CN115287774A - High-conductivity organic composite thermoelectric fiber, preparation method and application - Google Patents
High-conductivity organic composite thermoelectric fiber, preparation method and application Download PDFInfo
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- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
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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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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Abstract
The invention relates to a high-conductivity organic composite thermoelectric fiber, a preparation method and application thereof, wherein the preparation method comprises the following specific steps: s1: dispersing carbon nanotubes in water, performing ultrasonic treatment for 5-10min, adding PEDOT (Polytetrafluoroethylene-styrene) PSS (polyethylene terephthalate), and uniformly mixing to obtain a spinning solution; s2: and adding a proper amount of the spinning solution into a coagulating bath to form PEDOT (PSS)/carbon nanotube composite fiber, namely the high-conductivity organic composite thermoelectric fiber. The invention has the beneficial effects that the process is simple, the interaction among the components of the composite material is enhanced in the wet spinning process, the conductivity of the composite fiber is improved, and the thermoelectric property of the composite fiber is optimized.
Description
Technical Field
The invention relates to the technical field of organic thermoelectric materials, in particular to a high-conductivity organic composite thermoelectric fiber, a preparation method and application thereof.
Background
Thermal energy is the most common form of energy present in our living environment, mainly including heat from industrial waste, automobile engines, and electronic devices and even human bodies. In the past few years, thermoelectric materials that directly generate electricity from ambient thermal energy have received much attention. Through the TE technology, the energy conversion device has the unique advantages of long life, lossless release, no need for mechanical moving parts to operate, and the like. In this regard, high performance TE materials may be promising candidates for achieving sustainable power supply in a green manner.
The energy conversion efficiency of thermoelectric materials is generally evaluated by using a thermoelectric figure of merit ZT = S 2 σ T/κ, where S is Seebeck coefficient, σ is electrical conductivity, T is absolute temperature, κ is thermal conductivity, S 2 σ is defined as a power factor, and the thermal conductivity of the organic thermoelectric material is low and has small variation, so the power factor is widely used for measuring the thermoelectric performance of the organic material. The higher the ZT value is, the higher the thermoelectric conversion efficiency of the material is, and the conversion of heat energy to electric energy is more favorably realized.
The organic thermoelectric material has the advantages of low cost, solution processing, flexibility, light weight, low thermal conductivity and the like, and has great research value in the fields of industrial production and scientific research. The organic composite thermoelectric fiber reported in the related literature at present is mainly prepared by adhering a conductive polymer on the surface of a fiber material, and adopting a gelling and wet spinning mode, wherein the wet spinning mode is widely concerned because of continuous preparation, but the organic composite thermoelectric fiber is mainly used for pure conductive polymer spinning fiber at present, and the improvement of the thermoelectric performance of the organic thermoelectric fiber is limited. In the research of organic thin film thermoelectric materials, the organic composite thermoelectric materials can obtain better thermoelectric performance than simple conducting polymers, but the preparation research of the organic composite thermoelectric fibers is less at present, the thermoelectric performance is still at a lower level, and the development of the high-conductivity organic composite thermoelectric fibers has important significance.
According to the invention, the organic composite thermoelectric fiber is spun by a wet method, and the interaction among the components of the composite material is enhanced in the wet spinning process, so that the conductivity of the composite fiber is improved, and the thermoelectric performance of the composite fiber is further optimized.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-conductivity organic composite thermoelectric fiber, a preparation method and application, and aims to solve the problems in the prior art.
The technical scheme for solving the technical problems is as follows:
a preparation method of a high-conductivity organic composite thermoelectric fiber comprises the following specific steps:
s1: dispersing carbon nanotubes in water, performing ultrasonic treatment for 5-10min, adding PEDOT (Polytetrafluoroethylene-styrene) PSS (polyethylene terephthalate), and uniformly mixing to obtain a spinning solution;
s2: and adding a proper amount of the spinning solution into a coagulating bath to form PEDOT (PSS)/carbon nanotube composite fiber, namely the high-conductivity organic composite thermoelectric fiber.
The invention has the beneficial effects that: the invention has simple process, and enhances the interaction among the components of the composite material in the wet spinning process, thereby improving the conductivity of the composite fiber and further optimizing the thermoelectric property of the composite fiber.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the step S2 includes the following specific steps:
and S21: sucking 1-3mL of the spinning solution by using an injector, and adding the spinning solution into a coagulating bath to form fibers;
and S22: soaking the formed fiber in a coagulating bath for 1min-72h;
and S23: and collecting the fibers in the S22, washing the fibers with deionized water for multiple times, and drying to obtain the PEDOT-PSS/carbon nanotube composite fibers.
The further scheme has the beneficial effects that on one hand, the carbon nano tubes are added into the spinning solution through the injector, so that the carbon nano tubes form a certain ordered arrangement in the extrusion process, and the charge transmission of the composite material is optimized; on the other hand, the spinning solution is extruded, formed in a coagulating bath and then continuously soaked for a certain time, so that the interaction between PEDOT and PSS is weakened, the non-conductive PSS component is removed, and meanwhile, due to the hydrophobicity of the PEDOT and the carbon nano tube, the pi-pi interaction between the PEDOT and the carbon nano tube can be enhanced, and the conductivity of the PSS is improved.
Further, the speed of extruding the spinning solution by the injector in S21 is 0.01-0.2mL/min.
The further scheme has the advantages that the extrusion speed of the spinning solution is reasonable, the one-dimensional carbon nano tubes form certain ordered arrangement in the extrusion process, and the charge transmission of the composite material is optimized.
Furthermore, in the obtained PEDOT/PSS/CNT composite fiber, the content of the PEDOT/PSS is 90wt% -50wt%, and the content of the carbon nano tube is 10wt% -50wt%.
The beneficial effects of the further scheme are that the design is reasonable, and the conductivity of the PEDOT/PSS/carbon nano tube composite fiber prepared under the concentration is good.
Further, the carbon nanotube in S1 is any one or a mixture of a single-arm carbon nanotube, a double-arm carbon nanotube, or a multi-wall carbon nanotube.
The further scheme has the advantages of reasonable material selection, contribution to the rapid preparation of the PEDOT/PSS/CNT composite fiber and capability of ensuring the performance of the PEDOT/PSS/CNT composite fiber.
And further, the PEDOT/PSS material in the S1 is PEDOT which can be dispersed in water: (ii) a PSS dispersion.
The method has the advantages that the method is reasonable in material selection, can be quickly dissolved in water to prepare the PEDOT/PSS/CNT composite fiber, and greatly improves preparation efficiency.
Further, the coagulation bath in S2 is an acid solution.
The method has the advantages that the acid solution is used as the coagulating bath, so that the interaction between the PEDOT and the PSS is weakened, the non-conductive PSS component is removed, and meanwhile due to the hydrophobicity of the PEDOT and the carbon nano tube, the pi-pi interaction between the PEDOT and the carbon nano tube can be enhanced, so that the conductivity of the PSS is improved.
Further, the acid solution is one or a mixture of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and trifluoromethanesulfonic acid, and the acid concentration is 1-18.4 mol/L.
The further scheme has the advantages that the material selection is reasonable, the preparation of the PEDOT/PSS/CNT composite fiber is facilitated, and the conductivity of the prepared PEDOT/PSS/CNT composite fiber can be ensured.
The invention also relates to the organic composite thermoelectric fiber prepared by the preparation method of the high-conductivity organic composite thermoelectric fiber.
The organic composite thermoelectric fiber with high conductivity is provided by adopting the further scheme.
The invention also relates to an application of the organic composite thermoelectric fiber, which is applied to the field of wearable electronics.
The beneficial effect of adopting above-mentioned further scheme is that this scheme is applied to wearable electron field with organic compound thermoelectric fiber, and it is convenient to use.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a scanning electron microscope photograph of a PSS/CNT composite fiber of PEDOT at a CNT content of 50wt% in accordance with the present invention;
FIG. 3 is a scanned high magnification image of a PEDOT PSS/CNT composite fiber of the present invention having a CNT content of 50 wt%;
FIG. 4 is a graph showing the UV-visible absorption of the sulfuric acid coagulation bath before and after wet spinning of a composite fiber of PEDOT, PSS and CNT according to the present invention;
FIG. 5 is a Raman spectrum of a composite fiber of PEDOT, PSS and CNT in accordance with the present invention;
FIG. 6 is a Raman spectrum of pure PEDOT and pure CNT material of the present invention;
FIG. 7 is a graph of the thermoelectric performance of a composite fiber of PEDOT PSS and CNT in accordance with the present invention at various CNT contents;
fig. 8 is a graph of pure PEDOT in accordance with the present invention: thermoelectric performance plots of PSS fibers at different CNT contents.
Detailed Description
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate a number of the indicated technical features. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Example 1
As shown in fig. 1 to 8, the present embodiment provides a method for preparing a highly conductive organic composite thermoelectric fiber, including the following specific steps:
s1: dispersing a proper amount of Carbon Nano Tubes (CNT) in water, performing ultrasonic treatment for 5-10min, adding a proper amount of PEDOT (Polytetrafluoroethylene-ethylene terephthalate) PSS (Polytetrafluoroethylene-styrene), and uniformly mixing to obtain a spinning solution;
s2: and adding a proper amount of the spinning solution into a coagulating bath to form PEDOT (PSS)/carbon nanotube composite fiber, namely the high-conductivity organic composite thermoelectric fiber.
Preferably, in this embodiment, in S1, the carbon nanotubes are dispersed in deionized water.
The method has simple process, and enhances the interaction among the components of the composite material in the wet spinning process, thereby improving the conductivity of the composite fiber and further optimizing the thermoelectric property of the composite fiber.
Example 2
On the basis of embodiment 1, in this embodiment, the step S2 includes the following specific steps:
and S21: sucking 1-3mL of the spinning solution by using an injector and adding the spinning solution into a coagulating bath to form fibers;
and S22: soaking the formed fiber in a coagulating bath for 1min-72h;
and S23: and collecting the fibers in the S22, washing the fibers with deionized water for multiple times, and drying the fibers to obtain the PEDOT (PSS)/carbon nanotube composite fibers.
In the embodiment, on one hand, the carbon nanotubes are added into the spinning solution by an injector, so that the carbon nanotubes form a certain ordered arrangement in the extrusion process, and the charge transmission of the composite material is optimized; on the other hand, the spinning solution is extruded, formed in a coagulating bath and then continuously soaked for a certain time, so that the interaction between PEDOT and PSS is weakened, the non-conductive PSS component is removed, and meanwhile, due to the hydrophobicity of the PEDOT and the carbon nano tube, the pi-pi interaction between the PEDOT and the carbon nano tube can be enhanced, and the conductivity of the PSS is improved.
Preferably, in this embodiment, the spinning needle of the syringe has a gauge of 18G to 30G.
Example 3
Based on example 2, in this example, the rate of extruding the dope by the injector in S21 is 0.01-0.2mL/min.
In the scheme, the extrusion rate of the spinning solution is reasonably designed, so that the one-dimensional carbon nanotubes form a certain ordered arrangement in the extrusion process, and the charge transmission of the composite material is optimized.
Example 4
On the basis of the above embodiments, in the obtained PEDOT/PSS/carbon nanotube composite fiber, the content of the PEDOT/PSS is 90wt% to 50wt%, and the content of the carbon nanotube is 10wt% to 50wt%.
The scheme is reasonable in design, and the conductivity of the PEDOT/PSS/CNT composite fiber prepared under the concentration is good.
Example 5
In addition to the above embodiments, in this embodiment, the carbon nanotubes in S1 are any one or a mixture of more of single-arm carbon nanotubes, double-arm carbon nanotubes, or multi-wall carbon nanotubes.
The scheme has reasonable material selection, is beneficial to the rapid preparation of the PEDOT/PSS/CNT composite fiber, and can ensure the performance of the PEDOT/PSS/CNT composite fiber.
Example 6
On the basis of the above embodiments, in this embodiment, the PEDOT: PSS material in S1 is PEDOT: (ii) a PSS dispersion.
The scheme has reasonable material selection, can be quickly dissolved in water to prepare the PEDOT/PSS/CNT composite fiber, and greatly improves the preparation efficiency.
Preferably, in this embodiment, the weight ratio of PEDOT: the PSS dispersion may be used as Clevios PH1000.
Example 7
In addition to the above embodiments, in the present embodiment, the coagulation bath in S2 is an acid solution.
According to the scheme, an acid solution is used as a coagulating bath, the interaction between PEDOT and PSS is weakened, the non-conductive PSS component is removed, and meanwhile due to the hydrophobicity of PEDOT and carbon nanotubes, the pi-pi interaction between PEDOT and carbon nanotubes can be enhanced, so that the conductivity of the PSS is improved.
Example 8
In this embodiment, the acid solution is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and trifluoromethanesulfonic acid, and the acid concentration is 1 to 18.4mol/L.
The scheme has reasonable material selection, is beneficial to preparing the PEDOT/PSS/CNT composite fiber, and can ensure the conductivity of the prepared PEDOT/PSS/CNT composite fiber.
Example 9
On the basis of the above embodiments, the present embodiment also provides an organic composite thermoelectric fiber prepared by the above method for preparing a highly conductive organic composite thermoelectric fiber.
The scheme provides the organic composite thermoelectric fiber with higher conductivity.
Example 10
On the basis of the above embodiments, the present embodiment further provides an application of the organic composite thermoelectric fiber, which is applied to the field of wearable electronics.
The scheme applies the organic composite thermoelectric fiber to the field of wearable electronics, and is convenient to apply.
The high conductivity is of great significance for the improvement of thermoelectric performance, according to the former PF = S 2 Sigma, the electrical conductivity is improved, the thermoelectric power factor can be improved, and the material with the high thermoelectric power factor can be used for generating electricity by utilizing the temperature difference, such as the temperature difference between a human body and the environment, so that the thermoelectricity is converted into the electric energy, and the energy supply to the micro electronic device is realized.
The specific embodiment of the invention is as follows:
example 11
Ultrasonically treating 4mg of Carbon Nano Tube (CNT) in 1mL of deionized water for 5min to form a suspension, adding 2769 mu L of PEDOT: PSS (1.3 wt%) aqueous solution into the suspension, and stirring to uniformly mix the solution to obtain a spinning solution;
then, 1mL of the above spinning dope was sucked up by a syringe, a 23G stainless steel plain needle was inserted obliquely downward into a sulfuric acid (9.2 mol/L) coagulation bath, extruded at a rate of 0.2mL/min using a syringe pump, and the fiber was immersed in the coagulation bath for 3 hours after being molded, and then collected, washed 3 times with deionized water, and dried to obtain a PEDOT: PSS/CNT composite fiber having a CNT content of 10wt%, which was used directly for the measurement of conductivity.
The conductivity sigma of the conductive paste is 836S cm -1 The Seebeck coefficient S is 22.46 mu V K -1 The power factor PF is 42.48 μ W m -1 K -2 。
Example 12
Taking 4mg of Carbon Nano Tube (CNT) and carrying out ultrasonic treatment in 1mL of deionized water for 10min to form a suspension, adding 1231 mu L of PEDOT: PSS (1.3 wt%) aqueous solution into the suspension, and vibrating and stirring the mixture to uniformly mix the solution to obtain spinning solution;
then, 1mL of the spinning solution was sucked up by a syringe, a 23G stainless steel plain needle was inserted obliquely downward into a sulfuric acid (1 mol/L) coagulation bath, and extruded at a rate of 0.01mL/min using a syringe pump, and the fiber was immersed in the coagulation bath for 3 hours after being molded, and then collected, washed 3 times with deionized water, and dried to obtain a PEDOT: PSS/CNT composite fiber having a CNT content of 20wt%, which was used directly for the measurement of conductivity.
The electrical conductivity sigma is 1040S cm -1 The Seebeck coefficient S is 23.59 mu V K -1 The power factor PF is 47.78 μ W m -1 K -2 。
Example 13
Taking 6mg CNT to be subjected to ultrasonic treatment in 1.5mL deionized water for 10min, adding 1077 mu L PEDOT: PSS (1.3 wt%) aqueous solution into the suspension, and vibrating and stirring the mixture to uniformly mix the solution to obtain spinning solution;
then, 1mL of the spinning solution was sucked up by a syringe, a 23G stainless steel plain needle was inserted obliquely downward into a sulfuric acid (18.4 mol/L) coagulation bath, and extruded at a rate of 0.01mL/min using a syringe pump, and the fiber was immersed in the coagulation bath for 3 hours after being formed, and then collected, washed 3 times with deionized water, and dried to obtain a PEDOT: PSS/CNT composite fiber having a CNT content of 30wt%, which was used directly for the measurement of conductivity.
The conductivity of the conductive coating is 1348S cm -1 The Seebeck coefficient S is 24.42 mu V K -1 The power factor PF is 74.13 μ W m -1 K -2 。
Example 14:
taking 8mg of CNT to be subjected to ultrasonic treatment in 2mL of deionized water for 10min, adding 923 mu L of PEDOT: PSS (1.3 wt%) aqueous solution into the suspension, and stirring to uniformly mix the solution to obtain spinning solution;
then, 1mL of the above spinning dope was sucked up by a syringe, a 23G stainless steel plain needle was inserted obliquely downward into a sulfuric acid (18.4 mol/L) coagulation bath, extruded at a rate of 0.01mL/min using a syringe pump, and the fiber was immersed in the coagulation bath for 3 hours after being molded, and then collected, washed 3 times with deionized water, and dried to obtain a PEDOT: PSS/CNT composite fiber having a CNT content of 40wt%, which was used directly for the measurement of conductivity.
The conductivity of the material is 2175S cm < -1 >, the Seebeck coefficient S is 27.1 mu V K < -1 >, and the power factor PF is 158.56 mu W m < -1 > K < -2 >.
Example 15:
taking 8mg of CNT to be subjected to ultrasonic treatment in 2mL of deionized water for 10min, adding 615 mu L of PEDOT: PSS (1.3 wt%) aqueous solution into the suspension, and stirring to uniformly mix the solution to obtain spinning solution;
then, 1mL of the above spinning dope was sucked up by a syringe, a 23G stainless steel plain needle was inserted obliquely downward into a sulfuric acid (18.4 mol/L) coagulation bath, extruded at a rate of 0.01mL/min using a syringe pump, and the fiber was immersed in the coagulation bath for 3 hours after being molded, and then collected, washed 3 times with deionized water, and dried to obtain a PEDOT: PSS/CNT composite fiber having a CNT content of 50wt%, which was used directly for the measurement of conductivity.
The conductivity of the material is 2759S cm < -1 >, the Seebeck coefficient S is 28.7 mu V K < -1 >, and the power factor PF is 228.28 mu W m < -1 > K < -2 >.
Comparative example
Taking a PEDOT (PSS) (1.3 wt%) water solution as a spinning solution;
then, 1mL of the above spinning dope was sucked up by a syringe, a 23G stainless steel plain needle was inserted obliquely downward into a sulfuric acid (9.2 mol/L) coagulation bath, extruded at a rate of 0.2mL/min using a syringe pump, and the fiber was immersed in the coagulation bath for 3 hours after being molded, and then collected, washed 3 times with deionized water, and dried to obtain a PEDOT: PSS/CNT composite fiber having a CNT content of 10wt%, which was used directly for the measurement of conductivity.
The conductivity sigma of the solution is 836S cm -1 The Seebeck coefficient S is 22.46 mu V K -1 The power factor PF is 42.48 μ W m -1 K -2 。
From the results of the above examples, it can be seen that the higher the content ratio of CNT under the same conditions, the better the conductivity of the prepared PEDOT/PSS/CNT composite fiber.
The drawings of the invention are analyzed as follows:
FIG. 2 is a scanning electron microscope image of a PEDOT: PSS/CNT composite fiber with a CNT content of 50wt%, the surface of the fiber is not smooth and flat, due to the fact that due to the introduction of the CNT, the CNT is attached to the surface of the PEDOT: PSS due to pi-pi interaction between the CNT and the PEDOT: PSS.
FIG. 3 is a high magnification scan of a PEDOT PSS/CNT composite fiber at a CNT content of 50wt%, showing that the PEDOT PSS/CNT composite fiber has a significant orientation along the axial direction of the fiber.
In summary, the interconnected network of CNTs themselves, as well as the overall orientation of the fibers, are both favorable for charge transport, and therefore result in high electrical conductivity.
FIG. 4 is a graph of UV-visible absorption of sulfuric acid coagulation bath before and after wet spinning of PEDOT: PSS with CNT composite fibers. Wherein, the curve 1 is before the wet spinning, and the curve 2 is after the wet spinning. As can be seen from the figure, a peak characteristic of PSS appears near 225nm in curve 2, indicating the presence of PSS in the sulfuric acid coagulation bath. The sulfuric acid coagulation bath can remove a large amount of the insulated PSS in a short time, which is also a cause of the enhancement of the electrical conductivity.
FIG. 5 is a Raman spectrum of a PEDOT/PSS/CNT composite fiber, and FIG. 6 is a Raman spectrum of a pure PEDOT/CNT composite fiber and a pure CNT material. As can be seen, 1594cm-1 corresponds to the G peak of CNT, and in the PEDOT: PSS, SWCNT composite fiber, the G peak is red-shifted to 1592cm-1, which is mainly caused by the strong pi-pi interaction between CNT and PEDOT.
FIG. 7 is a graph of thermoelectric performance of PEDOT: PSS and CNT composite fibers at different CNT contents, and FIG. 8 is a graph of pure PEDOT: PSS fibers at different CNT contentsThermoelectric performance diagram. As can be seen, after CNT introduction, the ratio of CNT to PEDOT alone: PSS fiber (conductivity 583S cm -1 The Seebeck coefficient is 22.3 mu V K -1 The power factor is 28.6 μ W m -1 K -2 ) The conductivity of the organic composite fiber is obviously improved, and the conductivity is increased along with the increase of the content of the CNT, which is mainly due to the fact that the increase of the CNT conductive network is beneficial to charge transmission; seebeck is also a step-wise increase, mainly an enhancement of the interfacial interactions between the composites. Eventually leading to an overall thermoelectric power factor PF that increases with CNT content up to pure PEDOT: PSS fiber more than 7 times.
It should be noted that (a) and (b) in the drawings are only used for distinguishing the drawings, and have no other substantial meaning.
The invention provides a method for preparing high-conductivity organic composite thermoelectric fiber by wet spinning, which adopts acid as a coagulating bath to perform wet spinning PEDOT: the PSS and CNT dispersion liquid weakens the interaction between PEDOT and PSS through acid coagulation liquid, so that the non-conductive PSS component is removed, and meanwhile, due to the hydrophobicity of the PEDOT and the carbon nano tube, the pi-pi interaction between the PEDOT and the carbon nano tube can be enhanced, so that the high-conductivity organic composite thermoelectric material is obtained through a one-step spinning method.
In addition, the invention enhances the interaction among the components of the composite material in the wet spinning process, improves the conductivity of the composite fiber and further optimizes the thermoelectric property of the composite fiber. Relative to pure PEDOT: the electrical conductivity of the PSS fiber prepared by the method can be improved by more than 4 times, and the thermoelectric power factor can be improved by more than 7 times.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method has the advantages of simple preparation process conditions, high controllability and high stability, and is suitable for large-scale industrial production and application of the high-conductivity organic composite conductive fiber;
(2) The invention adopts PEDOT, PSS and carbon nano tube composite material, CNT with one-dimensional structure can form a conductive network, and provides a channel for directional transmission of charges. And due to pi-pi interaction between PEDOT and CNT, the molecular chain or chain segment of PEDOT can be orderly increased, and charge transmission is facilitated.
(3) The invention adopts acid solution to replace the traditional coagulating bath (organic solvent), the simple modification can remove the insulated PSS component in the fiber forming process in a short time, and the conductivity can be greatly improved without carrying out complex post-treatment process; meanwhile, the fibers are oriented and arranged along the axial direction of the fibers in the fiber forming process, so that charge transmission is facilitated, and the conductivity is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the high-conductivity organic composite thermoelectric fiber is characterized by comprising the following specific steps of:
s1: dispersing carbon nanotubes in water, performing ultrasonic treatment for 5-10min, adding PEDOT (Polytetrafluoroethylene-styrene) PSS (polyethylene terephthalate), and uniformly mixing to obtain a spinning solution;
s2: and adding a proper amount of the spinning solution into a coagulating bath to form PEDOT (PSS)/carbon nanotube composite fiber, namely the high-conductivity organic composite thermoelectric fiber.
2. The preparation method of the highly conductive organic composite thermoelectric fiber according to claim 1, wherein the step S2 comprises the following specific steps:
and S21: sucking 1-3mL of the spinning solution by using an injector, and adding the spinning solution into a coagulating bath to form fibers;
and S22: soaking the formed fiber in a coagulating bath for 1min-72h;
and S23: and collecting the fibers in the S22, washing the fibers with deionized water for multiple times, and drying the fibers to obtain the PEDOT (PSS)/carbon nanotube composite fibers.
3. The method for preparing the highly conductive organic composite thermoelectric fiber according to claim 2, wherein: the speed of extruding the spinning solution by the injector in the S21 is 0.01-0.2mL/min.
4. The method for preparing a highly conductive organic composite thermoelectric fiber according to any one of claims 1 to 3, characterized in that: in the obtained PEDOT/PSS/carbon nano tube composite fiber, the content of the PEDOT/PSS is 90wt% -50wt%, and the content of the carbon nano tube is 10wt% -50wt%.
5. The method for preparing a highly conductive organic composite thermoelectric fiber according to any one of claims 1 to 3, wherein: the carbon nano tube in the S1 is any one or mixture of a single-arm carbon nano tube, a double-arm carbon nano tube or a multi-wall carbon nano tube.
6. The method for preparing a highly conductive organic composite thermoelectric fiber according to any one of claims 1 to 3, characterized in that: PSS material in S1 is PEDOT dispersible in water: (ii) a PSS dispersion.
7. The method for preparing a highly conductive organic composite thermoelectric fiber according to any one of claims 1 to 3, wherein: and the coagulating bath in the S2 is an acid solution.
8. The method for preparing the highly conductive organic composite thermoelectric fiber according to claim 7, wherein: the acid solution is one or a mixture of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and trifluoromethanesulfonic acid, and the acid concentration is 1-18.4 mol/L.
9. An organic composite thermoelectric fiber produced by the method for producing a highly conductive organic composite thermoelectric fiber according to any one of claims 1 to 8.
10. Use of the organic composite thermoelectric fiber according to claim 9 in the field of wearable electronics.
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