate phase fluid to form jet flow, is cut by the water phase fluid to form liquid drops with uniform and controllable sizes, the liquid drops are irradiated by an ultraviolet lamp to serve as energy sources to initiate when passing through the small glass capillary, 1, 6-hexanediol diacrylate is subjected to cross-linking reaction and polymerization to form a shell, an organic phase change material containing a nucleating agent serves as a core material and is completely wrapped in the shell, and the phase change microcapsule with the controllable supercooling degree is obtained.
4. The production method according to claim 3, characterized in that: and replacing the oil phase fluid containing the nucleating agents with different concentrations to obtain capsules of the nucleating agents with different concentrations under the strict uniform inner and outer diameters, thereby realizing the accurate regulation and control of the supercooling degree.
5. The production method according to claim 3, characterized in that: the micro-fluidic chip is a double-emulsified glass capillary micro-fluidic chip in the Chinese invention patent with the application number of 201811008829.0.
6. The use of the phase-change microcapsule with controllable supercooling degree of claim 1 in the field of phase-change energy storage.
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CN114288955A (en) * 2021-12-31 2022-04-08 广东工业大学 Method for reducing supercooling degree of alkane phase change microcapsule by mixing multiple particle sizes, prepared phase change microcapsule and application
CN114288955B (en) * 2021-12-31 2024-03-29 广东工业大学 Method for reducing supercooling degree of alkane phase-change microcapsule by multi-particle-size mixing, prepared phase-change microcapsule and application
CN114797699A (en) * 2022-04-22 2022-07-29 广东工业大学 Method for eliminating supercooling degree of paraffin phase change microcapsule and causing no loss of phase change enthalpy, prepared phase change microcapsule and application thereof
CN114797699B (en) * 2022-04-22 2023-05-26 广东工业大学 Method for eliminating supercooling degree of paraffin phase-change microcapsule and loss-free phase-change enthalpy, prepared phase-change microcapsule and application thereof
CN116814224A (en) * 2023-06-29 2023-09-29 合肥芯能相变新材料科技有限公司 Low-supercooling-degree phase-change microcapsule and preparation method thereof
CN116814224B (en) * 2023-06-29 2024-03-08 合肥芯能相变新材料科技有限公司 Low-supercooling-degree phase-change microcapsule and preparation method thereof

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