CN112538191A - Preparation method of composite phase-change material - Google Patents
Preparation method of composite phase-change material Download PDFInfo
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- CN112538191A CN112538191A CN202011487810.6A CN202011487810A CN112538191A CN 112538191 A CN112538191 A CN 112538191A CN 202011487810 A CN202011487810 A CN 202011487810A CN 112538191 A CN112538191 A CN 112538191A
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- 239000012782 phase change material Substances 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 27
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000004964 aerogel Substances 0.000 claims abstract description 22
- 238000007710 freezing Methods 0.000 claims abstract description 20
- 230000008014 freezing Effects 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 20
- 239000001263 FEMA 3042 Substances 0.000 claims description 20
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 20
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical group OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 20
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010257 thawing Methods 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
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- 238000004132 cross linking Methods 0.000 description 3
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- 238000004146 energy storage Methods 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0504—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract
The invention relates to the field of phase-change materials, in particular to a preparation method of a composite phase-change material. The preparation method comprises the following steps: mixing polyethylene glycol and a polyvinyl alcohol solution, placing the mixture in a mold for circulating freezing, taking the mold out, and drying to prepare the aerogel type composite phase-change material; and soaking the aerogel type composite phase-change material in a hydrogen bond cross-linking agent aqueous solution to obtain the composite phase-change material. The preparation method is simple, rapid, green and environment-friendly, and the composite phase-change material with the shape memory effect can be prepared.
Description
Technical Field
The invention relates to the field of phase-change materials, in particular to a preparation method of a composite phase-change material.
Background
In recent years, the working performance of electronic devices is continuously improved, the integration degree of components is continuously improved, and poor heat dissipation causes continuous accumulation of heat and temperature rise, which are not favorable for the efficiency and reliability of the use of the electronic devices. Therefore, effective thermal management methods are critical to electronic devices. Active cooling strategies achieve good performance at the expense of noise, bulk and additional energy consumption, which limits their application in space and weight demanding scenarios. Taking into account that most intelligent electronic products have a time-varying workload, rather than a long continuous run, passive thermal regulation using the latent heat of phase change materials is an effective solution. In practical applications, delicate energy devices inevitably undergo many irreversible deformations, and long-term localized stress concentrations can lead to structural and functional fatigue. By integrating the shape memory function, potential damage can be eliminated, thereby extending the useful life of the electronic device. Shape memory phase change materials have the ability to remember and restore a permanent shape in response to an external stimulus (temperature), while storing and converting energy.
The solid-solid phase change material has the advantages of no liquid generation, small volume change, small supercooling degree, no corrosion, high heat efficiency, long service life and the like. Due to the requirements on ultra-small volume, low power consumption, low noise and even high quality experience, the application of solid-solid phase change materials to the heat dissipation of electronic devices is a trend at present. Although the solid-solid phase change material has the advantage of high thermal efficiency, the current solid-solid phase change material generally has poor mechanical properties, and cannot form a good contact surface with an electronic device to exert the advantage of high energy storage density, which directly influences the efficient heat dissipation of the electronic device.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a composite phase-change material.
In order to realize the purpose of the invention, the technical scheme is as follows:
the invention relates to a preparation method of a composite phase-change material, which at least comprises the following steps:
s1, mixing polyethylene glycol and a polyvinyl alcohol solution, placing the mixture in a mold for circulating freezing, taking the mold out, and drying to obtain the aerogel type composite phase change material;
s2, soaking the aerogel type composite phase change material in an aqueous solution of a hydrogen bond cross-linking agent to obtain the composite phase change material;
the hydrogen bond crosslinking agent is selected from compounds containing at least 20 groups for forming hydrogen bonds with hydroxyl groups;
the groups for hydrogen bonding with hydroxyl are respectively and independently selected from amino, hydrazine, carboxyl, sulfonic acid, fluorinion and hydroxyl.
Optionally, the polyethylene glycol is at least one selected from polyethylene glycol 2000, polyethylene glycol 6000, polyethylene glycol 8000 and polyethylene glycol 10000.
Optionally, the mass percentage concentration of the polyvinyl alcohol solution is 6-8%; the solvent of the polyvinyl alcohol solution is water;
preferably, the mass ratio of the polyvinyl alcohol to the polyethylene glycol is 4-8: 8 to 16.
Optionally, the mixing conditions are as follows: stirring the polyvinyl alcohol solution for 2-3 hours at the temperature of 90-98 ℃, cooling to 50-70 ℃, and adding polyethylene glycol for mixing; preferably, the rotating speed of stirring is 1400-1800 r/min.
Optionally, the conditions of the cycle freezing are as follows: freezing at-25 to-20 ℃ for 10 to 14 hours, and unfreezing at 4 to 8 ℃ for 6 to 10 hours as a cycle; preferably: freezing at-23 deg.C for 12h, and thawing at 6 deg.C for 8h to obtain a circulation;
more preferably, the cyclic freezing is performed 2 to 4 times, and still more preferably 3 times.
Optionally, the drying conditions are as follows: drying for 36-60 h by using a freeze dryer with the pressure of 25-35 mT and the temperature of-75-65 ℃, preferably: drying with a freeze dryer under pressure of 30mT and temperature of-70 deg.C for 48 hr.
Optionally, the hydrogen bonding cross-linking agent is selected from tannic acid; the concentration of the aqueous tannic acid solution is preferably: 5-300 mg/mL.
Optionally, the soaking time in the aqueous solution of tannic acid is 18-24 hours, preferably 20 hours.
Optionally, the preparation method further includes a step of soaking the composite phase change material in deionized water.
Optionally, the soaking time in deionized water is 2.5-3.5 days, and more preferably 3 days.
The invention has at least the following beneficial effects:
the invention provides a simple, rapid, green and environment-friendly preparation method of a shape memory composite phase change material, under the stimulation of temperature, the prepared composite phase change material can recover the original shape and wrap an electronic device, the contact area and the effective contact property of the phase change material and the electronic device are effectively improved, and the cooling efficiency of the composite phase change material on the electronic device is improved.
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 image of a composite phase change material obtained in example 1 of the present invention;
FIG. 2 is an XRD spectrum of the composite phase change material obtained in example 1 of the present invention;
FIG. 3 is a DSC spectrum of the composite phase change material obtained in example 1 of the present invention;
fig. 4 is an electronic photograph of the shape recovery of the composite phase change material obtained in example 1 of the present invention.
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. 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.
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.
According to the embodiment of the invention, polyvinyl alcohol and polyethylene glycol are used as raw materials, an aerogel type phase-change material is prepared by a circulating freeze thawing method, and then the aerogel type phase-change material is soaked in a hydrogen bond cross-linking agent aqueous solution to prepare the composite phase-change material with the shape memory function. And when the temperature of the device is lower than the phase change temperature, the phase change material is cut to be lower than the electronic device, and then the composite phase change material is stretched to the size of the electronic device by using the elasticity of the composite phase change material and is fixed, so that the formed first layer network structure is damaged. When the temperature rises to be higher than the phase change temperature, the phase change material responds to the temperature, the first layer of network structure tends to be restored, the phase change material is shrunk and finally completely attached to the surface of the electronic device, and the heat dissipation performance of the electronic device is improved. The shape memory composite phase change material prepared by the embodiment of the invention can effectively solve the problem of short circuit caused by the flow of the solid-liquid phase change material, and can intelligently adjust the size through the temperature change of the electronic device, thereby realizing the complete surface-to-surface bonding of the phase change material and the electronic device. The preparation method of the embodiment of the invention at least comprises the following steps:
s1, mixing polyethylene glycol and a polyvinyl alcohol solution, placing the mixture in a mold for circulating freezing, taking the mold out, and drying to obtain the aerogel type composite phase change material;
s2, soaking the aerogel type composite phase change material in a hydrogen bond cross-linking agent aqueous solution to obtain a composite phase change material;
the hydrogen bonding crosslinking agent is selected from compounds containing at least 20 groups for forming hydrogen bonds with hydroxyl groups;
the groups for hydrogen bonding with hydroxyl are independently selected from amino, hydrazine, carboxyl, sulfonic acid, fluoride ion and hydroxyl, preferably carboxyl and hydroxyl.
Optionally, the hydrogen bonding cross-linking agent is a compound containing at least 25 groups for forming hydrogen bonds with hydroxyl groups, and further optionally, the hydrogen bonding cross-linking agent is a compound containing at least 30 groups for forming hydrogen bonds with hydroxyl groups.
Further optionally, the hydrogen bond crosslinking agent is a compound containing carboxyl and hydroxyl, wherein the total number of carboxyl and hydroxyl is 35. Further preferred is tannic acid.
According to the embodiment of the invention, firstly, the aerogel type composite phase change material with a first layer of network structure is prepared by adopting a circulating freeze thawing method and freeze drying, and then the aerogel type composite phase change material is soaked in tannic acid to form the novel shape memory composite phase change material with a second layer of strong network structure. The method of the embodiment of the invention directly takes the phase-change material as the component for forming the network structure, can effectively solve the problem of short circuit caused by leakage of the solid-liquid phase-change material, and realizes the shape memory function with responsiveness to temperature through the rupture and recovery of the reversible first layer network structure. The phase-change material provided by the embodiment of the invention is soaked in the aqueous solution of tannic acid to obtain the gel with good mechanical property, and the composite phase-change material attached to the surface of the device can be prepared according to the size of the electronic device, so that the heat dissipation of the intelligent flexible electronic device is very satisfied, and the phase-change material has a wide application prospect.
Optionally, the polyethylene glycol is at least one selected from polyethylene glycol 2000, polyethylene glycol 6000, polyethylene glycol 8000 and polyethylene glycol 10000. The embodiment of the invention can select polyethylene glycol with different molecular weights for preparation, thereby meeting the requirement of high-efficiency heat dissipation of electronic devices in different temperature ranges. The phase-change temperature of the phase-change material prepared by adopting polyethylene glycol 2000 as a raw material is 54 ℃, the phase-change temperature of the phase-change material prepared by adopting polyethylene glycol 6000 as a raw material is 65 ℃, the phase-change temperature of the phase-change material prepared by adopting polyethylene glycol 8000 as a raw material is 63 ℃, and the phase-change temperature of the phase-change material prepared by adopting polyethylene glycol 10000 as a raw material is 70 ℃. Meanwhile, the required phase transition temperature can be obtained by adjusting the proportion of different types of polyethylene glycol.
Specifically, the mass percentage concentration of the polyvinyl alcohol solution is 6-8%, and the solvent of the polyvinyl alcohol solution is water.
Preferably, the mass ratio of the polyvinyl alcohol to the polyethylene glycol is 4-8: 8 to 16. If the content of the polyvinyl alcohol is too high, the corresponding proportion of the content of the polyethylene glycol in the phase-change core material is small, so that the packaging rate is small and the energy storage density is reduced; if the content is too low, there are not enough hydroxyl groups to crosslink to form a hydrogel.
Specifically, the mixing conditions are as follows: stirring the polyvinyl alcohol solution for 2-3 hours at the temperature of 90-98 ℃, cooling to 50-70 ℃, and adding polyethylene glycol for mixing; preferably, the rotating speed of stirring is 1400-1800 r/min.
Specifically, the shape of the mold is designed according to the shape of the electronic device to be heat-dissipated.
Specifically, the cyclic freeze-thaw physical crosslinking method is one of the important methods for preparing PVA hydrogels, and performs physical crosslinking through H bonds between PVA crystallites and PVA chains formed during freezing. Has the characteristic of environmental protection, and the process is relatively simple. Specifically, the conditions of the circulating refrigeration are as follows: freezing at-25 to-20 ℃ for 10 to 14 hours, and unfreezing at 4 to 8 ℃ for 6 to 10 hours as a cycle; preferably: freezing at-23 deg.C for 12h, and thawing at 6 deg.C for 8h to obtain a circulation; more preferably, the cyclic freezing is performed 2 to 4 times, and still more preferably 3 times.
Specifically, the drying conditions are as follows: drying for 36-60 h by using a freeze dryer with the pressure of 25-35 mT and the temperature of-75-65 ℃, preferably: drying with a freeze dryer under pressure of 30mT and temperature of-70 deg.C for 48 hr.
Specifically, the concentration of the aqueous tannic acid solution is as follows: 5-300 mg/mL. Tannic acid has 25 hydroxyl groups and 10 carboxyl groups, so that a large amount of strong hydrogen bond action can be formed with polyvinyl alcohol (PVA) containing a large amount of hydroxyl groups only by a small amount, gel type phase-change materials with different cross-linking networks can be obtained by adjusting the concentration of tannic acid, the concentration of tannic acid aqueous solution is higher, namely the density of a hydrogen bond cross-linking agent is increased, the tensile strength and the elastic modulus of the obtained composite phase-change material are also improved, so that a better deformation effect can be achieved, complete bonding between the phase-change material and the surface of a device can be intelligently realized according to the temperature change of an electronic device, and higher-level heat dissipation of the electronic device is realized.
The proportion of the tannic acid aqueous solution and the aerogel type composite phase-change material is not required, and the aerogel type composite phase-change material is only required to be completely soaked in the tannic acid solution for soaking.
Optionally, the soaking time in the aqueous solution of tannic acid is based on reaching the swelling equilibrium, specifically 18 to 24 hours, and preferably 20 hours.
Specifically, the preparation method of the embodiment of the invention further comprises the step of soaking the composite phase change material in deionized water. The soaking time in the deionized water is based on reaching the swelling balance, specifically 2.5-3.5 days, preferably 3 days.
Specifically, the shape memory function of the composite phase change material can be evaluated through the shape recovery rate, and the specific test method comprises the following steps: preparing a strip of hydrogel (60 mm. times.5 mm. times.1 mm), bending it 180 ° (given angle), then leaving in a test tube at room temperature for 3 hours, and then transferring the deformed gel strip into water at 60 ℃; measuring the included angle between the horizontal plane and the horizontal plane as a final angle;
shape recovery rate ═ (given angle-final angle)/given angle.
The embodiment of the invention also relates to the composite phase-change material prepared by the preparation method, and the composite phase-change material is used for heat dissipation of electronic devices. The composite phase change material has good elasticity, when in use, the composite phase change material is cut into a size smaller than that of an electronic element, the composite phase change material is stretched to the size of the electronic element by the elasticity of the composite phase change material and is fixed, when the temperature of the electronic element rises to the phase change temperature of the electronic element, the composite phase change material has the tendency of returning to the initial state and is contracted, and therefore the phase change material and the surface of the electronic device are completely attached.
The embodiment of the invention also relates to an electronic device which comprises the composite phase change material.
Example 1
1. Stirring polyvinyl alcohol at 95 deg.C for 2.5h, cooling to 50 deg.C, adding phase-change core material polyethylene glycol 2000, mixing completely, and pouring into a mold made of polytetrafluoroethylene plate. Freezing at-23 ℃ for 12h, then thawing at 6 ℃ for 8h, which is a cycle, for a total of 3 cycles. And (3) taking out the sample from the mold, and drying for 48 hours in a freeze dryer with the pressure of 30mT and the temperature of-70 ℃ to sublimate and remove water to obtain the aerogel type composite phase change material.
Wherein, SEM is shown in figure 1, XRD is shown in figure 2, and DSC is shown in figure 3.
2. 0.5g of aerogel type composite phase change material is immersed in 5mg/mL tannic acid aqueous solution for 20h, then immersed in deionized water for 3 days to reach a swelling equilibrium state, so as to obtain the composite phase change material with the shape memory function, the shape recovery rate is measured according to the method, and the photo of the shape recovery of the composite phase change material is shown in figure 4, wherein the left picture is the photo after the shape recovery, and the right picture is the photo bent by 180 degrees.
The phase transition temperature of the composite phase change material is 54 ℃.
The shape recovery rate of the composite phase-change material is (180-30) degree/180-degree is 83.3 percent
Example 2
1. Firstly, polyvinyl alcohol is vigorously stirred for 2.5 hours at the temperature of 95 ℃, then cooled to the temperature of 50 ℃, then phase-change core material polyethylene glycol 6000 is added, and after the materials are completely and uniformly mixed, the mixture is poured into a mold made of a polytetrafluoroethylene plate. Freezing at-23 ℃ for 12h, then thawing at 6 ℃ for 8h, which is a cycle, for a total of 3 cycles. And (3) taking out the sample from the mold, and drying for 48 hours in a freeze dryer with the pressure of 30mT and the temperature of-70 ℃ to sublimate and remove water to obtain the aerogel type composite phase change material.
2. 0.5g of aerogel type composite phase change material is immersed in 80mg/mL tannic acid aqueous solution for 20h, and then immersed in deionized water for 3 days to reach a swelling equilibrium state, so that the composite phase change material with the shape memory function is obtained.
The phase transition temperature of the composite phase change material is 65 ℃.
The shape recovery rate of the composite phase-change material is (180-20) degree/180-degree is 88.8 percent
Example 3
1. Firstly, polyvinyl alcohol is vigorously stirred for 2.5h at the temperature of 95 ℃, then cooled to the temperature of 50 ℃, then phase-change core material polyethylene glycol 8000 is added, and after complete and uniform mixing, the mixture is poured into a mold made of a polytetrafluoroethylene plate. Freezing at-23 ℃ for 12h, then thawing at 6 ℃ for 8h, which is a cycle, for a total of 3 cycles. And (3) taking out the sample from the mold, and drying for 48 hours in a freeze dryer with the pressure of 30mT and the temperature of-70 ℃ to sublimate and remove water to obtain the aerogel type composite phase change material.
2. 0.5g of aerogel type composite phase change material is immersed in 150mg/mL tannic acid aqueous solution for 20h, and then immersed in deionized water for 3 days to reach a swelling equilibrium state, so that the composite phase change material with the shape memory function is obtained.
The phase transition temperature of the composite phase change material is 63 ℃.
The shape recovery rate of the composite phase-change material is (180-10 degrees)/180 degrees is 94.4 percent
Example 4
1. Firstly, polyvinyl alcohol is vigorously stirred for 2.5 hours at the temperature of 95 ℃, then cooled to the temperature of 50 ℃, then phase-change core material polyethylene glycol 10000 is added, and after complete and uniform mixing, the mixture is poured into a mold made of a polytetrafluoroethylene plate. Freezing at-23 ℃ for 12h, then thawing at 6 ℃ for 8h, which is a cycle, for a total of 3 cycles. And (3) taking out the sample from the mold, and drying for 48 hours in a freeze dryer with the pressure of 30mT and the temperature of-70 ℃ to sublimate and remove water to obtain the aerogel type composite phase change material.
2. 0.5g of aerogel type composite phase change material is immersed in 300mg/mL tannic acid aqueous solution for 20h, and then immersed in deionized water for 3 days to reach a swelling equilibrium state, so that the composite phase change material with the shape memory function is obtained.
The phase transition temperature of the composite phase change material is 70 ℃.
The shape recovery rate of the composite phase-change material is (180-25) degree/180-degree is 86.1 percent
Example 5
The composite phase change material is cut into a size smaller than that of the electronic element, and the composite phase change material is stretched to the size of a mobile phone or a computer by means of the elasticity of the composite phase change material and is fixed, so that the electronic device containing the composite phase change material is obtained.
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 preparation method of the composite phase-change material is characterized by at least comprising the following steps:
s1, mixing polyethylene glycol and a polyvinyl alcohol solution, placing the mixture in a mold for circulating freezing, taking the mold out, and drying to obtain the aerogel type composite phase change material;
s2, soaking the aerogel type composite phase change material in an aqueous solution of a hydrogen bond cross-linking agent to obtain the composite phase change material;
the hydrogen bond crosslinking agent is selected from compounds containing at least 20 groups for forming hydrogen bonds with hydroxyl groups;
the groups for hydrogen bonding with hydroxyl are respectively and independently selected from amino, hydrazine, carboxyl, sulfonic acid, fluorinion and hydroxyl.
2. The method according to claim 1, wherein the polyethylene glycol is at least one selected from the group consisting of polyethylene glycol 2000, polyethylene glycol 6000, polyethylene glycol 8000 and polyethylene glycol 10000.
3. The preparation method according to claim 1, wherein the polyvinyl alcohol solution has a mass percent concentration of 6-8%; the solvent of the polyvinyl alcohol solution is water;
preferably, the mass ratio of the polyvinyl alcohol to the polyethylene glycol is 4-8: 8 to 16.
4. The method of claim 1, wherein the mixing conditions are: stirring the polyvinyl alcohol solution for 2-3 hours at the temperature of 90-98 ℃, cooling to 50-70 ℃, and adding polyethylene glycol for mixing; preferably, the rotating speed of stirring is 1400-1800 r/min.
5. The method of claim 1, wherein the conditions of the cyclic freezing are: freezing at-25 to-20 ℃ for 10 to 14 hours, and unfreezing at 4 to 8 ℃ for 6 to 10 hours as a cycle; preferably: freezing at-23 deg.C for 12h, and thawing at 6 deg.C for 8h to obtain a circulation;
more preferably, the cyclic freezing is performed 2 to 4 times, and still more preferably 3 times.
6. The method according to claim 1, wherein the drying conditions are: drying for 36-60 h by using a freeze dryer with the pressure of 25-35 mT and the temperature of-75-65 ℃, preferably: drying with a freeze dryer under pressure of 30mT and temperature of-70 deg.C for 48 hr.
7. The production method according to claim 1,
the hydrogen bond crosslinking agent is selected from tannic acid;
the concentration of the aqueous tannic acid solution is preferably: 5-300 mg/mL.
8. The method according to claim 7, wherein the immersion in the aqueous solution of tannic acid is carried out for 18 to 24 hours, preferably 20 hours.
9. The method according to claim 1, further comprising the step of immersing the composite phase change material in deionized water.
10. The method according to claim 9, wherein the soaking in deionized water is performed for 2.5 to 3.5 days, and more preferably for 3 days.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113131038A (en) * | 2021-03-30 | 2021-07-16 | 暨南大学 | Battery system and assembly method thereof |
| CN113174237A (en) * | 2021-03-30 | 2021-07-27 | 中国地质大学（武汉） | Composite phase-change material and preparation method thereof |
| CN114181666A (en) * | 2021-12-14 | 2022-03-15 | 中国地质大学（武汉） | Modified expanded perlite-based phase-change composite material and preparation method and application thereof |
| CN114474919A (en) * | 2022-03-25 | 2022-05-13 | 桂林理工大学 | Shape memory material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921382A (en) * | 2010-09-17 | 2010-12-22 | 上海交通大学 | Method for preparing shape memory polyurethane resin |
| CN109266314A (en) * | 2018-11-16 | 2019-01-25 | 北京师范大学 | A kind of flexible compound phase-change material and preparation method thereof |
| CN111602845A (en) * | 2020-04-27 | 2020-09-01 | 深圳烟草工业有限责任公司 | Cigarette cooling gel particles and application thereof |
-
2020
- 2020-12-16 CN CN202011487810.6A patent/CN112538191A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921382A (en) * | 2010-09-17 | 2010-12-22 | 上海交通大学 | Method for preparing shape memory polyurethane resin |
| CN109266314A (en) * | 2018-11-16 | 2019-01-25 | 北京师范大学 | A kind of flexible compound phase-change material and preparation method thereof |
| CN111602845A (en) * | 2020-04-27 | 2020-09-01 | 深圳烟草工业有限责任公司 | Cigarette cooling gel particles and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAILONG FAN: "Tough，Swelling-Resistant， Self-Healing,，and Adhesive Dual-Cross-Linked Hydrogels Based on Polymer−Tannic Acid Multiple Hydrogen Bonds", 《MACROMOLECULES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113131038A (en) * | 2021-03-30 | 2021-07-16 | 暨南大学 | Battery system and assembly method thereof |
| CN113174237A (en) * | 2021-03-30 | 2021-07-27 | 中国地质大学（武汉） | Composite phase-change material and preparation method thereof |
| CN114181666A (en) * | 2021-12-14 | 2022-03-15 | 中国地质大学（武汉） | Modified expanded perlite-based phase-change composite material and preparation method and application thereof |
| CN114474919A (en) * | 2022-03-25 | 2022-05-13 | 桂林理工大学 | Shape memory material and preparation method and application thereof |
| CN114474919B (en) * | 2022-03-25 | 2023-08-11 | 桂林理工大学 | Shape memory material and preparation method and application thereof |
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