CN109575911B - Strawberry-shaped thermochromic energy storage material and preparation method and application thereof - Google Patents
Strawberry-shaped thermochromic energy storage material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a strawberry-shaped thermochromic energy storage material, which comprises the following steps: (1) mixing styrene, divinyl benzene, acrylic acid, glycidyl methacrylate, polyvinylpyrrolidone and paraffin, adding an emulsifier and an initiator, cooling, and centrifuging to obtain pure phase-change microspheres; (2) mixing a leuco dye, an electron acceptor compound and a solvent to form a mixture, heating the mixture, fully stirring to form a solution, adding deionized water, tetraethyl orthosilicate, a silane coupling agent and an emulsifier, adding ammonia water under ultrasound to react, centrifuging, and drying at low temperature to obtain thermochromic silica gel capsule particles; (3) and mixing the phase-change microspheres and the thermochromic silica gel capsules to form a mixture, adding an emulsifier and a catalyst for reaction, centrifuging and drying to obtain the strawberry-shaped thermochromic energy storage material. The strawberry-shaped thermochromic energy storage material has the advantages of high enthalpy, high temperature-sensitive response speed, reversible color change, cyclic and repeated color change, stable property and the like, can be used as a novel intelligent material, and has wide application prospects in the fields of buildings, energy conservation, environmental protection, clothes, medical treatment and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a strawberry-shaped thermochromic energy storage material and a preparation method and application thereof.
Background
The energy storage material is a functional material for storing energy by utilizing physical or chemical changes of substances, and the stored energy forms comprise electric energy, thermal energy, mechanical energy, chemical energy and the like. Wherein the storage of thermal energy is achieved by absorbing external thermal radiation. The phase-change material can realize the storage and utilization of heat energy through the change of a phase state, is beneficial to improving the utilization efficiency of energy and promotes the development and the use of renewable energy. The defects in the art are that the latent heat of phase change of the phase change material is constant, when the phase change material reaches a saturated energy storage state or a complete energy release state, the phase change material does not store or release energy any more, and the energy storage condition of the phase change material is difficult to directly observe by naked eyes, so that if a simple method can be developed to indicate the energy storage state or the energy release state of the phase change material, the convenience of use of the phase change material is greatly improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a strawberry-shaped thermochromic energy storage material with the characteristics of high enthalpy and visual phase change, so as to overcome the defects of the prior art.
The invention also aims to solve the technical problem of providing a method for preparing the strawberry-shaped thermochromic energy storage material, which has the advantages of low cost, green and environment-friendly production process and the like.
The invention finally aims to solve the problem of providing the application of the strawberry-shaped thermochromic energy storage material in the fields of building, energy conservation, environmental protection, clothing, medical treatment and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a strawberry-shaped thermochromic energy storage material comprises the following steps:
(1) mixing divinylbenzene, styrene, acrylic acid, glycidyl methacrylate, polyvinylpyrrolidone and paraffin wax according to the weight ratio of 1: 10-20: 0.5-3: 1-5: 0.5-3: 2-25 to form a mixture, heating and uniformly stirring the mixture, adding an emulsifier and an initiator, stirring to react, cooling, centrifuging and cleaning to obtain phase-change microspheres;
(2) mixing a leuco dye, an electron acceptor compound and a solvent according to a weight ratio of 1: 10-50: 80-120 to obtain a thermochromic core material mixture, heating and stirring the thermochromic core material mixture to form a solution, then adding deionized water, tetraethyl orthosilicate, a silane coupling agent and an emulsifier according to a mass ratio of 1: 100-200: 1-5: 0.5-2: 0.005-0.5 to the thermochromic core material mixture, adding ammonia water under ultrasound to react, and after the reaction is finished, centrifuging and drying to obtain the thermochromic silica gel capsule;
(3) and (3) mixing the phase change microspheres obtained in the step (1) and the thermochromic silica gel capsules obtained in the step (2) to form a mixture, adding an emulsifier while stirring, adjusting the pH to 8.5-10 by using ammonia water, reacting, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material.
As one specific embodiment, the step (1) further comprises mixing divinylbenzene, styrene, acrylic acid, glycidyl methacrylate, polyvinylpyrrolidone and paraffin wax in a weight ratio of 1: 10-20: 0.5-3: 1-5: 0.5-3: 2-25 to form a mixture, heating the mixture to 70-90 ℃, uniformly stirring, adding an emulsifier and an initiator, stirring at 70-90 ℃, reacting, cooling, centrifuging, and cleaning to obtain the phase-change microspheres;
the emulsifier is one or a mixture of several of sodium dodecyl benzene sulfonate, oleic acid, stearic acid, fatty glyceride, alkylphenol ethoxylates and fatty polyoxyethylene, preferably sodium alkyl benzene sulfonate.
In the step (1), the initiator is one or a mixture of a plurality of azodiisobutyronidine hydrochloride, azodicyano valeric acid, azodiisobutyramidine hydrochloride and potassium persulfate, and preferably azodiisobutyronidine.
In the step (2), the leuco dye comprises one or a mixture of more of crystal violet lactone, phenolphthalein, phenol red, methyl red, bromocresol purple and bromocresol green, and preferably the crystal violet lactone and the bromocresol purple.
In the step (2), the electron acceptor compound comprises one or a mixture of more of boric acid, bisphenol A, magnesium chloride, aromatic sulfone, poly-beta-hydroxybutyric acid and stearic acid, preferably bisphenol A and stearic acid.
In the step (2), the solvent comprises one or more of dodecanol, tetradecanol, hexadecanol, octadecanol and behenyl alcohol, and is preferably dodecanol, tetradecanol and octadecanol.
In the step (2), the silane coupling agent is one or a combination of more than two of KH550, KH580, KH590, A-1130 and Y-5691, preferably KH580 and Y-5691.
As a specific embodiment, the step (2) further comprises mixing the leuco dye, the electron acceptor compound and the solvent according to a weight ratio of 1: 10-50: 80-120 to obtain a thermochromic core material mixture, heating the thermochromic core material mixture to 70-90 ℃, stirring to form a solution, adding deionized water, tetraethyl orthosilicate, a silane coupling agent and an emulsifier in a mass ratio of 1: 100-200: 1-5: 0.5-2: 0.005-0.5 to the thermochromic core material mixture, adding ammonia water under ultrasound to react and adjust the pH value to 8-11, and centrifuging and drying after the reaction is finished to obtain the thermochromic silica gel capsule.
In the step (1), the particle size of the phase-change microsphere is 300-400 nm, preferably 300-350 nm; in the step (2), the particle size of the thermochromic silica gel capsule is 10-60nm, preferably 10-30 nm, and in the step (3), the particle size of the thermochromic silica gel capsule is 300-500 nm, preferably 310-400 nm.
As one specific embodiment, the step (3) further comprises mixing the phase-change microspheres obtained in the step (1) and the thermochromic silica gel capsules obtained in the step (2) according to a mass ratio of 1: 3-6 to form a mixture, adding an emulsifier while stirring, adjusting the pH to 8.5-10 with ammonia water, reacting, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material.
As one of the preferred embodiments, the preparation method further may comprise:
(1) mixing divinyl benzene, styrene, acrylic acid, glycidyl methacrylate, polyvinylpyrrolidone and paraffin to form a mixture, heating the mixture, stirring and reacting the mixture for a period of time by using a homogenizer at a speed of about 4000-10000 rpm, adding an emulsifier and an initiator, continuously stirring and reacting for 12-36 hours, cooling, centrifuging and cleaning to obtain phase-change microspheres;
(2) mixing a leuco dye, an electron acceptor compound and a solvent to obtain a thermochromic core material mixture, heating the thermochromic core material mixture to 70-90 ℃, stirring to form a solution, adding deionized water, tetraethyl orthosilicate, a silane coupling agent and an emulsifier in a mass ratio of 1: 100-200: 1-5: 0.5-2: 0.005-0.5 to the thermochromic core material mixture, adding ammonia water under ultrasound to react and adjust the pH value to 8-11, and centrifuging and drying after the reaction is finished to obtain the thermochromic silica gel capsule;
(3) and (3) mixing the phase-change microspheres obtained in the step (1) and the thermochromic silica gel capsules obtained in the step (2) according to a mass ratio of 1: 3-6 to form a mixture, adding an emulsifier while stirring, adjusting the pH to 8.5-10 with ammonia water, reacting, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material.
The strawberry-shaped thermochromic energy storage material prepared by the preparation method of the strawberry-shaped thermochromic energy storage material is within the protection range of the invention.
The enthalpy of the strawberry-shaped thermochromic energy storage material is 120-138J/g, and the thermochromic rate is 0.10-0.18 s-1。
The strawberry-shaped thermochromic energy storage material is applied to the fields of building, energy conservation, environmental protection, clothing, medical treatment and the like as a novel intelligent material within the protection range of the invention.
As one of the preferred embodiments, the preparation method further may comprise:
(1) mixing divinyl benzene, styrene, acrylic acid, glycidyl methacrylate, polyvinylpyrrolidone and paraffin according to the weight ratio of 1: 10-20: 0.5-3: 1-5: 0.5-3: 2-25 to form a mixture, heating the mixture to 70-90 ℃, stirring the mixture for a period of time at the rotating speed of 4000-10000 rpm by using a homogenizer, adding an emulsifier and an initiator, then reacting the mixture for a period of time at the rotating speed of 500-1000 rpm under the condition of magnetic stirring at 70-90 ℃, cooling, centrifuging, and washing the mixture with a solvent to obtain pure phase-change microspheres;
(2) mixing a leuco dye, an electron acceptor compound and a solvent according to a weight ratio of 1: 10-50: 80-120 to form a thermochromic core material mixture, heating the mixture to 70-90 ℃, fully stirring to form a solution, then adding deionized water, tetraethyl orthosilicate, a silane coupling agent and an emulsifier in a mass ratio of 1: 100-200: 1-5: 0.5-2: 0.005-0.5 to the core material mixture, transferring the mixture into an ultrasonic instrument with a water bath temperature of 60-80 ℃, carrying out ultrasonic reaction, slowly dropwise adding 0.5M ammonia water to control the pH of a reaction system to be 8-11, reacting for a period of time, and after the reaction is finished, carrying out centrifugation and low-temperature drying to obtain thermochromic silica gel capsule particles;
(3) mixing the prepared phase-change microspheres and the thermochromic silica gel capsules according to the mass ratio of 1: 3-6 to form a mixture, adding an emulsifier under full stirring, dropwise adding 0.5M ammonia water to adjust the pH value to be 8.5-10, reacting for a period of time, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material.
More specifically, in one embodiment, the preparation method may include:
(A) mixing 1 part by weight of divinylbenzene, 10-20 parts by weight of styrene, 0.5-3 parts by weight of acrylic acid, 1-5 parts by weight of glycidyl methacrylate, 0.5-3 parts by weight of polyvinylpyrrolidone and 2-25 parts by weight of paraffin to form a mixture, heating the mixture to 70-90 ℃, stirring the mixture for 10-30 min at the rotation speed of 4000-10000 rpm by using a homogenizer, adding 0.005-0.5 part by weight of an emulsifier and 0.2-0.5 part by weight of an initiator, then reacting the mixture for 12-36 hours at the rotation speed of 500-1000 rpm by using magnetic stirring at the temperature of 70-90 ℃, cooling, and centrifuging and washing the mixture by using a solvent to obtain pure phase-change microspheres;
(B) mixing 1 part by weight of leuco dye, 10-50 parts by weight of electron acceptor compound and 80-120 parts by weight of solvent to form a thermochromic core material mixture, heating the mixture to 70-90 ℃ and fully stirring to form a solution, then adding 100-200 parts by weight of core material of deionized water, 1-5 parts by weight of tetraethyl orthosilicate, 0.5-2 parts by weight of silane coupling agent and 0.005-0.5 part by weight of emulsifier, transferring the mixture into an ultrasonic instrument with a water bath temperature of 60-80 ℃ for ultrasonic reaction for 1-12 hours, slowly dropwise adding 0.5M ammonia water to control the pH of the reaction system to be 8-11, and after the reaction is finished, centrifuging and drying at low temperature to obtain thermochromic silica gel capsule particles;
(C) mixing 1 part by weight of phase change microspheres and 3-6 parts by weight of thermochromic silica gel capsules to form a mixture, adding 0.0005-0.05 part by weight of emulsifier under full stirring, dropwise adding 0.5M ammonia water to adjust the pH value to be 8.5-10, reacting for a period of time, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material.
For example, one application scheme may be:
a method of making a color indicating thermal insulating fire protective garment, comprising: and coating the strawberry-shaped thermochromic energy storage material at a specific position of a textile.
Has the advantages that:
the advantages of the invention include: different wall materials are adopted to respectively prepare the phase change material and the thermochromic material into microcapsules with larger size difference, so that the influence on the energy storage capacity of the material due to the interaction between the two materials is avoided. The phase change energy storage material microcapsules and the thermochromic material microcapsules are assembled together through the interaction between the reaction functional groups on the surfaces of the capsules, and the strawberry-shaped thermochromic energy storage material is prepared. The material with the structure is compact in texture and large in specific surface area, and the silicon-based external shell material is beneficial to heat conduction of the microspheres, accelerates energy absorption of the energy storage material and improves the temperature change sensitivity of the thermochromic material. The real-time indication of the energy absorption degree of the energy storage material can be realized by adjusting the temperature change point of the thermochromic material. The reflectivity of the material to light can be adjusted by controlling the temperature-changing color of the thermochromic material, so that the rate of the energy storage material absorbing external energy is controlled. Meanwhile, through tests, the strawberry-shaped thermochromic energy storage material is also found to have super-hydrophobic property, and the property has great application value in certain antifouling fields. The strawberry-shaped thermochromic energy storage material has the advantages of high enthalpy, high temperature-sensitive response speed, reversible color change, cyclic and repeated color change, stable property and the like, can be used as a novel intelligent material, and has wide application prospects in the fields of buildings, energy conservation, environmental protection, clothes, medical treatment and the like.
Drawings
Fig. 1 is a scanning electron microscope photograph of the strawberry-shaped thermochromic energy storage material obtained in examples 1 to 5, and it can be seen from the photograph that the prepared material is spherical and has fine particles distributed on the surface, and is shaped like a strawberry.
Fig. 2 is a photograph of the strawberry-shaped thermochromic energy storage material obtained in examples 1 to 5 under a transmission electron microscope, from which it can be clearly seen that the material is in a capsule form, the inner core is filled with paraffin, and a layer of dense and fine thermochromic particles is adhered to the outer portion.
Fig. 3 is a photograph showing the effect of the strawberry-shaped thermochromic energy storage materials obtained in embodiments 1 to 5 after being applied to a model house.
Detailed Description
The invention is described in further detail below with reference to the drawings and several exemplary embodiments.
Example 1:
mixing 1g of divinylbenzene with 10g of styrene, 0.5g of acrylic acid, 1.5g of glycidyl methacrylate, 1g of polyvinylpyrrolidone and 3g of paraffin to form a mixture, heating the mixture to 70 ℃, stirring the mixture for 30min at 5500rpm by a homogenizer, adding 0.005g of sodium dodecyl benzene sulfonate and 0.2g of azodicyano valeric acid, reacting the mixture for 12 hours at 70 ℃ at 700rpm by magnetic stirring, cooling, centrifuging, and repeatedly washing the mixture for 3 times by ethanol to obtain pure phase change microspheres;
mixing 0.1g of crystal violet lactone, 1g of boric acid and 8g of tetradecanol to form a thermochromic core material mixture, heating the mixture to 70 ℃, fully stirring to form a solution, then adding 740g of deionized water, 20g of tetraethyl orthosilicate, 5g of KH550 and 0.05g of alkylphenol polyoxyethylene ether, transferring the mixture into an ultrasonic instrument with a water bath temperature of 60 ℃ for ultrasonic reaction for 3 hours, dropwise adding 0.5M ammonia water in the reaction process to control the pH of the system to be 8, and after the reaction is finished, centrifuging and drying at low temperature to obtain thermochromic silica gel capsule particles;
mixing 1g of phase-change microspheres and 3g of thermochromic silica gel capsules to form a mixture, adding 0.02g of emulsifier under full stirring, dropwise adding 0.5M ammonia water to adjust the pH value to be 9, reacting for a period of time, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic silica gel capsuleThe enthalpy of the material is as high as 138J/g, and the thermochromic rate is as fast as 0.17s-1The scanning electron micrograph and the transmission electron micrograph thereof are shown in FIGS. 1 and 2.
Example 2:
mixing 1g of divinylbenzene with 15g of styrene, 1g of acrylic acid, 2.5g of glycidyl methacrylate, 1.5g of polyvinylpyrrolidone and 10g of paraffin to form a mixture, heating the mixture to 75 ℃, stirring the mixture for 15min at the rotation speed of 4000rpm by using a homogenizer, adding 0.1g of polyoxyethylene fatty acid and 0.3g of azodiisobutyramidine hydrochloride, then reacting the mixture for 24 hours at 78 ℃ by using magnetic stirring at the rotation speed of 800rpm, cooling, centrifuging, and repeatedly washing the mixture for 3 times by using acetone to obtain pure phase-change microspheres;
mixing 0.1g of phenolphthalein, 1.5g of bisphenol A and 10g of dodecanol to form a thermochromic core material mixture, heating the mixture to 75 ℃, fully stirring to form a solution, then adding 1200g of deionized water, 18g of tetraethyl orthosilicate, 12g of KH580 and 2g of stearic acid, transferring the mixture into an ultrasonic instrument with a water bath temperature of 70 ℃ for ultrasonic reaction for 4 hours, dropwise adding 0.5M ammonia water in the reaction process to control the pH of the system to be 9, and after the reaction is finished, centrifuging and drying at low temperature to obtain thermochromic silica gel capsule particles;
mixing 1g of phase change microsphere and 6g of thermochromic silica gel capsule to form a mixture, adding 0.03g of fatty glyceride under full stirring, dropwise adding 0.5M ammonia water to adjust the pH value to be 8.5, reacting for a period of time, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material, wherein the enthalpy of the material is as high as 134J/g, and the thermochromic rate is as high as 0.12s-1The scanning electron micrograph and the transmission electron micrograph thereof were substantially the same as those of example 1.
Example 3:
mixing 1g of divinylbenzene with 20g of styrene, 3g of acrylic acid, 5g of glycidyl methacrylate, 3g of polyvinylpyrrolidone and 25g of paraffin to form a mixture, heating the mixture to 85 ℃, stirring the mixture for 30min at 8000rpm by using a homogenizer, adding 0.5g of oleic acid and 0.3g of potassium persulfate, then reacting the mixture for 36 hours at 85 ℃ by using magnetic stirring at 1000rpm, cooling, centrifuging, and repeatedly washing the mixture for 3 times by using acetone to obtain pure phase-change microspheres;
mixing 0.1g of phenol red, 5g of aromatic sulfone and 12g of octadecanol to form a thermochromic core material mixture, heating the mixture to 85 ℃, fully stirring to form a solution, then adding 2000g of deionized water, 85g of tetraethyl orthosilicate, 34g of KH590, 1g of oleic acid and 4g of stearic acid, transferring the mixture into an ultrasonic instrument with a water bath temperature of 60 ℃, carrying out ultrasonic reaction for 12 hours, dropwise adding 0.5M ammonia water in the reaction process to control the pH of the system to be 9.5, and after the reaction is finished, carrying out centrifugation and low-temperature drying to obtain thermochromic silica gel capsule particles;
mixing 1g of phase change microsphere and 5g of thermochromic silica gel capsule to form a mixture, adding 0.05g of sodium dodecyl benzene sulfonate while fully stirring, dropwise adding 0.5M ammonia water to adjust the pH value to be 8.5, reacting for a period of time, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material, wherein the enthalpy of the material is as high as 120J/g, and the thermochromic rate is as fast as 0.1s-1The scanning electron micrograph and the transmission electron micrograph thereof were substantially the same as those of example 1.
Example 4:
mixing 1g of divinylbenzene with 10g of styrene, 0.5g of acrylic acid, 2g of glycidyl methacrylate, 2.5g of polyvinylpyrrolidone and 18g of paraffin to form a mixture, heating the mixture to 90 ℃, stirring the mixture for 20min at 10000rpm by a homogenizer, adding 0.1g of oleic acid, 0.1g of stearic acid and 0.4g of azodiisobutyronitrile, reacting the mixture for 16 hours at 77 ℃ by magnetic stirring at 600rpm, cooling, centrifuging, and repeatedly washing the mixture for 3 times by using acetone to obtain pure phase-change microspheres;
mixing 0.1g of bromocresol purple with 2g of stearic acid and 8g of behenyl alcohol to form a thermochromic core material mixture, heating the mixture to 80 ℃, fully stirring to form a solution, adding 900g of deionized water, 12g of tetraethyl orthosilicate, 6g A-1130 and 2.2g of fatty glyceride, transferring the mixture into an ultrasonic instrument with a water bath temperature of 70 ℃ for ultrasonic reaction for 8 hours, dropwise adding 0.5M ammonia water in the reaction process to control the pH of the system to be 10, and after the reaction is finished, centrifuging and drying at low temperature to obtain thermochromic silica gel capsule particles;
mixing 1g of phase change microsphere and 4g of thermochromic silica gel capsule to form a mixture, adding 0.005g of sodium dodecyl benzene sulfonate while fully stirring, dropwise adding 0.5M ammonia water to adjust the pH value to be 8.5, reacting for a period of time, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material, wherein the enthalpy of the material is as high as 136J/g, and the thermochromic rate is as fast as 0.18s-1The scanning electron micrograph and the transmission electron micrograph thereof were substantially the same as those of example 1.
Example 5:
mixing 1g of divinylbenzene with 18g of styrene, 2.2g of acrylic acid, 1g of glycidyl methacrylate, 1.2g of polyvinylpyrrolidone and 22g of paraffin to form a mixture, heating the mixture to 83 ℃, stirring the mixture for 10min at 8500rpm by using a homogenizer, adding 0.15g of alkylphenol polyoxyethylene and 0.33g of azodiisobutylamine hydrochloride, then reacting the mixture for 28 hours at 83 ℃ by using magnetic stirring at 750rpm, cooling, centrifuging, and repeatedly washing the mixture for 3 times by using acetone to obtain pure phase-change microspheres;
mixing 0.1g of bromocresol green with 3g of stearic acid and 11g of hexadecanol to form a thermochromic core material mixture, heating the mixture to 80 ℃, fully stirring to form a solution, then adding 2600g of deionized water, 30g of tetraethyl orthosilicate, 15g of KH590, 1.5g of oleic acid and 2g of fatty glyceride, transferring the mixture to an ultrasonic instrument with a water bath temperature of 70 ℃ for ultrasonic reaction for 3 hours, dropwise adding 0.5M ammonia water in the reaction process to control the pH of the system to be 9.7, and after the reaction is finished, centrifuging and drying at low temperature to obtain thermochromic silica gel capsule particles;
mixing 1g of phase change microsphere and 5.5g of thermochromic silica gel capsule to form a mixture, adding 0.025g of polyoxyethylene fatty acid under full stirring, dropwise adding 0.5M ammonia water to adjust the pH value to be 8.5, reacting for a period of time, and after the reaction is finished, performing centrifugation and drying treatment to obtain the strawberry-shaped thermochromic energy storage material, wherein the enthalpy of the material is up to 137J/g, and the thermochromic rate is up to 0.16s-1The scanning electron micrograph and the transmission electron micrograph thereof were substantially the same as those of example 1.
FIG. 1 is a photograph of a Scanning Electron Microscope (SEM) of a strawberry-shaped thermochromic energy storage material, wherein the prepared material is spherical and is clearly seen from the photograph, and fine particles are distributed on the surface of the material, so that the material is similar to a strawberry;
FIG. 2 is a photograph of a strawberry-shaped thermochromic energy storage material under a transmission electron microscope, from which it can be clearly seen that the material is in a capsule form, the inner core is filled with paraffin, and a layer of dense and fine thermochromic particles is adhered to the outer part of the material;
FIG. 3 is a photograph showing the effect of a strawberry-shaped thermochromic energy storage material applied to a model house, wherein a layer of clay is coated on the surface of a white house, a layer of clay with the thickness equal to that of the white house but containing 1 wt% of the strawberry-shaped thermochromic energy storage material is coated on the surface of the blue house, the two houses are irradiated under infrared lamps at equal intervals, and the irradiation processes are shown in the diagrams (b) to (f), so that the temperature rise speed of the internal temperature of the blue house is remarkably lower than that of the white house, the maximum temperature difference reaches 7 ℃, which indicates that the strawberry-shaped thermochromic energy storage material has a good heat insulation effect, the diagrams (g) to (j) are cooling processes after irradiation is stopped, and the temperature drop speed of the internal temperature of the blue house is remarkably lower than that of the white house because the strawberry-shaped thermochromic energy storage material has an energy storage function, and slowly releases heat in a non-illumination environment, the heat preservation effect is presented, in addition, in the whole heating and cooling process, the blue house presents the color change of blue-colorless-blue, on one hand, the warning effect of the temperature sensor is embodied, and on the other hand, the reflection and absorption ratio of the light source can be automatically adjusted through the color change of the surface.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a strawberry-shaped thermochromic energy storage material is characterized by comprising the following steps:
(1) mixing divinylbenzene, styrene, acrylic acid, glycidyl methacrylate, polyvinylpyrrolidone and paraffin wax in a weight ratio of 1: 10-20: 0.5-3: 1-5: 0.5-3: 2-25 to form a mixture, heating and uniformly stirring the mixture, adding an emulsifier and an initiator, stirring for reaction, cooling, centrifuging, and cleaning to obtain phase-change microspheres;
(2) mixing a leuco dye, an electron acceptor compound and a solvent according to a weight ratio of 1: 10-50: 80-120 to obtain a thermochromic core material mixture, heating and stirring the thermochromic core material mixture to form a solution, then adding deionized water, tetraethyl orthosilicate, a silane coupling agent and an emulsifier according to a mass ratio of 1: 100-200: 1-5: 0.5-2: 0.005-0.5 to the thermochromic core material mixture, adding ammonia water under ultrasound to react, and after the reaction is finished, centrifuging and drying to obtain the thermochromic silica gel capsule;
(3) and (3) mixing the phase change microspheres obtained in the step (1) and the thermochromic silica gel capsules obtained in the step (2) to form a mixture, adding an emulsifier while stirring, adjusting the pH to 8.5-10 by using ammonia water, reacting, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material.
2. The preparation method of the strawberry-shaped thermochromic energy storage material according to claim 1, wherein in the step (1), divinylbenzene, styrene, acrylic acid, glycidyl methacrylate, polyvinylpyrrolidone and paraffin are mixed according to a weight ratio of 1: 10-20: 0.5-3: 1-5: 0.5-3: 2-25 to form a mixture, the mixture is heated to 70-90 ℃, stirred uniformly, added with an emulsifier and an initiator, stirred to react at 70-90 ℃, cooled, centrifuged and cleaned to obtain the phase-change microspheres.
3. The preparation method of the strawberry-shaped thermochromic energy storage material according to claim 1, wherein the emulsifier is one or a mixture of several of sodium dodecyl benzene sulfonate, oleic acid, stearic acid, fatty glyceride, alkylphenol ethoxylates and fatty polyoxyethylene ester; the initiator is one or a mixture of more of azodiisobutyronitrile, azodicyano valeric acid, azodiisobutyl amidine hydrochloride and potassium persulfate;
in the step (2), the leuco dye is one or a mixture of more of crystal violet lactone, phenolphthalein, phenol red, methyl red, bromocresol purple and bromocresol green;
in the step (2), the electron acceptor compound is one or a mixture of more of boric acid, bisphenol A, magnesium chloride, aromatic sulfone, poly-beta-hydroxybutyric acid and stearic acid;
in the step (2), the solvent is one or a mixture of several of decaol, dodecanol, tetradecanol, hexadecanol, octadecanol and behenyl alcohol;
in the step (2), the silane coupling agent is one or a composition of more than two of KH550, KH580, KH590, A-1130 and Y-5691.
4. The preparation method of the strawberry-shaped thermochromic energy storage material according to claim 1, wherein in the step (2), the leuco dye, the electron acceptor compound and the solvent are mixed according to a weight ratio of 1: 10-50: 80-120 to obtain a thermochromic core material mixture, the thermochromic core material mixture is heated to 70-90 ℃ and stirred to form a solution, then deionized water, tetraethyl orthosilicate, a silane coupling agent and an emulsifier are added into the thermochromic core material mixture according to a mass ratio of 1: 100-200: 1-5: 0.5-2: 0.005-0.5, ammonia water is added under ultrasound to react and adjust the pH value to 8-11, and after the reaction is finished, the thermochromic silica gel capsule is obtained through centrifugation and drying.
5. The preparation method of the strawberry-shaped thermochromic energy storage material according to claim 1, wherein in the step (1), the particle size of the phase-change microspheres is 300-400 nm; in the step (2), the grain diameter of the thermochromic silica gel capsule is 10-60nm, and in the step (3), the grain diameter of the strawberry-shaped thermochromic energy storage material is 300-500 nm.
6. The preparation method of the strawberry-shaped thermochromic energy storage material according to claim 1, wherein in the step (3), the phase-change microspheres obtained in the step (1) and the thermochromic silica gel capsules obtained in the step (2) are mixed according to a mass ratio of 1: 3-6 to form a mixture, an emulsifier is added while stirring, the pH value is adjusted to 8.5-10 by ammonia water, the reaction is carried out, and centrifugation and drying are carried out after the reaction is finished, so that the strawberry-shaped thermochromic energy storage material is obtained.
7. A method for preparing a strawberry shaped thermochromic energy storage material according to any of claims 1-6, comprising the steps of:
(1) mixing divinyl benzene, styrene, acrylic acid, glycidyl methacrylate, polyvinylpyrrolidone and paraffin to form a mixture, heating the mixture, stirring and reacting for 10-30 min at the speed of 4000-10000 rpm by using a homogenizer, adding an emulsifier and an initiator, continuously stirring and reacting, cooling, centrifuging and cleaning to obtain phase-change microspheres;
(2) mixing a leuco dye, an electron acceptor compound and a solvent to obtain a thermochromic core material mixture, heating the thermochromic core material mixture to 70-90 ℃, stirring to form a solution, adding deionized water, tetraethyl orthosilicate, a silane coupling agent and an emulsifier in a mass ratio of 1: 100-200: 1-5: 0.5-2: 0.005-0.5 to the thermochromic core material mixture, adding ammonia water under ultrasound to react and adjust the pH value to 8-11, and centrifuging and drying after the reaction is finished to obtain the thermochromic silica gel capsule;
(3) and (3) mixing the phase-change microspheres obtained in the step (1) and the thermochromic silica gel capsules obtained in the step (2) according to a mass ratio of 1: 3-6 to form a mixture, adding an emulsifier while stirring, adjusting the pH to 8.5-10 with ammonia water, reacting, and centrifuging and drying after the reaction is finished to obtain the strawberry-shaped thermochromic energy storage material.
8. The strawberry-shaped thermochromic energy storage material prepared according to any one of claims 1 to 6.
9. The strawberry-shaped thermochromic energy storage material of claim 8, wherein the enthalpy of the strawberry-shaped thermochromic energy storage material is 120-138J/g, and the thermochromic rate is 0.10-0.18 s-1。
10. Use of the strawberry shaped thermochromic energy storage material according to claim 8 or 9 as a smart material in the fields of construction, energy saving, environmental protection, clothing, medical care.
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