CN112226209B - Preparation and application of hollow tubular conductive polymer composite fiber aerogel material - Google Patents
Preparation and application of hollow tubular conductive polymer composite fiber aerogel material Download PDFInfo
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Abstract
The invention discloses a preparation method of a hollow tubular conductive polymer composite fiber aerogel, belonging to the field of novel composite materials. The method comprises the steps of carrying out in-situ polymerization on a conductive polymer on the inner wall and the outer wall of natural kapok fibers to form a conductive polymer coating, then assembling to form hollow tubular conductive polymer composite fiber aerogel, and combining the aerogel with an organic phase change material to obtain the composite phase change material. The preparation method has the advantages that the preparation process of the conductive polymer composite fiber aerogel is simple, the raw materials are natural hollow fibers, and the raw materials are cheap and easily available, green and environment-friendly; the prepared hollow tubular conductive polymer composite fiber aerogel has low density and high porosity; the aerogel composite phase change material has no leakage, high latent heat of phase change, high heat conductivity and good thermal cycle stability, and lays a foundation for the application of the aerogel composite phase change material in the fields of energy storage, electrodes, catalysis and the like.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a hollow tubular conductive polymer composite fiber aerogel and an energy storage application thereof.
Background
The organic phase-change material is widely applied to the field of phase-change energy storage as a material with high heat storage density, stable chemical performance, no toxicity and no corrosiveness. Common organic phase change materials include paraffins, alkanes, unsaturated alcohols, fatty acids, and the like. However, the organic phase change material is easy to leak in the solid-liquid phase change process, so that the repeatable utilization rate of the material is reduced, and in addition, the organic phase change material generally has the defects of poor heat conductivity and low thermal conductivity.
At present, a porous network structure material and an organic phase change material are often selected to prevent the organic phase change material from leaking, the porous material is selected to contain aerogel materials, metal foams, polymer networks and the like, a heat conducting medium and the organic phase change material are often combined to improve the heat conductivity of the composite material in the aspect of improving the heat conducting performance, and the common heat conducting medium is carbon materials, metals, conductive polymers and the like. However, the preparation process of the porous material is generally complicated, the application of the phase-change material is limited, the improvement of the thermal conductivity of the composite material is limited due to the direct addition of a small amount of the heat-conducting medium, and the excessive addition of the heat-conducting medium can reduce the heat storage density of the composite phase-change material and the heat storage performance of the composite phase-change material.
Kapok fiber is a natural biomass material with a hollow tubular structure, can be polymerized on the inner wall and the outer wall of a hollow pipeline to form a conductive polymer coating, the kapok fiber modified by the conductive polymer coating is prepared into a porous aerogel structure to form hollow tubular conductive polymer composite fiber aerogel, and the aerogel material is combined with an organic phase-change material, so that the leakage of the organic phase-change material in a solid-liquid phase-change process can be prevented, the heat conduction performance of the composite phase-change material can be improved, and meanwhile, higher phase-change material load rate and heat storage density can be kept. The hollow tubular conductive polymer composite fiber aerogel has good conductive and heat-conducting properties, and can be widely applied to the fields of energy storage materials, electrode materials, catalytic materials and the like.
Disclosure of Invention
The invention aims to provide a method for preparing a hollow tubular conductive polymer composite fiber aerogel and a phase-change composite material thereof. Taking natural kapok fibers with a hollow tubular structure as a template, carrying out in-situ oxidative polymerization on the inner wall and the outer wall of a kapok fiber pipeline to generate a continuous conductive polymer coating, and assembling the kapok fibers modified by the conductive polymer coating to generate the hollow tubular conductive polymer composite fiber aerogel. The composite fiber aerogel is used for effectively loading the phase-change material by a melt impregnation method, a solution impregnation method and the like to obtain the composite phase-change material. The preparation method adopts natural biomass as a template, has wide raw material source, low cost, simple process, no pollution and easy large-scale industrial production.
The invention also aims to provide a hollow tubular conductive polymer composite fiber aerogel and a phase-change composite material thereof. The obtained aerogel material successfully reserves the hollow tubular structure of the kapok fiber, the porosity of the aerogel can be greatly improved, meanwhile, the kapok fiber modified by the conductive polymer coating is mutually overlapped to form the aerogel with a three-dimensional porous network structure, a heat conduction and electric conduction channel and rich organic functional groups containing oxygen, nitrogen, sulfur and the like are provided, and the composite fiber aerogel material has the characteristics of low density, high porosity, large pore volume and rich functional groups. The obtained composite phase change material has high load rate, large latent heat of phase change, high thermal conductivity and good thermal cycle stability.
The invention discloses a preparation method of a hollow tubular conductive polymer composite fiber aerogel, which is implemented by the following technical scheme: adopting natural kapok fiber with a hollow tubular structure as a template, and carrying out pretreatment on the template by a solvent or a chemical method to remove lipid on the surface of the kapok fiber so as to obtain the kapok fiber with good hydrophilicity; adding conductive polymer monomers such as pyrrole, aniline and thiophene and an oxidant, and carrying out in-situ oxidative polymerization on the inner and outer tube walls of the kapok fiber to generate conductive polymer coatings such as polypyrrole, polyaniline and polythiophene; then assembling the kapok fiber modified by the conductive polymer coating, and then obtaining hollow tubular conductive polymer composite aerogel by a freeze-drying method; and loading the organic phase-change material in the composite aerogel by adopting a melt impregnation method, a solution method and the like to obtain the composite phase-change material, and inspecting the energy storage efficiency and the heat conduction performance of the composite phase-change material.
The preparation method of the hollow tubular conductive polymer composite fiber aerogel specifically comprises the following steps:
step 1: soaking the kapok fiber in 0.1-10wt% sodium hydroxide solution, treating at 20-120 deg.c for 10-240min to eliminate fiber surface lipid, washing with ethanol and water separately, and drying to obtain hydrophilic kapok fiber.
Step 2: adding a certain amount of hydrophilic kapok fiber into water for uniform dispersion, then adding a certain amount of conductive polymer monomer and oxidant into the solution, fully mixing and reacting for 0.5-24h at-10-120 ℃ to ensure that the conductive polymer monomer is oxidized and polymerized on the inner and outer pipe walls of the kapok fiber, and filtering after the reaction is finished to obtain the conductive polymer coating modified kapok fiber.
And step 3: in order to obtain hollow tubular conductive polymer composite fiber aerogels with different densities, kapok fibers modified by the conductive polymer coating obtained in the above steps are fully mixed with water according to the mass ratio of 1:5-100, physical crosslinking is formed among the fibers, then liquid nitrogen is used for quickly freezing the mixed solution, and the frozen sample is subjected to freeze drying to obtain the hollow tubular conductive polymer composite fiber aerogels with low density and high porosity.
And 4, step 4: and (3) efficiently compounding the hollow tubular conductive polymer composite fiber aerogel obtained in the step (3) with an organic phase change material under the vacuum condition of 60-200 ℃ to obtain the shaped composite phase change material with enhanced heat conductivity.
Further, the conductive polymer monomer includes: pyrrole, aniline, thiophene.
Further, the initiator comprises: ferric salts such as ferric chloride, ferric sulfate and ferric nitrate, peroxides such as ammonium persulfate and potassium persulfate.
Further, the organic phase change material comprises: paraffin, octadecanoic acid, tetradecanoic acid, octadecanol, polyethylene glycol with different molecular masses, octadecane, tetradecane and the like.
The invention has the following remarkable advantages:
(1) the preparation raw materials of the hollow tubular conductive polymer composite fiber aerogel are green, cheap and easily available, the preparation process is simple, convenient and easy to operate, the preparation process is environment-friendly and pollution-free, and the large-scale production is easy to realize.
(2) This hollow tubular conductive polymer composite fiber aerogel has kept the original hollow pipeline structure of kapok fiber, and its low density, high porosity characteristic can ensure the high load factor of organic phase change material, promote composite phase change material's heat-retaining density, can effectively prevent organic phase change material at the emergence of revealing of solid-liquid phase change in-process simultaneously, improve composite phase change material's structural stability.
(3) The hollow tubular conductive polymer composite fiber aerogel prepared by the method is in a three-dimensional porous network structure formed by mutually lapping kapok fibers modified by a conductive polymer coating, effectively provides a heat conduction and electric conduction channel, and organic functional groups rich in oxygen, nitrogen, sulfur and the like on the surface can further take charge of other catalytic materials and energy materials, so that a foundation is laid for the application of the hollow tubular conductive polymer composite fiber aerogel in the fields of energy storage, electrodes, catalysis and the like.
(4) The conductive polymer composite aerogel has good light-heat conversion characteristics, and the composite phase-change material is endowed with the same high-efficiency light-heat conversion function.
Drawings
FIG. 1 is a scanning electron micrograph of a hollow kapok fiber according to example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the hollow tubular conductive polymer composite aerogel obtained in example 1 of the present invention.
FIG. 3 is a scanning electron microscope image of the composite phase change material obtained in example 2 of the present invention.
FIG. 4 is a DSC chart of the composite phase change material obtained in example 2 of the present invention.
Detailed Description
In order to make the features and advantages of the present invention more obvious, the following embodiments are further described.
Example 1
Step 1: soaking the kapok fiber in a sodium hydroxide solution with the mass concentration of 1wt%, treating at 20 ℃ for 10min to remove lipid on the surface of the fiber, then washing with ethanol and water respectively, and drying to obtain the hydrophilic kapok fiber.
Step 2: adding a certain amount of hydrophilic kapok fiber into water for uniform dispersion, then adding a certain amount of pyrrole monomer and ferric chloride into the solution, fully mixing and reacting for 0.5h at-10 ℃ so that the pyrrole monomer is oxidized and polymerized on the inner and outer tube walls of the kapok fiber, and filtering after the reaction is finished to obtain the polypyrrole coating modified kapok fiber.
And step 3: fully mixing the polypyrrole coating modified kapok fibers obtained in the step with water according to the mass ratio of 1:5 to form a uniform mixed solution, quickly freezing the mixed solution by using liquid nitrogen, and freeze-drying the frozen sample to obtain the hollow tubular polypyrrole composite fiber aerogel with low density and high porosity.
And 4, step 4: and (4) efficiently compounding the hollow tubular polypyrrole composite fiber aerogel obtained in the step (3) with paraffin under the vacuum condition of 80 ℃ to obtain the heat-conducting property-enhanced shaped composite phase-change material.
The stable load rate of the paraffin in the obtained composite phase-change material is 88 percent, the melting enthalpy value is 167J/g, and the heat conductivity increasing rate is 300 percent
Example 2
Step 1: soaking the kapok fiber in a sodium hydroxide solution with the mass concentration of 3wt%, treating at 60 ℃ for 30min to remove lipid on the surface of the fiber, then washing with ethanol and water respectively, and drying to obtain the hydrophilic kapok fiber.
Step 2: adding a certain amount of hydrophilic kapok fiber into water for uniform dispersion, then adding a certain amount of pyrrole monomer and ammonium persulfate into the solution, fully mixing and reacting for 2 hours at 10 ℃ so that the pyrrole monomer is oxidized and polymerized on the inner and outer tube walls of the kapok fiber, and filtering after the reaction is finished to obtain the polypyrrole coating modified kapok fiber.
And step 3: fully mixing the polypyrrole coating modified kapok fibers obtained in the step with water according to the mass ratio of 1:10 to form a uniform mixed solution, quickly freezing the mixed solution by using liquid nitrogen, and freeze-drying the frozen sample to obtain the hollow tubular polypyrrole composite fiber aerogel with low density and high porosity.
And 4, step 4: and (3) efficiently compounding the hollow tubular polypyrrole composite fiber aerogel obtained in the step (3) with octadecanoic acid under the vacuum condition of 120 ℃ to obtain the heat-conducting property-enhanced shaped composite phase change material.
The stable load rate of octadecanoic acid in the obtained composite phase change material is 85 percent, the melting enthalpy value is 207J/g, and the heat conductivity improvement rate is 290 percent
Example 3
Step 1: soaking the kapok fiber in a sodium hydroxide solution with the mass concentration of 5wt%, treating at 80 ℃ for 60min to remove lipid on the surface of the fiber, then washing with ethanol and water respectively, and drying to obtain the hydrophilic kapok fiber.
Step 2: adding a certain amount of hydrophilic kapok fiber into water for uniform dispersion, then adding a certain amount of aniline monomer and ferric sulfate into the solution, fully mixing and reacting for 6 hours at 60 ℃ to ensure that the aniline monomer is oxidized and polymerized on the inner and outer pipe walls of the kapok fiber, and filtering after the reaction is finished to obtain the polyaniline coating modified kapok fiber.
And step 3: fully mixing the polyaniline coating modified kapok fiber obtained in the step with water according to the mass ratio of 1:20 to form a uniform mixed solution, quickly freezing the mixed solution by using liquid nitrogen, and freeze-drying the frozen sample to obtain the hollow tubular polyaniline composite fiber aerogel with low density and high porosity.
And 4, step 4: and (3) efficiently compounding the hollow tubular polyaniline composite fiber aerogel obtained in the step (3) with octadecanol under the vacuum condition of 140 ℃ to obtain the shaped composite phase change material with enhanced heat conductivity.
The stable load rate of octadecanol in the obtained composite phase change material is 85%, the melting enthalpy value is 192J/g, and the heat conductivity improvement rate is 320%.
Example 4
Step 1: soaking the kapok fiber in a sodium hydroxide solution with the mass concentration of 8wt%, treating at 100 ℃ for 90min to remove lipid on the surface of the fiber, then washing with ethanol and water respectively, and drying to obtain the hydrophilic kapok fiber.
Step 2: adding a certain amount of hydrophilic kapok fiber into water for uniform dispersion, then adding a certain amount of aniline monomer and potassium persulfate into the solution, fully mixing and reacting for 8 hours at 80 ℃ so that the aniline monomer is subjected to oxidative polymerization on the inner and outer pipe walls of the kapok fiber, and filtering after the reaction is finished to obtain the polyaniline coating modified kapok fiber material.
And step 3: fully mixing the polyaniline coating modified kapok fiber obtained in the step with water according to the mass ratio of 1:40, after a uniform mixed solution is formed, quickly freezing the mixed solution by using liquid nitrogen, and freeze-drying a frozen sample to obtain the hollow tubular polyaniline composite fiber aerogel with low density and high porosity.
Example 5
Step 1: soaking the kapok fiber in a sodium hydroxide solution with the mass concentration of 10wt%, treating at 120 ℃ for 150min to remove lipid on the surface of the fiber, then washing with ethanol and water respectively, and drying to obtain the hydrophilic kapok fiber.
Step 2: adding a certain amount of hydrophilic kapok fiber into water for uniform dispersion, then adding a certain amount of thiophene monomer and ferric nitrate into the solution, fully mixing and reacting for 20 hours at 10 ℃ so that the thiophene monomer is oxidized and polymerized on the inner and outer tube walls of the kapok fiber, and filtering after the reaction is finished to obtain the polythiophene coating modified kapok fiber material.
And step 3: fully mixing the polythiophene coating modified kapok fiber obtained in the step with water according to the mass ratio of 1:80 to form a uniform mixed solution, quickly freezing the mixed solution by using liquid nitrogen, and freeze-drying the frozen sample to obtain the hollow tubular polythiophene composite fiber aerogel material with low density and high porosity.
And 4, step 4: and (4) efficiently compounding the hollow tubular polythiophene composite fiber aerogel obtained in the step (3) with tetradecane at the temperature of 200 ℃ under a vacuum condition to obtain the heat-conducting property-enhanced shaped composite phase change material.
The stable tetradecane loading rate of the obtained composite phase change material is 80%, the melting enthalpy value is 157J/g, and the heat conductivity improvement rate is 360%.
Claims (4)
1. A preparation method of hollow tubular conductive polymer composite fiber aerogel is characterized in that natural kapok fibers with hollow tubular structures are used as templates, and are pretreated by a solvent or a chemical method to remove lipid on the surfaces of the kapok fibers, so that the kapok fibers with good hydrophilicity are obtained; adding a conductive polymer monomer and an oxidant, and carrying out in-situ oxidative polymerization on the inner and outer tube walls of the kapok fiber to generate a polypyrrole or polyaniline or polythiophene conductive polymer coating; then assembling the kapok fiber modified by the conductive polymer coating, and then obtaining hollow tubular conductive polymer composite aerogel by a freeze-drying method; loading an organic phase-change material in the composite aerogel by adopting a melt impregnation and solution method to obtain the composite phase-change material, and specifically comprising the following steps of:
step 1: soaking kapok fiber in 0.1-10wt% sodium hydroxide solution, treating at 20-120 deg.C for 10-240min to remove fiber surface lipid, washing with ethanol and water respectively, and drying to obtain hydrophilic kapok fiber;
step 2: adding hydrophilic kapok fibers into water for uniform dispersion, then adding a conductive polymer monomer and an oxidant into the solution, fully mixing and reacting for 0.5-24h at-10-120 ℃, so that the conductive polymer monomer is subjected to oxidative polymerization on the inner and outer tube walls of the kapok fibers, and filtering after the reaction is finished to obtain conductive polymer coating modified kapok fibers;
and step 3: in order to obtain hollow tubular conductive polymer composite fiber aerogels with different densities, kapok fibers modified by the conductive polymer coating obtained in the previous step are fully mixed with water according to the mass ratio of 1:5-100, physical crosslinking is formed among the fibers, then liquid nitrogen is used for quickly freezing the mixed solution, and the frozen sample is frozen and dried to obtain hollow tubular conductive polymer composite fiber aerogels with low density and high porosity;
and 4, step 4: and (3) efficiently compounding the hollow tubular conductive polymer composite fiber aerogel obtained in the step (3) with an organic phase change material under the vacuum condition of 60-200 ℃ to obtain the shaped composite phase change material with enhanced heat conductivity.
2. The method for preparing a hollow tubular conductive polymer composite fiber aerogel according to claim 1, wherein the conductive polymer monomer comprises: pyrrole or aniline or thiophene.
3. The method for preparing the hollow tubular conductive polymer composite fiber aerogel according to claim 1, wherein the oxidizing agent comprises: one of ferric chloride, ferric sulfate, ferric nitrate, ammonium persulfate and potassium persulfate.
4. The method for preparing the hollow tubular conductive polymer composite fiber aerogel of claim 1, wherein the organic phase change material comprises: paraffin, octadecanoic acid, tetradecanoic acid, octadecanol, octadecane and tetradecane.
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