CN110685033A - Flexible composite phase change energy storage line and preparation method thereof - Google Patents
Flexible composite phase change energy storage line and preparation method thereof Download PDFInfo
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- CN110685033A CN110685033A CN201910961500.4A CN201910961500A CN110685033A CN 110685033 A CN110685033 A CN 110685033A CN 201910961500 A CN201910961500 A CN 201910961500A CN 110685033 A CN110685033 A CN 110685033A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention provides a flexible composite phase change energy storage line and a preparation method thereof, which are prepared by adopting prepared heat-conducting porous polyvinylidene fluoride fiber to package a phase change energy storage material, wherein the heat-conducting porous polyvinylidene fluoride fiber is a polyvinylidene fluoride fiber which has a compact skin layer structure and a porous internal supporting structure and is modified by heat-conducting fillers. The problems that the existing flexible packaging substrate polymer hollow fiber is low in thermal conductivity, and the thermal response rate of the prepared braided composite phase change material is still low due to the low thermal conductivity are solved. The invention belongs to the technical field of energy storage materials.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a flexible composite phase change energy storage line and a preparation method thereof.
Background
Energy is an indispensable part in our lives, and the development of economy and the progress of society are difficult without energy. The research on energy storage is carried out in the early 60 th 19 th century, and the energy storage material is widely applied to different fields of electronic computers, buildings, textiles, industry, aviation and the like through continuous development mainly for recovering solar energy and wind energy waste heat so as to save energy. The main mode of thermal energy storage is latent heat storage (phase change energy storage) technology, which uses a large amount of latent heat absorbed or released by the phase change energy storage material when its own state changes. The phase change energy storage material is classified into a gas-liquid system, a solid-gas system and a solid-liquid system through a phase change mode, phase change can occur at specific temperature, molecular arrangement of substances is rapidly changed between order and disorder, and the environment temperature is adjusted along with absorption or release of heat energy, so that specific application of the materials is achieved. This process is reversible and the phase change material can be reused. The phase-change energy storage material is a novel functional material which can adjust self phase change through ambient temperature so as to absorb heat in the environment or release the self stored heat, and has the advantages of high energy storage density, constant temperature, easy process control and the like, thereby having wide application prospect in the field of energy storage.
However, there are two major disadvantages to commonly used organic phase change energy storage materials, namely, easy leakage in liquid state and low thermal conductivity. In view of the application problem, research in recent years mainly focuses on the packaging of phase change energy storage materials and the improvement of heat conductivity. The reported support materials mainly include porous inorganic materials such as carbon foam, expanded graphite, metal foam, expanded vermiculite and the like. However, these porous substrates have limited the variety of shapes that can be obtained by encapsulating the phase change material. It has also been reported that flexible fibrous phase change energy storage materials would be advantageous. The combination of the phase-change energy storage material and the textile technology can obtain the intelligent textile for controlling the temperature. They can be used for outdoor wear, blankets, duvets, mattresses and pillow cases, etc., and also in the electronics computer industry.
Flexible phase change materials used for smart textiles typically require phase change energy storage materials to be encapsulated in fibers. The main packaging modes reported at present are mainly three, namely, a phase change energy storage material is prepared into microcapsules and mixed into fibers; secondly, attaching the energy storage material on the surface of the fiber; and thirdly, encapsulating the phase change energy storage material in the hollow part of the hollow fiber. The flexible fiber prepared by the two methods not only has low packaging amount, but also has poor thermal response rate in the fiber due to low thermal conductivity; the latter may cause leakage due to the large diameter of the hollow fiber, and also cause a poor thermal response rate inside the fiber due to the low thermal conductivity of the polymer. Patents CN108084969A and CN108130046A report a braided composite phase-change energy storage material and a preparation method thereof. In the two patents, the phase change energy storage material is packaged by the polymer hollow fiber, so that the high packaging amount of the phase change energy storage material is realized, but the polymer hollow fiber in the patent still takes the polymer with low thermal conductivity as a raw material, and the thermal response rate of the prepared braided composite phase change material is still very low. Therefore, the development of the flexible composite phase change energy storage line with high packaging capacity and high thermal conductivity and the preparation method thereof have very important significance and wide application prospect in the aspects of energy storage material design and application.
Disclosure of Invention
The invention aims to: the flexible composite phase change energy storage line and the preparation method thereof are provided to solve the problems that the existing flexible packaging substrate polymer hollow fiber has low thermal conductivity, and the thermal response rate of the prepared braided composite phase change material is still low due to the low thermal conductivity.
The invention is realized by the following technical scheme:
the utility model provides a flexible compound phase transition energy storage line adopts the heat conduction porous polyvinylidene fluoride fibre encapsulation phase change energy storage material of preparation to make, heat conduction porous polyvinylidene fluoride fibre have fine and close cortex structure and porous inside bearing structure, the polyvinylidene fluoride fibre of modification by heat conduction filler simultaneously.
In the flexible composite phase change energy storage line, the phase change energy storage material is one of paraffin, fatty acid and eutectic mixture thereof, 1-dodecanol, 1-tetradecanol, propyl palmitate, methyl stearate, ethylene glycol distearate, acetamide, dodecyl carbonate, tetradecyl carbonate, hexadecyl carbonate and octadecyl carbonate;
in the flexible composite phase-change energy storage line, the heat-conducting filler is one or more mixed one-dimensional or two-dimensional heat-conducting fillers of hydroxyl, aminated single-walled or multi-walled carbon nanotubes, hydroxyl, aminated graphene or hydroxylated MXene, and the addition amount is 0-5 wt%;
the preparation method of the flexible composite phase change energy storage line comprises the following steps: firstly, preparing heat-conducting filler modified polyvinylidene fluoride fiber by adopting a non-solvent induced phase method to obtain heat-conducting porous polyvinylidene fluoride fiber; then, the obtained heat-conducting porous polyvinylidene fluoride fiber is soaked in a phase change energy storage material which is heated and is in a liquid state, and the phase change energy storage material is packaged in the heat-conducting porous polyvinylidene fluoride fiber by combining ultrasonic assistance and capillary effect to prepare a flexible composite phase change energy storage line;
the preparation method of the heat-conducting porous polyvinylidene fluoride fiber comprises the following steps:
1) and drying the polyvinylidene fluoride powder and the heat-conducting filler in a vacuum drying oven for 12 hours at the temperature of 60 ℃ for later use. Stirring 0-5 wt% of heat-conducting filler, 0-5 wt% of compatilizer, 0-5 wt% of pore-forming agent and 60-75 wt% of solvent for 5 hours at 70 ℃, and performing ultrasonic treatment for 30min to graft the heat-conducting filler on the compatilizer and uniformly disperse the heat-conducting filler in the solvent.
2) Inverting the solution obtained in the step 1) and 15 wt% -25 wt% of polyvinylidene fluoride together in a reaction kettle, stirring for 24 hours at 70 ℃, and performing vacuum defoaming to form uniform and transparent homogeneous spinning solution.
3) Preparing the heat-conducting porous polyvinylidene fluoride fiber by adopting a non-solvent induced phase method, spraying the homogeneous spinning solution in the step 2) through a spinneret plate, then cooling the sprayed homogeneous spinning solution in ionized water after passing through an air gap with the length of 0.5-2 cm, and winding the cooled homogeneous spinning solution into the fiber, wherein the winding speed is 20-30 m/min. And soaking the obtained nascent fiber in deionized water for 1 week, taking out and airing to obtain the heat-conducting porous polyvinylidene fluoride fiber.
The solvent is one or two mixed solvents of dimethylacetamide, dimethylformamide, dimethyl sulfoxide, methyl pyrrolidone or triethyl phosphate, and the addition amount is 60-75 wt%.
The compatilizer is one of styrene-maleic anhydride copolymer, polyvinylidene fluoride grafted acrylic acid or polyvinylidene fluoride grafted glycidyl methacrylate, and the addition amount is 0-5 wt%.
The pore-foaming agent is one of polyethylene glycol, polyvinylpyrrolidone, lithium chloride or lithium perchlorate, and the addition amount is 0-5 wt%.
The packaging method of the phase change energy storage material comprises the following steps: heating the phase change energy storage material to be fully melted, putting the prepared heat-conducting porous polyvinylidene fluoride fiber into the melted phase change energy storage material to be soaked for 2-5 hours, and carrying out ultrasonic treatment for 15min to enable the phase change energy storage material to fully fill the pores in the fiber to obtain the flexible composite phase change energy storage line.
The principle of the invention is as follows: the polyvinylidene fluoride fiber with a compact skin layer structure and a porous internal supporting structure is prepared by a non-solvent induced phase method, and the heat-conducting porous polyvinylidene fluoride fiber is prepared by modifying polyvinylidene fluoride by a heat-conducting filler. The heat-conducting filler and the compatilizer are subjected to grafting reaction firstly in the preparation process, and the heat-conducting filler can be uniformly dispersed in the fiber in the subsequent spinning process. And encapsulating the phase change energy storage material in the heat-conducting porous polyvinylidene fluoride fiber to prepare the flexible composite phase change energy storage line.
Compared with the prior art, the invention has the following advantages: aiming at the deficiency in the field of phase change energy storage, a flexible composite phase change energy storage line and a preparation method thereof are provided. The flexible composite phase change energy storage line has high phase change energy storage material packaging amount and high heat conductivity. Meanwhile, the appearance of the fabric is in a flexible linear shape, so that the fabric has strong shape diversity, can be used for intelligent textiles and the field of electronic computers, and is very favorable for practical popularization and application. In addition, the preparation method of the flexible composite phase change energy storage line provided by the invention is simple and feasible, has low cost, can realize large-scale production by adopting the existing equipment, and is very favorable for popularization and practical application.
Drawings
FIG. 1 is a microstructure of the thermally conductive porous polyvinylidene fluoride fiber of example 1;
FIG. 2 is an SEM image of a flexible composite phase change energy storage line in example 1;
FIG. 3 is a microstructure of the thermally conductive porous polyvinylidene fluoride fiber of example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below.
Example 1
The preparation method of the flexible composite phase change energy storage line comprises the following steps:
1) and (3) drying the polyvinylidene fluoride powder (Suwei 6020) and the hydroxyl functionalized multi-wall carbon nano-tube in a vacuum drying oven at 60 ℃ for 12 hours for later use. 5 wt% of hydroxyl functionalized multi-walled carbon nanotubes (length of 2-8 μm), 5 wt% of styrene-maleic anhydride, 1 wt% of polyethylene glycol 2000 and 70 wt% of dimethylacetamide are stirred at 70 ℃ for 5h, and ultrasonic treatment is carried out for 30min (frequency of 200HZ) so that the multi-walled carbon nanotubes are grafted on the styrene-maleic anhydride and uniformly dispersed in the solvent.
2) Inverting the solution obtained in the step 1) and 19 wt% of polyvinylidene fluoride together in a reaction kettle, stirring for 24 hours at the temperature of 70 ℃, wherein the stirring speed is 40r/min, and then carrying out vacuum defoaming to form uniform and transparent homogeneous spinning solution.
3) Preparing heat-conducting porous polyvinylidene fluoride fiber by adopting a non-solvent induced phase method, spraying the homogeneous spinning solution in the step 2) through a spinning nozzle with the diameter of 4mm, then passing through an air gap with the length of 1cm, then cooling the spinning solution in ionized water, and winding the spinning solution into fiber, wherein the winding speed is 25 m/min. And soaking the obtained nascent fiber in deionized water for 1 week, taking out and airing to obtain the heat-conducting porous polyvinylidene fluoride fiber.
4) Heating paraffin (section paraffin, the melting point is 48-50 ℃) at 70 ℃ to be fully melted, putting the prepared heat-conducting porous polyvinylidene fluoride fiber into the melted paraffin to be soaked for 2 hours, carrying out ultrasonic treatment for 15min (the frequency is 200HZ) to enable the paraffin to fully fill the pores in the fiber, and adsorbing the paraffin on the surface of the fiber completely by using filter paper to obtain the flexible composite phase-change energy storage line. The relevant structure and performance parameters are shown in table 1.
Example 2
The preparation method of the flexible composite phase change energy storage line comprises the following steps:
1) and (3) drying the polyvinylidene fluoride powder (Suwei 6020) and the hydroxyl functionalized multi-wall carbon nano-tube in a vacuum drying oven at 60 ℃ for 12 hours for later use. Stirring 3 wt% of hydroxyl-functionalized multi-walled carbon nanotubes (with the length of 2-8 μm), 5 wt% of styrene-maleic anhydride, 1 wt% of polyethylene glycol 2000 and 72 wt% of dimethylacetamide at 70 ℃ for 5h, and ultrasonically treating for 30min (with the frequency of 200HZ) to graft the multi-walled carbon nanotubes on the styrene-maleic anhydride and uniformly disperse the multi-walled carbon nanotubes in the solvent.
2) Inverting the solution obtained in the step 1) and 19 wt% of polyvinylidene fluoride together in a reaction kettle, stirring for 24 hours at the temperature of 70 ℃, wherein the stirring speed is 40r/min, and then carrying out vacuum defoaming to form uniform and transparent homogeneous spinning solution.
3) Preparing heat-conducting porous polyvinylidene fluoride fiber by adopting a non-solvent induced phase method, spraying the homogeneous spinning solution in the step 2) through a spinning nozzle with the diameter of 4mm, then passing through an air gap with the length of 1cm, then cooling the spinning solution in ionized water, and winding the spinning solution into fiber, wherein the winding speed is 25 m/min. And soaking the obtained nascent fiber in deionized water for 1 week, taking out and airing to obtain the heat-conducting porous polyvinylidene fluoride fiber.
4) Heating paraffin (section paraffin, the melting point is 48-50 ℃) at 70 ℃ to be fully melted, putting the prepared heat-conducting porous polyvinylidene fluoride fiber into the melted paraffin to be soaked for 2 hours, carrying out ultrasonic treatment for 15min (the frequency is 200HZ) to enable the paraffin to fully fill the pores in the fiber, and adsorbing the paraffin on the surface of the fiber completely by using filter paper to obtain the flexible composite phase-change energy storage line. The relevant structure and performance parameters are shown in table 1.
Example 3
The preparation method of the flexible composite phase change energy storage line comprises the following steps:
1) and (3) drying the polyvinylidene fluoride powder (Suwei 6020) and the hydroxyl functionalized multi-wall carbon nano-tube in a vacuum drying oven at 60 ℃ for 12 hours for later use. Stirring 1 wt% of hydroxyl-functionalized multi-walled carbon nanotubes (with the length of 2-8 μm), 5 wt% of styrene-maleic anhydride, 1 wt% of polyethylene glycol 2000 and 74 wt% of dimethylacetamide at 70 ℃ for 5h, and ultrasonically treating for 30min (with the frequency of 200HZ) to graft the multi-walled carbon nanotubes on the styrene-maleic anhydride and uniformly disperse the multi-walled carbon nanotubes in a solvent.
2) Inverting the solution obtained in the step 1) and 19 wt% of polyvinylidene fluoride together in a reaction kettle, stirring for 24 hours at the temperature of 70 ℃, wherein the stirring speed is 40r/min, and then carrying out vacuum defoaming to form uniform and transparent homogeneous spinning solution.
3) Preparing heat-conducting porous polyvinylidene fluoride fiber by adopting a non-solvent induced phase method, spraying the homogeneous spinning solution in the step 2) through a spinning nozzle with the diameter of 4mm, then passing through an air gap with the length of 1cm, then cooling the spinning solution in ionized water, and winding the spinning solution into fiber, wherein the winding speed is 25 m/min. And soaking the obtained nascent fiber in deionized water for 1 week, taking out and airing to obtain the heat-conducting porous polyvinylidene fluoride fiber.
4) Heating paraffin (section paraffin, the melting point is 48-50 ℃) at 70 ℃ to be fully melted, putting the prepared heat-conducting porous polyvinylidene fluoride fiber into the melted paraffin to be soaked for 2 hours, carrying out ultrasonic treatment for 15min (the frequency is 200HZ) to enable the paraffin to fully fill the pores in the fiber, and adsorbing the paraffin on the surface of the fiber completely by using filter paper to obtain the flexible composite phase-change energy storage line. The relevant structure and performance parameters are shown in table 1.
Example 4
The preparation method of the flexible composite phase change energy storage line comprises the following steps:
1) and (3) drying the polyvinylidene fluoride powder (Suwei 6020) and the hydroxyl functionalized multi-wall carbon nano-tube in a vacuum drying oven at 60 ℃ for 12 hours for later use. 5 wt% of hydroxyl functionalized multi-walled carbon nanotubes (length of 2-8 μm), 5 wt% of styrene-maleic anhydride, 3 wt% of polyethylene glycol 2000 and 68 wt% of dimethylacetamide are stirred at 70 ℃ for 5h, and ultrasonic treatment is carried out for 30min (frequency of 200HZ) so that the multi-walled carbon nanotubes are grafted on the styrene-maleic anhydride and uniformly dispersed in the solvent.
2) Inverting the solution obtained in the step 1) and 19 wt% of polyvinylidene fluoride together in a reaction kettle, stirring for 24 hours at the temperature of 70 ℃, wherein the stirring speed is 40r/min, and then carrying out vacuum defoaming to form uniform and transparent homogeneous spinning solution.
3) Preparing heat-conducting porous polyvinylidene fluoride fiber by adopting a non-solvent induced phase method, spraying the homogeneous spinning solution in the step 2) through a spinning nozzle with the diameter of 4mm, then passing through an air gap with the length of 1cm, then cooling the spinning solution in ionized water, and winding the spinning solution into fiber, wherein the winding speed is 25 m/min. And soaking the obtained nascent fiber in deionized water for 1 week, taking out and airing to obtain the heat-conducting porous polyvinylidene fluoride fiber.
4) Heating paraffin (section paraffin, the melting point is 48-50 ℃) at 70 ℃ to be fully melted, putting the prepared heat-conducting porous polyvinylidene fluoride fiber into the melted paraffin to be soaked for 2 hours, carrying out ultrasonic treatment for 15min (the frequency is 200HZ) to enable the paraffin to fully fill the pores in the fiber, and adsorbing the paraffin on the surface of the fiber completely by using filter paper to obtain the flexible composite phase-change energy storage line. The relevant structure and performance parameters are shown in table 1.
Example 5
The preparation method of the flexible composite phase change energy storage line comprises the following steps:
1) and (3) drying the polyvinylidene fluoride powder (Suwei 6020) and the hydroxyl functionalized multi-wall carbon nano-tube in a vacuum drying oven at 60 ℃ for 12 hours for later use. 5 wt% of hydroxyl functionalized multi-walled carbon nanotubes (length of 2-8 μm), 5 wt% of styrene-maleic anhydride, 5 wt% of polyethylene glycol 2000 and 66 wt% of dimethylacetamide are stirred at 70 ℃ for 5h, and ultrasonic treatment is performed for 30min (frequency of 200HZ) to graft the multi-walled carbon nanotubes on the styrene-maleic anhydride and uniformly disperse the multi-walled carbon nanotubes in the solvent.
2) Inverting the solution obtained in the step 1) and 19 wt% of polyvinylidene fluoride together in a reaction kettle, stirring for 24 hours at the temperature of 70 ℃, wherein the stirring speed is 40r/min, and then carrying out vacuum defoaming to form uniform and transparent homogeneous spinning solution.
3) Preparing heat-conducting porous polyvinylidene fluoride fiber by adopting a non-solvent induced phase method, spraying the homogeneous spinning solution in the step 2) through a spinning nozzle with the diameter of 4mm, then passing through an air gap with the length of 1cm, then cooling the spinning solution in ionized water, and winding the spinning solution into fiber, wherein the winding speed is 25 m/min. And soaking the obtained nascent fiber in deionized water for 1 week, taking out and airing to obtain the heat-conducting porous polyvinylidene fluoride fiber.
4) Heating paraffin (section paraffin, the melting point is 48-50 ℃) at 70 ℃ to be fully melted, putting the prepared heat-conducting porous polyvinylidene fluoride fiber into the melted paraffin to be soaked for 2 hours, carrying out ultrasonic treatment for 15min (the frequency is 200HZ) to enable the paraffin to fully fill the pores in the fiber, and adsorbing the paraffin on the surface of the fiber completely by using filter paper to obtain the flexible composite phase-change energy storage line. The relevant structure and performance parameters are shown in table 1.
TABLE 1 Performance parameters of thermally conductive porous polyvinylidene fluoride fibers and flexible composite phase-change energy storage lines
As can be seen from fig. 1, the heat-conducting porous polyvinylidene fluoride fiber prepared in example 1 has a black appearance, a cross section having a through porous structure, and a pore size of about 1 μm. Examples 1-3 differ by the addition of different amounts of multi-walled carbon nanotubes, in descending order. As can be seen from Table 1, the thermal conductivity of the fibers with the addition of 5 wt% multi-walled carbon nanotubes was 0.601W/(m.K), which is about 2 times higher than that of the pure polyvinylidene fluoride fibers. Along with the reduction of the content of the multi-wall carbon nano tubes, the thermal conductivity of the heat-conducting porous polyvinylidene fluoride fiber is in a reduction trend, and the porosity is basically unchanged. As can be seen from fig. 2, in example 1, after paraffin encapsulation is performed, the paraffin fills the micropores of the entire fiber, the encapsulation amount reaches 76.7%, and with the increase of the multi-walled carbon nanotubes, the encapsulation amount of the paraffin is basically unchanged, but the thermal conductivity of the composite phase-change energy storage line is in a downward trend, which is consistent with the thermal conductivity change trend of the heat-conducting porous polyvinylidene fluoride fiber.
Fig. 3 is a microstructure diagram of the thermally conductive porous polyvinylidene fluoride fiber prepared in example 5, and shows a larger pore size and a more uniform microporous structure compared to fig. 1. It is shown that the pore diameter and porosity of the fiber can be effectively improved by adding more pore-forming agent. Examples 1 and 4, 5 differ in that different amounts of porogen polyethylene glycol 2000 are added, in increasing order. As can be seen from table 1, as the content of the porogen polyethylene glycol 2000 increases, the thermal conductivity and the porosity of the thermal conductive porous polyvinylidene fluoride fiber decrease, which indicates that the thermal conductivity of the fiber is also decreased due to the increase of the porosity. After paraffin encapsulation, the amount of paraffin encapsulation increased with increasing fiber porosity, reaching 87.1% when 5 wt% polyethylene glycol 2000 was added. But the thermal conductivity of the composite phase change energy storage line also shows a descending trend, which is consistent with the thermal conductivity change trend of the heat-conducting porous polyvinylidene fluoride fiber. In conclusion, the heat-conducting porous polyvinylidene fluoride fiber prepared by the non-solvent induced phase method has higher heat conductivity and flexible weaving property. And after paraffin encapsulation, the composite phase change energy storage line with high encapsulation amount, high heat conduction and flexibility can be obtained.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The utility model provides a flexible compound phase transition energy storage line which characterized in that: the prepared heat-conducting porous polyvinylidene fluoride fiber packaged phase change energy storage material is adopted to prepare the material, the heat-conducting porous polyvinylidene fluoride fiber has a compact skin layer structure and a porous internal supporting structure, and meanwhile, the polyvinylidene fluoride fiber is modified by heat-conducting filler.
2. The flexible composite phase-change energy storage line according to claim 1, wherein: the phase change energy storage material is one of paraffin, fatty acid and eutectic mixture thereof, 1-dodecanol, 1-tetradecanol, propyl palmitate, methyl stearate, ethylene glycol distearate, acetamide, dodecyl carbonate, tetradecyl carbonate, hexadecyl carbonate and octadecyl carbonate.
3. The flexible composite phase-change energy storage line according to claim 1, wherein: the heat-conducting filler is one or more mixed one-dimensional or two-dimensional heat-conducting fillers of hydroxyl or aminated single-walled or multi-walled carbon nanotubes, hydroxyl or aminated graphene, or hydroxylated MXene, and the addition amount of the one-dimensional or two-dimensional heat-conducting fillers is 0-5 wt%.
4. A preparation method of the flexible composite phase-change energy storage line as claimed in any one of claims 1 to 3, wherein the specific preparation method comprises the following steps: firstly, preparing heat-conducting filler modified polyvinylidene fluoride fiber by adopting a non-solvent induced phase method to obtain heat-conducting porous polyvinylidene fluoride fiber; and then, soaking the obtained heat-conducting porous polyvinylidene fluoride fiber in a phase change energy storage material which is in a liquid state after being heated, and packaging the phase change energy storage material in the heat-conducting porous polyvinylidene fluoride fiber by combining ultrasonic assistance and capillary effect to prepare the flexible composite phase change energy storage wire.
5. The preparation method of the flexible composite phase-change energy storage line according to claim 4, wherein the preparation method of the heat-conducting porous polyvinylidene fluoride fiber comprises the following steps:
1) and drying the polyvinylidene fluoride powder and the heat-conducting filler in a vacuum drying oven for 12 hours at the temperature of 60 ℃ for later use. Stirring 0-5 wt% of heat-conducting filler, 0-5 wt% of compatilizer, 0-5 wt% of pore-forming agent and 60-75 wt% of solvent for 5 hours at 70 ℃, and performing ultrasonic treatment for 30min to graft the heat-conducting filler on the compatilizer and uniformly disperse the heat-conducting filler in the solvent.
2) Inverting the solution obtained in the step 1) and 15 wt% -25 wt% of polyvinylidene fluoride together in a reaction kettle, stirring for 24 hours at 70 ℃, and performing vacuum defoaming to form uniform and transparent homogeneous spinning solution.
3) Preparing the heat-conducting porous polyvinylidene fluoride fiber by adopting a non-solvent induced phase method, spraying the homogeneous spinning solution in the step 2) through a spinneret plate, then cooling the sprayed homogeneous spinning solution in ionized water after passing through an air gap with the length of 0.5-2 cm, and winding the cooled homogeneous spinning solution into the fiber, wherein the winding speed is 20-30 m/min. And soaking the obtained nascent fiber in deionized water for 1 week, taking out and airing to obtain the heat-conducting porous polyvinylidene fluoride fiber.
6. The preparation method of the flexible composite phase-change energy storage line according to claim 4, wherein the preparation method comprises the following steps: the solvent is one or two mixed solvents of dimethylacetamide, dimethylformamide, dimethyl sulfoxide, methyl pyrrolidone or triethyl phosphate, and the addition amount is 60-75 wt%.
7. The preparation method of the flexible composite phase-change energy storage line according to claim 4, wherein the preparation method comprises the following steps: the compatilizer is one of styrene-maleic anhydride copolymer, polyvinylidene fluoride grafted acrylic acid or polyvinylidene fluoride grafted glycidyl methacrylate, and the addition amount is 0-5 wt%.
8. The preparation method of the flexible composite phase-change energy storage line according to claim 4, wherein the preparation method comprises the following steps: the pore-foaming agent is one of polyethylene glycol, polyvinylpyrrolidone, lithium chloride or lithium perchlorate, and the addition amount is 0-5 wt%.
9. The preparation method of the flexible composite phase-change energy storage line according to claim 4, wherein the preparation method comprises the following steps: the packaging method of the phase change energy storage material comprises the following steps: heating the phase change energy storage material to be fully melted, putting the prepared heat-conducting porous polyvinylidene fluoride fiber into the melted phase change energy storage material to be soaked for 2-5 hours, and carrying out ultrasonic treatment for 15min to enable the phase change energy storage material to fully fill the pores in the fiber to obtain the flexible composite phase change energy storage line.
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| CN112981582A (en) * | 2021-02-09 | 2021-06-18 | 华中科技大学 | Temperature control fiber integrating heat superconducting and refrigerating functions and preparation method and application thereof |
| CN115125629A (en) * | 2022-08-31 | 2022-09-30 | 江苏领智健康科技有限公司 | Textile fiber material with heat storage and temperature adjustment functions and preparation method thereof |
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