CN113403834B - High-strength high-toughness carbon nano tube composite phase change fiber, preparation method and application thereof - Google Patents

High-strength high-toughness carbon nano tube composite phase change fiber, preparation method and application thereof Download PDF

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CN113403834B
CN113403834B CN202110784316.4A CN202110784316A CN113403834B CN 113403834 B CN113403834 B CN 113403834B CN 202110784316 A CN202110784316 A CN 202110784316A CN 113403834 B CN113403834 B CN 113403834B
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phase change
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nano tube
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CN113403834A (en
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赵静娜
王娇娇
李清文
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Abstract

The invention discloses a high-strength high-toughness carbon nano tube composite phase change fiber, a preparation method and application thereof. The composite phase change fiber comprises carbon nano tube fibers and phase change materials, wherein the phase change materials are uniformly distributed in the carbon nano tube fibers or a network structure formed by the carbon nano tube fibers. The preparation method comprises the following steps: the carbon nano tube fiber is uniformly expanded under the action of gas generated by electrolysis; and immersing the obtained carbon nano tube fiber with the expansion network structure in a phase change material solution to enable the phase change material in the carbon nano tube fiber to fully infiltrate into the interior of the expansion network structure of the carbon nano tube fiber, and then performing densification treatment to obtain the high-strength high-toughness carbon nano tube composite phase change fiber. The high-strength high-toughness carbon nano tube composite phase change fiber prepared by the invention has higher temperature resistance, high strength, wide phase change temperature adjustable range and high phase change latent heat, is soluble in various paraffin materials of organic solvents, and is expected to have very wide application prospects in energy collection devices of wearable environments in the future.

Description

High-strength high-toughness carbon nano tube composite phase change fiber, preparation method and application thereof
Technical Field
The invention relates to a carbon nano tube composite material, in particular to a high-strength high-toughness carbon nano tube composite phase change fiber and a preparation method and application thereof, and belongs to the technical field of nano science.
Background
With the rapid development of Carbon Nanotube (CNT) fibers, multifunctional carbon nanotube composite fibers have also been developed. When the carbon nano tube fiber and the composite fiber formed by compounding different materials have different functionalities, the composite fiber can be applied to various fields such as artificial muscles, intelligent wearing, super capacitors, light-weight wires, composite materials and the like. If the carbon nano tube fiber is taken as a substrate, the copper plating is carried out on the carbon nano tube fiber to prepare a lightweight cable, the interface combination problem between the carbon nano tube and copper is well treated, and the conductivity of the cable can be improved by nearly two orders of magnitude compared with that of the fibril (nanoscales, 2011,3 (10): 4215-4219); coating a titanium dioxide Nano layer on the surface of the carbon Nano tube fiber, utilizing titanium dioxide to adsorb dye to generate photocharge and rapidly transferring the photocharge to the carbon Nano tube fiber to prepare a linear dye sensitized solar cell of the carbon Nano tube fiber (Nano letters,2012,12 (5): 2568-2572); by twisting a group of carbon nano tube yarns with layered structure, the electrochemical yarn with ultra-large type rapid contraction driving is prepared, and the carbon nano tube yarns have high muscle circulation stability and large driving quantity (Materials Horizons,2020,7 (11): 3043-3050).
Polyethylene glycol (PEG) is known to be used as a phase change energy storage material and has the advantages of high phase change enthalpy, stable performance, no corrosiveness and the like. Carbon nanotubes are used as medium supporting materials, and polyethylene glycol and carbon nanotube fibers are compounded to obtain the composite phase change fiber material with excellent mechanical properties and structural strength. The phase change heat storage belongs to latent heat storage, and has the advantages of high energy density, simple device, energy conservation, high efficiency and the like. At present, the phase change energy storage material has important application value and wide development prospect in various fields such as aerospace, solar energy utilization, textile industry, heat storage building and the like. However, the pure polyethylene glycol is used as a phase change material to realize heat storage and energy storage in a solid-liquid conversion mode, which leads to difficulty in realizing practical engineering due to large morphology difference of the polyethylene glycol in the energy storage process.
In summary, the prior art mainly has the following disadvantages: 1) Pure polyethylene glycol is used as a phase change material, and solid-liquid phase transformation can occur in the phase change process, so that a certain form is difficult to maintain; 2) At present, the preparation method of the composite phase change heat storage material using polyethylene glycol as a working substance mainly comprises a chemical method and a blending method, and the preparation process is relatively complex; 3) In addition, the mechanical properties of the composite phase change material using polyethylene glycol as a working substance are relatively weak; 4) Polyethylene glycol is poor in thermal response and flammability when compounded with organic polymers, and poor in toughness and brittleness when compounded with inorganic substances.
Disclosure of Invention
The invention mainly aims to provide a high-strength high-toughness carbon nano tube composite phase change fiber and a preparation method thereof, so as to overcome the defects in the prior art.
The invention also aims at providing application of the high-strength high-toughness carbon nano tube composite phase change fiber.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a high-strength high-toughness carbon nano tube composite phase-change fiber, which comprises carbon nano tube fibers and phase-change materials, wherein the phase-change materials are uniformly distributed in the carbon nano tube fibers and/or in a network structure formed by the carbon nano tube fibers, the content of the phase-change materials in the high-strength high-toughness carbon nano tube composite phase-change fiber is 35 to 70 weight percent, the phase-change temperature of the high-strength high-toughness carbon nano tube composite phase-change fiber is 50 to 65 ℃, the phase-change latent heat is more than 105.9J/g, the tensile strength is more than 2GPa, the conversion and the storage of electric energy to heat energy can be carried out under any shape, and the density is 0.5 to 1.5g/cm 3 。
The embodiment of the invention also provides a preparation method of the high-strength high-toughness carbon nano tube composite phase change fiber, which comprises the following steps:
the method comprises the steps of using carbon nanotube fibers as a cathode, and constructing an electrochemical reaction system together with an anode and electrolyte, wherein the electrolyte is an aqueous phase system containing electrolyte; electrifying the electrochemical reaction system, and uniformly expanding the carbon nano tube fibers in the radial direction and/or the length direction under the action of gas generated by electrolysis;
and immersing the obtained carbon nano tube fiber with the expansion network structure in a phase change material solution to enable the phase change material in the carbon nano tube fiber to fully infiltrate into the interior of the expansion network structure of the carbon nano tube fiber, and then performing densification treatment to obtain the high-strength high-toughness carbon nano tube composite phase change fiber.
In some embodiments, the phase change material solution comprises a phase change material and a solvent, wherein the phase change material comprises any one or a combination of two or more of stearic acid, palmitic acid, myristic acid, lauric acid, n-octadecane, paraffin wax, polyethylene glycol, and the like.
The embodiment of the invention also provides the high-strength high-toughness carbon nano tube composite phase change fiber prepared by the method.
Correspondingly, the embodiment of the invention also provides application of the high-strength high-toughness carbon nano tube composite phase change fiber in preparing a wearable environment energy collection device.
Compared with the prior art, the invention has the advantages that:
1) The invention adopts electrolyzed water to release hydrogen, utilizes interface foaming to prepare the carbon nano tube-phase change material composite phase change fiber which has good uniformity, the phase change material can further strengthen densified carbon nano tube fiber, the twisted composite fiber has higher tensile strength, and various paraffin materials which have low density, wide adjustable range of phase change temperature, high phase change enthalpy or latent heat and are soluble in organic solvents;
2) The high-strength high-toughness carbon nanotube-phase-change material composite phase-change fiber prepared by the method has good structural uniformity, still keeps a solid form in the phase-change process, and is well bound in a carbon nanotube network structure by an in-situ impregnation method, so that the phase-change material is effectively prevented from leaking out in the phase-change process;
3) The method for preparing the high-strength high-toughness carbon nano tube composite phase change fiber does not relate to toxic dangerous goods, and electrolytes such as sulfuric acid and the like can be recycled, so that the method accords with the concept of green environmental protection;
4) The preparation method of the high-strength high-toughness carbon nanotube composite phase-change fiber provided by the invention is simple and efficient, can expand continuous production, realizes industrialization, and is expected to have a very wide application prospect in energy collection devices in the wearable environment in the future.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic illustration of the mechanism by which electrolysis of water generates hydrogen gas to expand a carbon nanotube fiber network in an exemplary embodiment of the present invention;
FIGS. 2A-2D are graphs depicting morphologies of CNT-PEG composite phase change fibers in accordance with an exemplary embodiment of the present invention;
FIG. 3 is a thermogravimetric plot of a pure CNT fiber and a CNT-PEG composite phase change fiber of varying PEG loading in accordance with an exemplary embodiment of the present invention;
FIG. 4 is a stress-strain graph of a CNT-PEG composite phase-change fiber with varying amounts of PEG loading and pure CNT fiber in an exemplary embodiment of the present invention;
FIG. 5 is a DSC graph of a CNT-PEG composite phase change fiber of pure PEG and varying PEG loading in an exemplary embodiment of the present invention;
FIG. 6 is a graph of electrical to thermal energy conversion and storage for a pure CNT fiber and a PEG loaded (67%) CNT-PEG composite phase change fiber in accordance with an exemplary embodiment of the present invention;
FIGS. 7A and 7B are graphs depicting the flexibility characteristics of a CNT-PEG composite phase change fiber in accordance with an exemplary embodiment of the present invention;
FIGS. 8A and 8B are IR thermal imaging diagrams of a CNT-PEG composite phase change fiber during power up and down in accordance with an exemplary embodiment of the invention.
Detailed Description
In view of the shortcomings in the prior art, the inventor prepares a carbon nanotube (hereinafter may be simply referred to as CNT) -phase change material (e.g., polyethylene glycol) (preferably CNT-PEG) composite phase change fiber based on excellent mechanical and thermal conductivity of the carbon nanotube fiber and a stable one-dimensional structure through long-term research and a great deal of practice, so that not only can a solid structure be maintained in the phase change process, but also the carbon nanotube with high thermal conductivity greatly improves the thermal conductivity of the phase change material (e.g., polyethylene glycol).
The technical conception of the invention mainly comprises the following steps: the method of hydrogen evolution by electrolysis of water is adopted, and the carbon nano tube composite phase change fiber is prepared by interface foaming. The composite phase change fiber realizes faster electrothermal response under low voltage, and the method further develops the phase change material with low power consumption. And is expected to realize application in future intelligent energy storage equipment. The super-strong carbon nano tube-phase change material (such as polyethylene glycol) (preferably CNT-PEG) composite phase change fiber is expected to have a very wide application prospect in a wearable environment energy collection device in the future. Therefore, the hydrogen-separating and expanding carbon nano tube fiber by utilizing the electrolytic water is not only beneficial to the reassembly of the CNT, but also beneficial to the preparation of the high-performance and multifunctional CNT composite fiber, and widens the road for preparing the multifunctional CNT composite fiber in the future.
The technical scheme, the implementation process, the principle and the like are further explained as follows.
An aspect of the embodiment of the invention provides a high-strength and high-toughness carbon nanotube composite phase-change fiber, which comprises carbon nanotube fibers and phase-change materials, wherein the phase-change materials are uniformly distributed in the carbon nanotube fibers and/or in a network structure formed by the carbon nanotube fibers, the content of the phase-change materials in the high-strength and high-toughness carbon nanotube composite phase-change fiber is 35-70 wt%, the phase-change temperature of the high-strength and high-toughness carbon nanotube composite phase-change fiber is 50-65 ℃, the phase-change latent heat is more than 105.9J/g, the tensile strength is more than 2GPa, the conversion and storage of electric energy to heat energy can be carried out under any shape, and the density is 0.5-1.5 g/cm 3 。
In some embodiments, the phase change material includes any one or a combination of two or more of stearic acid, palmitic acid, myristic acid, lauric acid, n-octadecane, paraffin wax, polyethylene glycol, and the like, but is not limited thereto.
Further, the paraffin may be paraffin C16 to C18, paraffin C20 to C33, paraffin C22 to C45, paraffin C21 to C50, etc., but is not limited thereto.
Further, the polyethylene glycol may be PEG3500, or may be replaced by other PEG types, such as PEG600, PEG1000, PEG6000, and the like.
Another aspect of the embodiments of the present invention provides a method for preparing a high-strength and high-toughness carbon nanotube composite phase change fiber, which includes:
the method comprises the steps of using carbon nanotube fibers as a cathode, and constructing an electrochemical reaction system together with an anode and electrolyte, wherein the electrolyte is an aqueous phase system containing electrolyte; electrifying the electrochemical reaction system, and uniformly expanding the carbon nano tube fibers in the radial direction and/or the length direction under the action of gas generated by electrolysis;
and immersing the obtained carbon nano tube fiber with the expansion network structure in a phase change material solution to enable the phase change material in the carbon nano tube fiber to fully infiltrate into the interior of the expansion network structure of the carbon nano tube fiber, and then performing densification treatment to obtain the high-strength high-toughness carbon nano tube composite phase change fiber.
In some embodiments, the invention mainly utilizes electrolyzed water to release hydrogen to foam the carbon nanotube fiber interface to prepare the carbon nanotube composite phase change fiber. Meanwhile, the sulfuric acid only plays a role in transferring charges due to the water electrolyzed in the whole process, so that the electrolyte can be replaced by any one of soluble ionic compounds such as sodium chloride, sodium hydroxide, zinc sulfate, potassium hydroxide, potassium chloride and the like. Note that when the electrolyte is sodium chloride or potassium chloride, the cathode evolves hydrogen and the anode generates chlorine.
Furthermore, the high-strength high-toughness carbon nano tube composite phase change fiber prepared by the method does not relate to toxic dangerous goods, and electrolytes such as sulfuric acid and the like can be recycled, so that the method accords with the concept of green environmental protection.
In some exemplary embodiments, the preparation method specifically includes: applying a voltage between two selected stations on the carbon nanotube fibers or applying a current to the carbon nanotube fibers so as to generate gas, and then uniformly expanding the carbon nanotube fibers to 400-2000 times of the original carbon nanotube fibers in the radial and/or length directions, wherein the two selected stations are distributed at different positions on the carbon nanotube fibers in the length directions; preferably, the current is 30-90 mA.
In some exemplary embodiments, the phase change material solution includes a phase change material including any one or a combination of two or more of stearic acid, palmitic acid, myristic acid, lauric acid, n-octadecane, paraffin wax, polyethylene glycol, and the like, and a solvent including any one or a combination of two or more of water, diethyl ether, xylene, acetone, and the like.
Further, the concentration of the phase change material in the phase change material solution is 10-30wt%.
In some exemplary embodiments, the preparation method specifically includes: densification of the carbon nanotube fibers infiltrated with the phase change material is performed at least by twisting.
In some exemplary embodiments, the preparation method specifically includes:
the invention takes the mixed solution of sulfuric acid and polyethylene glycol polymer as an electrolyte solvent as an example, can lead the carbon nano tube fiber to realize the expansion of ultra-high volume ratio, lead the polyethylene glycol to fully enter the inside of the carbon nano tube fiber, lead the polyethylene glycol with polyhydroxy structure to further strengthen the densified carbon nano tube fiber, and lead the strength of the composite fiber after twisting to exceed 2GPa.
In summary, the invention utilizes the electrolytic water to release hydrogen to lead the carbon nano tube fiber to expand from inside to outside without damage, the carbon nano tube fiber can realize instant expansion after being electrified, the expansion is uniform and the efficiency is high, the simplicity and the efficiency are higher, the safety are higher, the continuous production can be expanded, and the industrialization is realized.
The preparation method of the high-strength high-toughness carbon nano tube composite phase-change fiber is simple and efficient, can expand continuous production and realizes industrialization.
Another aspect of an embodiment of the present invention provides a high strength, high toughness carbon nanotube composite phase change fiber prepared by the foregoing method.
In summary, the invention adopts the electrolytic water to produce the gas for expanding the carbon nano tube fiber, and utilizes the interface foaming to prepare the carbon nano tube-phase change material composite phase change fiber which has good uniformity, the phase change material can further strengthen the densified carbon nano tube fiber, and the twisted composite fiber has higher tensile strength and various paraffin materials with low density, wide adjustable range of phase change temperature, high phase change enthalpy or latent heat and solubility in organic solvents.
The high-strength high-toughness carbon nanotube-phase-change material composite phase-change fiber prepared by the method has good structural uniformity, still keeps a solid form in the phase-change process, and is well bound in a carbon nanotube network structure by an in-situ impregnation method, so that the phase-change material is effectively prevented from leaking out in the phase-change process.
Further, another aspect of the embodiment of the invention also provides an application of the high-strength high-toughness carbon nano tube composite phase change fiber in preparing a wearable environment energy collection device.
Furthermore, the super-strong CNT/phase-change material composite phase-change fiber is expected to have a very wide application prospect in a wearable environment energy collection device in the future.
The technical solution of the present invention will be described in further detail below with reference to a number of preferred embodiments and accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
Example 1
The specific technical steps of this embodiment are as follows:
1) Carbon nanotube fiber: carbon nanotube fibers prepared by chemical deposition (CVD) using a floating catalyst. (purchased from Suzhou Jiedi nanotechnology Co., ltd.)
2) Carbon nano tube/phase change material composite phase change fiber (mixed solution of sulfuric acid and polyethylene glycol polymer is used as electrolyte solvent)
Preparing a solution of 0.2mol/L sulfuric acid as an electrolyte: 450ml of deionized water was prepared in a 500ml beaker, 10g of 98% concentrated sulfuric acid was accurately weighed, and in a cold water bath, the concentrated sulfuric acid was slowly added to the deionized water while stirring the glass rod. Finally adding deionized water to 500ml, and stirring to uniformity.
3) Electrolytic water swelling fiber process: 700mL of electrolyte is added into an electrolytic tank, the anode is an inert electrode, and the cathode is carbon nanotube fiber. Respectively adopting a voltage method and a current method (the current is 30-90 mA, the voltage is changed along with the current), and carrying out hydrogen evolution by electrolyzed water to enable the carbon nanotube fiber to realize the expansion of the ultra-high volume ratio, thus obtaining the carbon nanotube fiber with an expansion network structure;
4) The dipping process comprises the following steps: the carbon nano tube fiber with the expansion network structure is immersed in polyethylene glycol (PEG) aqueous solution with the concentration of 10-30wt%, so that the PEG fully permeates into the expansion network structure of the carbon nano tube fiber, the polyethylene glycol with the polyhydroxy structure can further strengthen and densify the carbon nano tube fiber, and then densification treatment is carried out, so that a series of CNT-PEG composite phase-change fibers with different PEG loading amounts (35 wt% and 67 wt%) are prepared.
5) Electrothermal conversion and energy storage: and respectively twisting and combining 5-10 CNT fibers and 5-10 CNT-PEG (67%) composite phase-change fibers to obtain the CNT yarn and the CNT-PEG composite yarn. The conversion and storage of electrical energy to thermal energy under a current of 0.275A was compared for 67% CNT/PEG phase-change composite fiber and fibril CNT fiber, respectively.
In the embodiment, the carbon nano tube fiber with the expanded network structure obtained after expansion is immersed in the PEG solution with the phase change in the low temperature region, and the PEG can be loaded in the composite CNT fiber by more than 64.3 percent by adjusting the concentration of the PEG, so that the CNT/PEG composite phase change fiber has higher temperature resistance property compared with the PEG. The composite phase-change fiber has obvious phase change at 50-65 ℃ and the latent heat of the phase change can reach 105.9J/g. In addition, the PEG with polyhydroxy structure can further strengthen the densified CNT fiber, and the strength of the twisted composite fiber can exceed 2GPa. The super-strong CNT/PEG phase-change fiber is expected to have a very wide application prospect in a wearable environment energy collection device in the future.
Further, the solvent water in the polyethylene glycol (PEG) aqueous solution in this embodiment may be replaced with diethyl ether, xylene, acetone, or the like, but is not limited thereto.
Furthermore, the CNT-PEG composite phase-change fiber still maintains a solid form in the phase-change process, and polyethylene glycol is well bound in a carbon nano-tube network structure by an in-situ impregnation method, so that polyethylene glycol leakage in the phase-change process is effectively prevented. In addition, the solid-liquid state transformation in the traditional polyethylene glycol phase transformation process is changed after the carbon nano tube and the polyethylene glycol are compounded, namely the CNT-PEG composite phase transformation fiber can still keep the solid state even in a molten state.
In the invention, the CNT network is expanded mainly by utilizing hydrogen generated by electrolysis of water, and the expansion mechanism is as shown in figure 1:
FIG. 1 is H 2 Evolution of bubbles and force balance model of bubbles under carbon nanotube restraint. First, the present inventors consider H 2 This is related to the conduction of current through CNT assembly. Because of the skin effect, the current inside the carbon nanotube assembly is conducted primarily along the surface of the large-sized carbon nanotube bundles, while conducting along the small-sized bundles or individual carbon nanotubes creates a much greater electrical resistance. Thus H 2 The evolution is mainly at the surface of the large-size beam, especially at the junction between them, as geometric irregularities are an efficient way of gas molecule aggregation. Thus H 2 The bubbles may grow gradually between the large-sized CNT bundles.
Second, it is necessary to analyze the forces acting on the bubbles, revealing the mechanism of bubble expansion. When the external pressure P of the circular bubble 0 (ambient pressure around the bubble) and internal pressure P i When equilibrium (i.e., the surface tension of the bubbles) is reached, the bubbles can exist stably. Namely P i -P 0 =2t/r, where r is the radius of the bubble. When bubbles form initially in the carbon nanotube assembly, they are generally not spherical, but rather more elliptical. With the growth of bubbles, the equilibrium is destroyed, i.e. P i -P 0 >At 2T/r, the bubble is restricted by the CNT network, and the bubble becomes longer and narrower from a circular shape. At the long bubble end, the constraint is the weakest, the curvature radius is the smallest, and r min ≈2T/(P i -P 0 ) The method comprises the steps of carrying out a first treatment on the surface of the Whereas in the middle part the radius of curvature is maximized by the constraint, r max ≈2T/(P i –P 0 –P c ) Wherein P is c Pressure is constrained for the CNT network.
The characterization result of the high-strength high-toughness carbon nano tube composite phase change fiber obtained by the embodiment is as follows:
FIGS. 2A-2D are topographical representations of CNT-PEG composite phase change fibers, from which it can be seen that a large amount of polyethylene glycol is enriched in the carbon nanotube network structure. Polyethylene glycol is well bound in the carbon nano tube network structure by an in-situ impregnation method, and has good uniformity, so that the leakage of polyethylene glycol caused by the CNT-PEG composite phase-change fiber in the phase-change process is effectively prevented.
FIG. 3 is a thermogravimetric plot of pure CNT fibers and CNT-PEG composite phase change fibers of varying PEG loading. The CNT-PEG composite phase-change fiber is prepared by an in-situ impregnation method by respectively adopting two kinds of phase-change material solutions with PEG content of 10% (v/w) and 30%, and the two kinds of CNT-PEG composite phase-change fiber with PEG content of 32wt% and 64wt% are respectively obtained, and the thermogravimetric curve is shown in figure 3.
FIG. 4 is a stress-strain curve for pure CNT fibers and CNT-PEG composite phase change fibers of varying PEG loading. The tensile stress of the CNT/PEG composite phase-change fiber with the PEG content of 35 weight percent is 2.19GPa, and the tensile stress of the CNT/PEG composite phase-change fiber with the PEG content of 67 weight percent is 1.61GPa. The CNT/PEG composite phase change fibers are improved to a different degree than the mechanical properties of pure CNT fibers (1.46 GPa) because the polyhydroxy structured PEG can further enhance densification of the CNT fibers.
FIG. 5 is a DSC curve of a CNT-PEG composite phase change fiber with pure PEG and varying PEG loadings. The composite phase change fiber performs energy storage at 56-64 ℃ and energy release at 35-43 ℃, which is consistent with the phase change temperature region of pure PEG. The phase change latent heat of the CNT/PEG composite phase change fiber with the content of 35 weight percent is only 33.7J/g, and the phase change latent heat of the CNT/PEG composite phase change fiber with the content of 67 weight percent can reach 136.2J/g, and the phase change enthalpy can reach 59 percent of pure PEG. Under the condition of maintaining a certain mechanical strength, the CNT-PEG composite phase-change fiber with the content of 67 weight percent has good phase-change latent heat. The problems of weak thermal response and poor flammability of PEG and organic polymer composite, and poor toughness and brittleness of inorganic compound are solved.
FIG. 6 is a graph of electrical to thermal energy conversion and storage curves for pure CNT fibers and CNT-PEG (67 wt%) composite phase change fibers. The conversion and storage of electrical energy to thermal energy under the effect of a current of 0.275A was compared for 67wt% CNT/PEG composite phase-change fiber and fibril CNT fiber, respectively. Although 67wt% PEG is compounded in the CNT fibers, the CNT fibers still have a faster electrothermal response rate, and the temperature reaches 65 ℃ after being electrified for 50 seconds. And the power supply is turned off, and compared with the fibrils, the composite phase change fiber has an exothermic platform at 40 ℃ and continuously releases heat for 60 seconds. This is due to the solid-liquid phase transition of PEG from crystalline to amorphous. The CNT-PEG composite phase change fiber realizes faster electrothermal response under low voltage, and the method further develops the phase change material with low power consumption.
FIGS. 7A and 7B are illustrations of the flexibility characteristics of a CNT-PEG composite phase change fiber in an exemplary embodiment. The composite CNT-PEG composite phase-change fiber has good flexibility, and can convert and store electric energy to heat energy under any shape.
FIGS. 8A and 8B are IR thermal imaging diagrams of a CNT-PEG composite phase change fiber during power up and power down in an exemplary embodiment. As can be seen from the figure, the CNT-PEG composite phase change fiber can achieve rapid temperature rise after being electrified. After power failure, the composite fiber can realize a heat preservation process of 1 min.
Example 2
The specific technical steps of this embodiment are as follows:
1) Carbon nanotube fiber: carbon nanotube fibers prepared by chemical deposition (CVD) using a floating catalyst. (purchased from Suzhou Jiedi nanotechnology Co., ltd.)
2) And (3) preparing an electrolyte: zinc sulfate of 0.1mol/L was used as the electrolyte.
3) Configuration of phase-change solution: 10% paraffin solution and 30% paraffin solution were prepared using xylene and diethyl ether as solvents, respectively.
3) Electrolytic water swelling fiber process: 700mL of electrolyte is added into an electrolytic tank, the anode is an inert electrode, and the cathode is carbon nanotube fiber. Adjusting the current to 50mA, and carrying out hydrogen evolution by using electrolyzed water to enable the carbon nano tube fiber to realize the expansion of the ultra-high volume ratio, so as to obtain the carbon nano tube fiber with the expansion network structure;
4) The dipping process comprises the following steps: immersing the carbon nano tube fiber with the expansion network structure in paraffin solution to enable paraffin in the carbon nano tube fiber to fully penetrate into the expansion network structure of the carbon nano tube fiber, and then performing densification treatment to obtain a series of CNT composite phase-change fibers with different paraffin loadings.
The performance parameters of the paraffin-loaded CNT composite phase-change fiber obtained in this example were tested to be substantially the same as in example 1.
Example 3
The specific technical steps of this embodiment are as follows:
1) Carbon nanotube fiber: carbon nanotube fibers prepared by chemical deposition (CVD) using a floating catalyst. (purchased from Suzhou Jiedi nanotechnology Co., ltd.)
2) And (3) preparing an electrolyte: sulfuric acid of 0.1mol/L was used as the electrolyte.
3) Configuration of phase-change solution: toluene and benzene were used as solvents to prepare 15% and 20% stearic acid solutions, respectively.
3) Electrolytic water swelling fiber process: 700mL of electrolyte is added into an electrolytic tank, the anode is an inert electrode, and the cathode is carbon nanotube fiber. Adjusting the current to 50mA, and carrying out hydrogen evolution by using electrolyzed water to enable the carbon nano tube fiber to realize the expansion of the ultra-high volume ratio, so as to obtain the carbon nano tube fiber with the expansion network structure;
4) The dipping process comprises the following steps: and immersing the carbon nano tube fiber with the expansion network structure in a stearic acid solution, enabling paraffin in the carbon nano tube fiber to fully penetrate into the expansion network structure of the carbon nano tube fiber, and then performing densification treatment to obtain a series of CNT composite phase-change fibers with different stearic acid loadings.
The stearic acid-loaded CNT composite phase-change fibers obtained in this example were tested for performance parameters substantially consistent with example 1.
In addition, the inventors have also conducted experiments with reference to the foregoing examples, using other raw materials, process operations, process conditions, etc. as described in the present specification, for example, using palmitic acid, myristic acid, lauric acid, n-octadecane, etc. instead of polyethylene glycol, stearic acid and paraffin as in the foregoing examples 1-3, and using sodium chloride, sodium hydroxide, potassium chloride, etc. instead of sulfuric acid, zinc sulfate, etc. as in the foregoing examples 1-2, respectively, and have obtained preferable results.
In summary, the above embodiment adopts electrolyzed water to release hydrogen, and utilizes the interfacial foaming of the carbon nanotube fiber to prepare the CNT-PEG composite phase-change fiber, the method is novel, unique, green and efficient, the obtained CNT-PEG composite phase-change fiber has good structural uniformity, the PEG with polyhydroxy structure is well bound in the carbon nanotube network structure, and simultaneously the polyhydroxy structure of polyethylene glycol is beneficial to further enhancing the densified CNT fiber of the carbon nanotube fiber, and the twisted composite fiber has higher tensile strength.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (2)

1. The application of the high-strength high-toughness carbon nano tube composite phase change fiber in preparing the wearable environment energy collection device comprises the following steps:
the method comprises the steps of taking carbon nanotube fibers as a cathode, constructing an electrochemical reaction system together with an anode and electrolyte, wherein the electrolyte is an aqueous phase system containing electrolyte, and the electrolyte is selected from any one or more than two of sulfuric acid, sodium chloride, sodium hydroxide, zinc sulfate, potassium hydroxide and potassium chloride;
applying voltage between two selected stations on the carbon nano tube fiber, or applying current to the carbon nano tube fiber so as to generate gas, and then enabling the carbon nano tube fiber to uniformly expand to 400-2000 times of the original carbon nano tube fiber in the radial direction and/or the length direction, wherein the two selected stations are distributed at different positions on the carbon nano tube fiber in the length direction; the current is 30-90 mA, and the gas generated by electrolysis is selected from hydrogen;
immersing the obtained carbon nano tube fiber with the expansion network structure in a phase change material solution to enable the phase change material in the carbon nano tube fiber to fully permeate into the expansion network structure of the carbon nano tube fiber, and then performing densification treatment to obtain the high-strength high-toughness carbon nano tube composite phase change fiber; the phase change material solution comprises a phase change material and a solvent, wherein the phase change material is selected from any one or more than two of stearic acid, palmitic acid, myristic acid, lauric acid, n-octadecane, paraffin and polyethylene glycol, the solvent is selected from any one or more than two of water, diethyl ether, dimethylbenzene and acetone, and the concentration of the phase change material in the phase change material solution is 10-30wt%;
the high-strength high-toughness carbon nano tube composite phase change fiber comprises carbon nano tube fibers and phase change materials, wherein the phase change materials are uniformly distributed in the carbon nano tube fibers and/or in a network structure formed by the carbon nano tube fibers, the content of the phase change materials in the high-strength high-toughness carbon nano tube composite phase change fiber is 35-70wt%, the phase change temperature of the high-strength high-toughness carbon nano tube composite phase change fiber is 50-65 ℃, the phase change latent heat is above 105.9J/g, the tensile strength is above 2GPa, the conversion and storage of electric energy to heat energy can be carried out under any shape, and the density is 0.5-1.5 g/cm 3 。
2. Use according to claim 1, characterized in that it comprises: densification treatment is carried out on the carbon nano tube fiber permeated with the phase change material in a twisting mode.
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