CN112226207A - High-stability solid-solid composite phase change material and preparation method thereof - Google Patents
High-stability solid-solid composite phase change material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-stability solid-solid composite phase change material and a preparation method thereof, belongs to the technical field of phase change energy storage materials, and aims to solve the problems that polyethylene glycol is easy to leak in a molten state, low in heat storage/release rate and difficult to popularize and apply as a solid-liquid phase change material. The raw materials for preparing the material comprise 10ml of modified polyethylene glycol solution, 10ml of chitosan solution and inorganic framework material; the mass of the inorganic framework material is 0.5-10 times of the mass of chitosan in 10ml of chitosan solution. The method comprises the following steps: preparing a modified polyethylene glycol aqueous solution, preparing a chitosan solution, adding an inorganic framework material, mixing raw materials and preparing a product to obtain the high-stability solid-solid composite phase change material. The composite phase-change material prepared by the formula and the method has a loose and porous three-dimensional network structure and has the characteristic of solid-solid phase change; and the heat storage performance is excellent, and the latent heat can reach 149.6J/g.
Description
Technical Field
The invention belongs to the technical field of phase change energy storage materials, and particularly relates to a high-stability solid-solid composite phase change material and a preparation method thereof.
Background
The energy storage technology is one of the most effective methods for relieving the problems of energy supply and demand mismatching and environmental pollution, and can obviously improve the utilization rate of intermittent unstable energy. The phase-change energy storage technology utilizes the phase-change material to store or release heat energy, has the advantages of high heat energy storage density, easy system operation and control, approximately constant temperature of the system in the phase-change process and the like, and is widely applied to the fields of solar energy, buildings, aerospace, drug transmission and the like.
The phase change heat storage is generally classified into four types, solid-solid phase change, solid-liquid phase change, liquid-gas phase change and solid-gas phase change, according to the type of the phase change. The latter two phase change modes are accompanied by a large amount of gas in the phase change process, so that the volume change of the material is large, and the two phase change modes are rarely selected in practical application despite large phase change heat, and the solid-solid phase change and the solid-liquid phase change are more phase change types in practice.
In the prior art, polyethylene glycol is a typical solid-liquid phase change material and is widely used due to the advantages of high heat storage density, no toxicity, no corrosion, wide phase change temperature range and the like, but molten polyethylene glycol has fluidity and is easy to leak, and the heat storage/release rate of the polyethylene glycol is low, so that the popularization and the application of the polyethylene glycol are limited to a certain extent.
Graft copolymerization, one of the techniques for preparing shaped composite phase change materials, grafts appropriate branches or functional side groups onto a macromolecular chain by chemical reaction. At present, some reports related to the preparation of phase change composite materials by using polyethylene glycol and chitosan exist, in the report adopting a graft copolymerization method, the grafting copolymerization method is adopted by modifying chitosan and then copolymerizing the chitosan and the polyethylene glycol, and the heat storage capacity, especially the heat conduction performance of the prepared composite phase change materials have larger space for improving.
Therefore, how to more conveniently utilize polyethylene glycol to produce the high-stability solid-solid composite phase change material and improve the heat conduction rate of the solid-solid composite phase change material on the basis of ensuring the heat storage capacity of the solid-solid composite phase change material becomes a research and development direction of technicians in the field.
Disclosure of Invention
The invention aims to provide a high-stability solid-solid composite phase change material to solve the problems that polyethylene glycol is easy to leak in a molten state and has low heat storage/release rate when being used as a solid-liquid phase change material.
The invention also aims to provide a preparation method of the high-stability solid-solid composite phase-change material, the method is convenient and easy to control, and the prepared composite phase-change material has better heat storage performance and heat conduction performance.
The technical scheme of the invention is as follows:
a high-stability solid-solid composite phase change material is prepared from the following raw materials: 10ml of modified polyethylene glycol solution, 10ml of chitosan solution and inorganic framework material; the mass of the inorganic framework material is 0.5-10 times of the mass of chitosan in 10ml of chitosan solution.
Further, the chitosan solution is a mixed solution of 0.1-1.2g of chitosan dispersed in a solution containing 99.5ml of deionized water and 0.5ml of acetic acid.
Further, the inorganic framework material is one or more of halloysite, sepiolite, carbon nanotubes or attapulgite.
Further, the concentration of the modified polyethylene glycol is 5-60 wt%.
Further, the modified polyethylene glycol aqueous solution is a double-end aldehyde group polyethylene glycol aqueous solution or a double-end carboxyl group polyethylene glycol aqueous solution.
The preparation method of the high-stability solid-solid composite phase change material comprises the following steps:
step A, preparing a modified polyethylene glycol aqueous solution:
preparing 5-60wt% of double-end aldehyde group polyethylene glycol aqueous solution or double-end carboxyl polyethylene glycol aqueous solution;
step B, preparing a chitosan solution:
weighing 0.1-1.2g of chitosan, and dispersing the chitosan into a mixed solution containing 99.5ml of deionized water and 0.5ml of acetic acid solution to prepare a chitosan solution for later use;
step C, adding an inorganic framework material:
adding 0.5-10 times of inorganic framework material of chitosan into 10ml of modified polyethylene glycol aqueous solution, and performing ultrasonic dispersion for 10min to obtain uniformly dispersed mixed solution;
step D, raw material mixing and product preparation:
mixing 10ml of chitosan solution with the mixed solution, and reacting for 24 hours at the temperature of 60 ℃; and then drying the mixture at normal pressure or freeze drying the mixture to obtain the product, namely the high-stability solid-solid composite phase change material.
Further, the aqueous solution of the double-end aldehyde group polyethylene glycol in the step a is prepared as follows:
adding 2.50mmol of polyethylene glycol, 6.00-10.00mmol of p-aldehyde benzoic acid, 7.50mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 7.50mmol of pyridine into 250ml of dichloromethane in sequence, stirring at normal temperature for 48h, removing the dichloromethane by rotary evaporation, washing with glacial ethyl ether for 5 times, and drying under vacuum at 25 ℃ for 12h to obtain the double-end aldehyde group polyethylene glycol; dissolving the double-end aldehyde group polyethylene glycol into deionized water to prepare a 5-60wt% double-end aldehyde group polyethylene glycol aqueous solution for later use.
Further, an aqueous solution of carboxyl-terminated polyethylene glycol was prepared as follows:
taking 2.50mmol of polyethylene glycol, 5.00-10.00mmol of maleic anhydride and 7.50mmol of pyridine in a container with an air condenser, a stirrer, a thermometer and a nitrogen inlet pipe2Mixing in four-mouth bottle of the protection device, and introducing N2Heating, reacting at 160 ℃ for 6h, cooling to room temperature, and separating out a product; washing the product with glacial ethyl ether for 5 times, and drying in vacuum at 25 ℃ for 12h to obtain carboxyl-terminated polyethylene glycol; dissolving the carboxyl-terminated polyethylene glycol into deionized water to prepare 5-60wt% of carboxyl-terminated polyethylene glycol aqueous solution for later use.
Further, the molar mass of the polyethylene glycol used for preparing the aqueous solution of the aldehyde-terminated polyethylene glycol and the aqueous solution of the carboxyl-terminated polyethylene glycol in the step A is 600-12000 g/mol.
The invention has the following beneficial effects:
(1) in the formula, the high-stability solid-solid composite phase change material is prepared by matching the inorganic framework, the chitosan and the modified polyethylene glycol. As a novel phase-change heat storage material, the phase-change heat storage material has high stability, heat storage capacity and heat storage/release efficiency. The novel material is provided for people, the application range of the polyethylene glycol as the heat storage phase-change material is widened, and the product performance and the application field are obviously improved compared with the traditional polyethylene glycol-based composite phase-change material.
(2) The method comprises the following steps:
firstly, modifying polyethylene glycol characterized by double-end hydroxyl groups into polyethylene glycol characterized by double-end aldehyde groups or carboxyl groups; and grafting the modified polyethylene glycol onto chitosan with higher strength and more stable structure by a chemical reaction by adopting a graft copolymerization method to prepare the solid-solid phase change material. The strong chemical bond formed between the modified polyethylene glycol and the chitosan can effectively limit the fluidity of the phase-change material in a molten state, so that the composite phase-change material has the characteristic of solid-solid phase change, namely, the storage and release of heat energy are completed through the phase change between solid states. Therefore, the prepared solid-solid phase change material has excellent shape stability, and the problem that the phase change material is easy to leak in use is fundamentally solved.
Inorganic framework materials with excellent heat conductivity are selected as heat conductivity reinforcement. On one hand, the inorganic framework material has good heat-conducting property and can provide a heat-conducting channel for the phase-change material, the heat-conducting rate of the phase-change material is improved, and the problem of low heat storage/release rate of the phase-change material is solved; on the other hand, the added inorganic framework material can generate physical interaction with the solid-solid phase change material formed by the reaction of the modified polyethylene glycol and the chitosan, and the strength of the inorganic framework material is higher, so that the strength of the composite phase change material can be greatly improved, and the solid-solid composite phase change material with excellent heat conductivity and higher strength can be obtained.
(3) The method is simple to operate, easy to control, easy to obtain raw materials, safe and environment-friendly. Researches prove that the composite phase change material prepared by the formula and the method has a loose and porous three-dimensional network structure and shows the characteristic of solid-solid phase change; the solid-solid composite phase change material prepared by the invention has excellent heat storage performance, and the latent heat can reach 149.6J/g.
Drawings
FIG. 1 is a schematic diagram of the preparation of polyethylene glycol having two terminal aldehyde groups in example 1;
FIG. 2 is a schematic diagram showing the mechanism of preparing a solid-solid phase change material by reacting a double-end aldehyde group polyethylene glycol with chitosan in example 2;
FIG. 3 is an infrared spectrum of a polyethylene glycol having two terminal aldehyde groups and a conventional polyethylene glycol in example 3;
FIG. 4 is a scanning electron micrograph of a solid-solid composite phase change material according to example 4;
FIG. 5 is a DSC of polyethylene glycol and a solid-solid composite phase change material of example 5;
FIG. 6 is a schematic diagram of the mechanism for preparing carboxyl-terminated polyethylene glycol in example 6;
FIG. 7 is a schematic diagram illustrating the mechanism of preparing a solid-solid phase change material by the chemical reaction of carboxyl-terminated polyethylene glycol and chitosan in example 7.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
Example 1
The high-stability solid-solid composite phase-change material described in this example was prepared according to the following formulation and procedure.
Step one, preparing a double-end aldehyde group polyethylene glycol aqueous solution:
the preparation mechanism is shown in figure 1, and the specific operation process is as follows:
dissolving 2.50mmol of polyethylene glycol with the molar mass of 600, 6.00mmol of p-aldehyde benzoic acid, 7.50mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 7.50mmol of pyridine into 250ml of dichloromethane in sequence, stirring at normal temperature for 48 hours, removing the dichloromethane by rotary evaporation, washing with glacial ethyl ether for 5 times, and drying under vacuum at 25 ℃ for 12 hours to obtain the double-end aldehyde group polyethylene glycol; dissolving the double-end aldehyde group polyethylene glycol into deionized water to prepare a 60wt% double-end aldehyde group polyethylene glycol aqueous solution for later use.
Step two, preparing a chitosan solution:
a chitosan solution was prepared by weighing 0.75g of chitosan and dissolving it in a mixed solution containing 99.5ml of deionized water and 0.5ml of acetic acid.
Step three, adding an inorganic framework material:
adding 10 times of sepiolite of chitosan mass into 10ml of modified polyethylene glycol aqueous solution, and performing ultrasonic dispersion for 10min to obtain uniformly dispersed mixed solution.
Step four, mixing raw materials and preparing a product:
mixing 10ml of chitosan solution with the mixed solution, and reacting for 24 hours at the temperature of 60 ℃; and freeze-drying to obtain the solid-solid composite phase change material.
Example 2
Step one, preparing a double-end aldehyde group polyethylene glycol aqueous solution:
dissolving 2.50mmol of polyethylene glycol with the molar mass of 2000, 7.50mmol of p-aldehyde benzoic acid, 7.50mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 7.50mmol of pyridine in 250ml of dichloromethane in sequence, stirring at normal temperature for 48h, removing the dichloromethane by rotary evaporation, washing with glacial ethyl ether for 5 times, and drying under vacuum at 25 ℃ for 12h to obtain the double-end aldehyde group polyethylene glycol; dissolving the double-end aldehyde group polyethylene glycol into deionized water to prepare a 50wt% double-end aldehyde group polyethylene glycol aqueous solution for later use.
Step two, preparing a chitosan solution:
a chitosan solution was prepared by weighing 1.2g of chitosan and dissolving it in a mixed solution containing 99.5ml of deionized water and 0.5ml of acetic acid.
Step three, adding an inorganic framework material:
adding a mixture of carbon nanotubes and halloysite which are 3 times of the mass of chitosan into 10ml of modified polyethylene glycol aqueous solution, and performing ultrasonic dispersion for 10min to obtain uniformly dispersed mixed solution.
Step four, mixing raw materials and preparing a product:
mixing 10ml of chitosan solution with the mixed solution, and reacting for 24 hours at the temperature of 60 ℃; and freeze-drying to obtain the solid-solid composite phase change material.
The embodiment verifies the mechanism shown in fig. 2, that is, the aldehyde group in the double-end aldehyde group polyethylene glycol and the amino group in the chitosan undergo schiff base reaction to form the solid-solid phase change material with a three-dimensional network structure on a microscopic scale, and specific verification of electron microscope images and detailed description are shown in the summary part of the embodiment.
Example 3
Step one, preparing a double-end aldehyde group polyethylene glycol aqueous solution:
dissolving 2.50mmol of polyethylene glycol with the molar mass of 4000, 10.00mmol of p-aldehyde benzoic acid, 7.50mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 7.50mmol of pyridine into 250ml of dichloromethane in sequence, stirring at normal temperature for 48 hours, removing the dichloromethane by rotary evaporation, washing with glacial ethyl ether for 5 times, and drying under vacuum at 25 ℃ for 12 hours to obtain the double-end aldehyde group polyethylene glycol; dissolving the double-end aldehyde group polyethylene glycol into deionized water to prepare 40wt% of double-end aldehyde group polyethylene glycol aqueous solution for later use.
Step two, preparing a chitosan solution:
0.35g of chitosan was weighed out and dissolved in a solution containing 99.5ml and 0.5ml of acetic acid to prepare a chitosan solution for use.
Step three, adding an inorganic framework material:
adding halloysite and attapulgite with the mass 6 times that of chitosan into 10ml of modified polyethylene glycol aqueous solution, and performing ultrasonic dispersion for 10min to obtain uniformly dispersed mixed solution.
Step four, mixing raw materials and preparing a product:
mixing 10ml of chitosan solution with the mixed solution, and reacting for 24 hours at the temperature of 60 ℃; and freeze-drying to obtain the solid-solid composite phase change material.
At the same time of product preparation, the double-end aldehyde group polyethylene glycol for experimental analysis is prepared in parallel according to the method of the embodiment, and infrared spectroscopic analysis is carried out on the double-end aldehyde group polyethylene glycol prepared in the embodiment and polyethylene glycol which is purchased conventionally in the market.
As shown in FIG. 3, it can be seen that the peak of the stretching vibration of the hydroxyl group in the double-end aldehyde group polyethylene glycol prepared in this example is much weaker than that of the hydroxyl group in the conventional polyethylene glycol (3182-3684 cm)-1Here), this indicates that the number of hydroxyl groups in the double-ended aldehyde polyethylene glycol is much lower than that in the conventional polyethylene glycol; in addition, the map of the double-end aldehyde group polyethylene glycol is 1717cm-1A new characteristic peak appears, which is caused by the stretching vibration of C = O, and this shows that the method of the embodiment can successfully prepare the double-end aldehyde group polyethylene glycol.
Example 4
Step one, preparing a double-end carboxyl polyethylene glycol aqueous solution:
2.50mmol of polyethylene glycol with a molar mass of 6000, 5.00mmol of maleic anhydride and 7.50mmol of pyridine are placed in a container with an air condenser, a stirrer, a thermometer and N2Mixing in four-mouth bottle of the protection device, and introducing N2Heating, reacting at 160 ℃ for 6h, cooling to room temperature, and separating out a product; washing the product with glacial ethyl ether for 5 times, and vacuum drying at 25 deg.C for 12h to obtain carboxyl-terminated polyethylene glycol; dissolving carboxyl-terminated polyethylene glycol into deionized water to prepare 30wt% of carboxyl-terminated polyethylene glycol aqueous solution for later use.
Step two, preparing a chitosan solution:
a chitosan solution was prepared by weighing 0.5g of chitosan and dissolving it in a mixed solution containing 99.5ml of deionized water and 0.5ml of acetic acid.
Step three, adding an inorganic framework material:
adding carbon nano tubes with the mass 3 times of that of the chitosan into 10ml of modified polyethylene glycol aqueous solution, and performing ultrasonic dispersion for 10min to obtain uniformly dispersed mixed solution.
Step four, mixing raw materials and preparing a product:
mixing 10ml of chitosan solution with the mixed solution, and reacting for 24 hours at the temperature of 60 ℃; and freeze-drying to obtain the solid-solid composite phase change material with the three-dimensional network structure.
Example 5
Step one, preparing a double-end aldehyde group polyethylene glycol aqueous solution:
dissolving 2.50mmol of polyethylene glycol with the molar mass of 6000, 8.50mmol of p-aldehyde benzoic acid, 7.50mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 7.50mmol of pyridine into 250ml of dichloromethane in sequence, stirring at normal temperature for 48 hours, removing the dichloromethane by rotary evaporation, washing with glacial ethyl ether for 5 times, and drying under vacuum at 25 ℃ for 12 hours to obtain the double-end aldehyde group polyethylene glycol; dissolving the double-end aldehyde group polyethylene glycol into deionized water to prepare a 15wt% double-end aldehyde group polyethylene glycol aqueous solution for later use.
Step two, preparing a chitosan solution:
a chitosan solution was prepared for use by weighing 0.1g of chitosan and dissolving it in a mixed solution containing 99.5ml of deionized water and 0.5ml of acetic acid.
Step three, adding an inorganic framework material:
adding attapulgite with the mass of 0.5 time that of the chitosan into 10ml of modified polyethylene glycol aqueous solution, and performing ultrasonic dispersion for 10min to obtain uniformly dispersed mixed solution.
Step four, mixing raw materials and preparing a product:
mixing 10ml of chitosan solution with the mixed solution, and reacting for 24 hours at the temperature of 60 ℃; and freeze-drying to obtain the solid-solid composite phase change material.
At the same time of product preparation, the product for experimental analysis was prepared in parallel according to the method of this example, and polyethylene glycol and the final product, which were purchased conventionally, were analyzed.
The DSC of both of them is shown in FIG. 5, and it can be seen that: the phase change temperature of the solid-solid composite phase change material prepared by the embodiment is 62.3 ℃, and the latent heat of phase change is 149.6J/g; the phase transition temperature of polyethylene glycol which is purchased from the market conventionally is 62.7 ℃, and the latent heat of phase transition is 172.6J/g. For the exclusion reasons, it was demonstrated that the reduction in the phase transition temperature of the final product of this example is caused by the improvement in the thermal conductivity of the raw material.
Example 6
Step one, preparing a double-end carboxyl polyethylene glycol aqueous solution:
the preparation mechanism is shown in fig. 6, and the specific operation process is as follows:
2.50mmol of polyethylene glycol with the molar mass of 8000, 7.00mmol of maleic anhydride and 7.50mmol of pyridine are put in a container with an air condenser, a stirrer, a thermometer and a nitrogen inlet pipe2Mixing in four-mouth bottle of the protection device, and introducing N2Heating, reacting at 160 ℃ for 6h, cooling to room temperature, and separating out a product; washing the product with glacial ethyl ether for 5 times, and vacuum drying at 25 deg.C for 12h to obtain carboxyl terminated polyethylene glycol (figure 6); dissolving carboxyl-terminated polyethylene glycol into deionized water to prepare 10wt% of carboxyl-terminated polyethylene glycol aqueous solution for later use.
Step two: preparing a chitosan solution.
0.8g of chitosan was weighed and dissolved in a mixed solution containing 99.5ml of deionized water and 0.5ml of acetic acid to prepare a chitosan solution for use.
Step three, adding an inorganic framework material:
adding attapulgite with the mass 5 times that of the chitosan into 10ml of modified polyethylene glycol aqueous solution, and performing ultrasonic dispersion for 10min to obtain uniformly dispersed mixed solution.
Step four, mixing raw materials and preparing a product:
mixing 10ml of chitosan solution with the mixed solution, and reacting for 24 hours at the temperature of 60 ℃; and drying at normal pressure to obtain the solid-solid composite phase change material.
Example 7
Step one, preparing a double-end carboxyl polyethylene glycol aqueous solution:
2.50mmol of polyethylene glycol with a molar mass of 12000, 10.00mmol of maleic anhydride and 7.50mmol of pyridine are introduced into a reaction vessel equipped with an air condenser, a stirrer, a thermometer and a nitrogen inlet2Mixing in four-mouth bottle of the protection device, and introducing N2Heating, reacting at 160 ℃ for 6h, cooling to room temperature, and separating out a product; washing the product with glacial ethyl ether for 5 times, and vacuum drying at 25 deg.C for 12h to obtain carboxyl-terminated polyethylene glycol; dissolving carboxyl-terminated polyethylene glycol into deionized water to prepare 5wt% of carboxyl-terminated polyethylene glycol aqueous solution for later use.
Step two, preparing a chitosan solution:
a chitosan solution was prepared by weighing 6.0g of chitosan and dissolving it in a mixed solution containing 99.5ml of deionized water and 0.5ml of acetic acid.
Step three, adding an inorganic framework material:
adding carbon nano tubes with the mass 7 times that of the chitosan into 10ml of modified polyethylene glycol aqueous solution, and performing ultrasonic dispersion for 10min to obtain uniformly dispersed mixed solution.
Step four, mixing raw materials and preparing a product:
mixing 10ml of chitosan solution with the mixed solution, and reacting for 24 hours at the temperature of 60 ℃; and freeze-drying to obtain the solid-solid composite phase change material.
The embodiment verifies the mechanism shown in fig. 7, the carboxyl group in the carboxyl-terminated polyethylene glycol and the amino group in the chitosan can perform an amide reaction to form a solid-solid phase change material with a microscopically three-dimensional network structure, and specific verification electron microscope images and detailed description are shown in the summary part of the embodiment.
Summary of the embodiments
The final products of the above embodiments are subjected to electron microscope scanning, and an electron microscope image is shown in fig. 4, which proves that the products prepared by the above embodiments are solid-solid composite phase change materials with stable three-dimensional network structures.
For reasons of space, only representative 7 examples are given, and the modified polyethylene glycol of the present invention is verified from several perspectives, namely: the feasibility of the double-end aldehyde group polyethylene glycol aqueous solution and the double-end carboxyl polyethylene glycol aqueous solution prepared according to the formula and the method, the feasibility and the advantages of the double-end aldehyde group polyethylene glycol aqueous solution and the double-end carboxyl polyethylene glycol aqueous solution for preparing the solid-solid composite phase change material, and the finally prepared product is verified to be of a three-dimensional network structure and has high stability.
Claims (9)
1. A high-stability solid-solid composite phase change material is characterized in that: the preparation raw materials comprise: 10ml of modified polyethylene glycol solution, 10ml of chitosan solution and inorganic framework material; the mass of the inorganic framework material is 0.5-10 times of the mass of chitosan in 10ml of chitosan solution.
2. The high-stability solid-solid composite phase-change material as claimed in claim 1, wherein: the chitosan solution is a mixed solution of 0.1-1.2g of chitosan dispersed in a solution containing 99.5ml of deionized water and 0.5ml of acetic acid.
3. The high-stability solid-solid composite phase-change material as claimed in claim 1, wherein: the inorganic framework material is one or the combination of more of halloysite, sepiolite, carbon nano tubes or attapulgite.
4. The high-stability solid-solid composite phase-change material as claimed in claim 1, wherein: the concentration of the modified polyethylene glycol is 5-60 wt%.
5. The high-stability solid-solid composite phase-change material as claimed in claim 4, wherein: the modified polyethylene glycol aqueous solution is a double-end aldehyde group polyethylene glycol aqueous solution or a double-end carboxyl polyethylene glycol aqueous solution.
6. A method for preparing the high-stability solid-solid composite phase-change material as claimed in any one of claims 1 to 5, wherein: the method comprises the following steps:
step A, preparing a modified polyethylene glycol aqueous solution:
preparing 5-60wt% of double-end aldehyde group polyethylene glycol aqueous solution or double-end carboxyl polyethylene glycol aqueous solution;
step B, preparing a chitosan solution:
weighing 0.1-1.2g of chitosan, and dispersing the chitosan into a solution containing 99.5ml of deionized water and 0.5ml of acetic acid to obtain a chitosan solution for later use;
step C, adding an inorganic framework material:
adding 0.5-10 times of inorganic framework material of chitosan into 10ml of modified polyethylene glycol aqueous solution, and performing ultrasonic dispersion for 10min to obtain uniformly dispersed mixed solution;
step D, raw material mixing and product preparation:
mixing 10ml of chitosan solution with the mixed solution, and reacting for 24 hours at the temperature of 60 ℃; then the product, namely the high-stability solid-solid composite phase-change material, is prepared after normal pressure drying or freeze drying.
7. The method for preparing the solid-solid composite phase-change material with high stability as claimed in claim 6, wherein: the preparation of the double-end aldehyde group polyethylene glycol aqueous solution in the step A is as follows:
adding 2.50mmol of polyethylene glycol, 6.00-10.00mmol of p-aldehyde benzoic acid, 7.50mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 7.50mmol of pyridine into 250ml of dichloromethane in sequence, stirring at normal temperature for 48h, removing the dichloromethane by rotary evaporation, washing with glacial ethyl ether for 5 times, and drying under vacuum at 25 ℃ for 12h to obtain the double-end aldehyde group polyethylene glycol; dissolving the double-end aldehyde group polyethylene glycol into deionized water to prepare a 5-60wt% double-end aldehyde group polyethylene glycol aqueous solution for later use.
8. The method for preparing the solid-solid composite phase-change material with high stability as claimed in claim 6, wherein: the aqueous solution of carboxyl-terminated polyethylene glycol was prepared as follows:
2.50mmol of polyethylene glycol, 5.00-10.00mmol of maleic anhydride and 7.50mmol of pyridine are takenIn a device with an air condenser, a stirrer, a thermometer and a nitrogen inlet2Mixing in four-mouth bottle of the protection device, and introducing N2Heating, reacting at 160 ℃ for 6h, cooling to room temperature, and separating out a product; washing the product with glacial ethyl ether for 5 times, and drying in vacuum at 25 ℃ for 12h to obtain carboxyl-terminated polyethylene glycol; dissolving the carboxyl-terminated polyethylene glycol into deionized water to prepare 5-60wt% of carboxyl-terminated polyethylene glycol aqueous solution for later use.
9. The method for preparing a solid-solid composite phase change material with high stability as claimed in claim 7 or 8, wherein: the molar mass of the polyethylene glycol used for preparing the aqueous solution of the aldehyde-terminated polyethylene glycol and the aqueous solution of the carboxyl-terminated polyethylene glycol in the step A is 600-12000 g/mol.
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| CN113403038A (en) * | 2021-06-15 | 2021-09-17 | 山东理工大学 | Preparation method of composite phase change energy storage material based on straw waste |
| CN113621348A (en) * | 2021-08-16 | 2021-11-09 | 山东建筑大学 | Chitin-derived carbon-based high-thermal-conductivity phase change material, preparation method thereof and heat storage application |
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| CN113621348B (en) * | 2021-08-16 | 2023-08-15 | 山东建筑大学 | High-heat-conductivity phase change material based on chitin derived carbon, preparation method and heat storage application thereof |
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