CN115522279A - High-performance ion-electron composite thermoelectric fiber and preparation method thereof - Google Patents
High-performance ion-electron composite thermoelectric fiber and preparation method thereof Download PDFInfo
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- 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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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- 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
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
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Abstract
The invention provides a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, wherein the composite thermoelectric fiber comprises an ionic liquid gel fiber core layer and an electron thermoelectric coating for coating the ionic liquid gel fiber core layer; the ionic liquid gel fiber core layer comprises the following components: 50-90% of ionic liquid, 7-47% of organic polymer and 3-30% of anisotropic inorganic nano filler; the electronic thermoelectric coating comprises an organic electronic thermoelectric material and an ionic liquid. The electronic thermoelectric coating utilizes the temperature gradient to perform thermoelectric conversion to cause temperature fluctuation, and the ionic liquid fiber core layer utilizes the temperature fluctuation to perform thermoelectric conversion so as to improve the thermoelectric voltage and the thermoelectric power. According to the invention, the structure of the ionic liquid gel fiber, the structure of the electronic thermoelectric coating and the interface combination of the ionic liquid gel fiber and the electronic thermoelectric coating are controlled, so that the composite thermoelectric fiber with excellent thermoelectric property and mechanical property is obtained, and the composite thermoelectric fiber is more suitable for preparing high-performance wearable thermoelectric materials.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof.
Background
The thermoelectric material is a green and environment-friendly functional material, realizes the interconversion of heat energy and electric energy by the movement of carriers in the solid, and has wide application prospect in the aspects of thermoelectric generation and refrigeration. The conventional thermoelectric material has poor mechanical properties, and is broken and deformed when being subjected to external pressure, so that the service life and the range of the material are greatly reduced. Compared with the traditional inorganic thermoelectric material, the organic thermoelectric material has improved mechanical property and is mainly used in the field of flexible electronic materials; but the electrical properties of organic thermoelectric materials differ too much from those of inorganic materials. Therefore, how to improve the electrical properties of the organic thermoelectric material is of great significance for the application of the organic thermoelectric material in the thermoelectric field.
The invention patent (application number is CN 201810586502.5) discloses a preparation method of high-performance flexible PEDOT: PSS thermoelectric fiber, the prepared thermoelectric material is p-type semiconductor material, sulfuric acid is added into commercial PEDOT: PSS aqueous solution dispersion liquid, mixed solution is sealed in a capillary, the fiber is blown into absolute ethyl alcohol after constant temperature, and then vacuum drying is carried out to obtain the high-performance flexible PEDOT: PSS thermoelectric fiber material, the preparation method is simple, the cost is low, and the thermoelectric performance of the thermoelectric fiber is good; however, sulfuric acid is added in the preparation process of the material, so that the material cannot be directly applied to the field of wearable energy materials, and the actual application range is limited.
The invention patent (CN 202010176233.2) discloses an organic/inorganic composite thermoelectric fiber and preparation and application thereof, wherein the organic component of the thermoelectric fiber is poly (3, 4-ethylenedioxythiophene) -poly (styrene sulfonate) PEDOT: PSS, the inorganic component is tellurium nanowire Te NWs, and the Te NWs is oriented and distributed in the PEDOT: PSS fiber and prepared by wet spinning; PSS is improved by introducing Te NWs thermoelectric material, so that the composite fiber has good thermoelectric property.
Compared with the common organic thermoelectric material, the two thermoelectric fibers have high electrical conductivity, but the Seebeck coefficient of the thermoelectric fibers is far lower than the working voltage of a small wearable electronic device, so that the requirements of the application field are difficult to meet.
In view of the above, there is a need for an improved high performance ion-electron composite thermoelectric fiber and a method for preparing the same to solve the above problems.
Disclosure of Invention
The invention aims to provide a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof. The electronic thermoelectric coating of the composite thermoelectric fiber can convert heat into electric energy by utilizing the Seebeck effect under the temperature difference; the ionic liquid gel fiber core layer can convert thermal energy into electric energy by utilizing temperature fluctuation caused by thermoelectric conversion of the electronic thermoelectric coating; the composite thermoelectric fiber can realize power generation by utilizing temperature difference and temperature fluctuation at the same time, improves thermoelectric conversion efficiency, and is more suitable for preparing high-performance wearable thermoelectric materials.
In order to achieve the above purpose, the present invention provides a high-performance ion-electron composite thermoelectric fiber, which includes an ionic liquid gel fiber core layer and an electron thermoelectric coating layer coating the ionic liquid gel fiber core layer; the ionic liquid gel fiber core layer has an organic-inorganic hybrid network structure with an oriented structure, and comprises the following components in percentage by mass: 50-90% of ionic liquid, 7-47% of organic polymer and 3-30% of anisotropic inorganic nano filler; the electronic thermoelectric coating includes an organic electronic thermoelectric material.
As a further improvement of the invention, the ionic liquid is an ionic liquid with thermoelectric properties; the inorganic nano filler is in an anisotropic shape structure; the organic polymer is a hydrophilic organic polymer containing a polar functional group.
As a further improvement of the invention, the electronic thermoelectric coating further comprises ionic liquid, and the addition amount of the ionic liquid accounts for 1.0-3.5% of the total mass of the electronic thermoelectric coating material; the ionic liquid of the electronic thermoelectric coating and the ionic liquid in the ionic liquid gel fiber core layer are the same substance.
As a further improvement of the invention, the thickness of the electronic thermoelectric coating is 0.5-20 μm; the electronic thermoelectric coating further comprises a modifier to regulate the performance of the electronic thermoelectric coating and promote the interfacial bonding of the electronic thermoelectric coating and the ionic liquid gel fiber core layer.
As a further improvement of the invention, the preparation of the ionic liquid gel fiber core layer specifically comprises the following steps:
s1, carrying out surface modification on anisotropic inorganic nano-filler by adopting a surfactant to obtain modified inorganic nano-filler;
s2, dissolving an organic polymer in a solvent, adding the modified inorganic nano filler, the ionic liquid and the cross-linking agent in the step S1, blending, fully stirring and dispersing to obtain an ionic liquid gel mixed solution;
s3, adopting a spinning method: pre-gelling the ionic liquid gel mixed solution obtained in the step S2, wherein the pre-gelling time is 0.5-3 h and the temperature is 25-90 ℃; extruding the fiber into a mould by using an extrusion needle, and finally performing gelation treatment to prepare the ionic liquid gel fiber core layer;
or adopting a coating method: soaking the pretreated fiber base material in the ionic liquid gel mixed solution obtained in the step S2 to enable the ionic liquid gel to form a uniform coating on the surface of the fiber base material; repeatedly soaking and drying to obtain the ionic liquid gel fiber core layer; the thickness of the ionic liquid gel coating is 5-100 mu m.
As a further improvement of the invention, in step S3, when a spinning method is adopted, the hole diameter range of the extrusion needle is 0.1-2 mm, and the chamfer angle range of the needle is 10-60 °; when the coating method is adopted, the concentration of the ionic liquid gel mixed solution is 5-20%.
As a further improvement of the invention, the inorganic nanofiller comprises nano SiO 2 、TiO 2 One or more of halloysite nanotubes, attapulgite and graphene oxide; the ionic liquid comprises one or more of 1-ethyl-3-methylimidazole dicyanamide salt, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and N-methyl, N-propyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt; the organic polymer comprises one or more of poly (vinylidene fluoride-co-hexafluoropropylene), polyethylene oxide, cellulose, polyvinyl alcohol and polyurethane.
As a further improvement of the invention, the modifier comprises one or more of an ionic liquid, dimethyl sulfoxide, ethylene glycol, potassium hydroxide, concentrated sulfuric acid or an ionic liquid.
As a further improvement of the invention, the organic electronic thermoelectric material comprises one of PEDOT, PSS, polypyrrole and polythiophene organic matters.
As a further improvement of the present invention, in step S1, the surfactant includes one of a silane coupling agent or sodium dodecyl sulfate to improve the dispersibility of the inorganic nanofiller and its interaction with the organic polymer; in step S2, the solvent comprises one of dimethyl sulfoxide, acetone, or dimethylformamide; the cross-linking agent comprises one or more of polyethylene glycol, polyethylene glycol diacrylate and formic acid.
According to the preparation method of the high-performance ion-electron composite thermoelectric fiber, the electronic thermoelectric coating containing the modifier is uniformly coated on the surface of the ionic liquid gel fiber core layer, and the high-performance ion-electron composite thermoelectric fiber is obtained.
The beneficial effects of the invention are:
1. the invention relates to a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, wherein the composite thermoelectric fiber comprises an ionic liquid gel fiber core layer and an electron thermoelectric coating for coating the ionic liquid gel fiber core layer; the ionic liquid gel fiber core layer comprises the following components: ionic liquid, organic polymer and inorganic nano-filler with anisotropy; the electronic thermoelectric coating includes an organic electronic thermoelectric material. The ionic liquid gel fiber and the electronic thermoelectric coating are compounded, so that the components and the structure of the ionic liquid gel fiber, the structure of the electronic thermoelectric coating and the interface combination of the ionic liquid gel fiber and the electronic thermoelectric coating are controlled, and the composite thermoelectric fiber with excellent thermoelectric performance and mechanical performance is obtained. The electronic thermoelectric coating of the composite thermoelectric fiber converts heat into electric energy by utilizing the Seebeck effect under the temperature difference; the ionic liquid gel fiber core layer can convert thermal energy into electric energy by utilizing temperature fluctuation caused by thermoelectric conversion of the electronic thermoelectric coating; the composite thermoelectric fiber is used for generating electricity by utilizing temperature difference and temperature fluctuation, the thermoelectric conversion efficiency is improved by 4-6 times compared with that of the traditional electronic thermoelectric material, and the composite thermoelectric fiber is more suitable for preparing high-performance wearable thermoelectric materials.
2. The ionic liquid gel fiber core layer and the electronic thermoelectric coating are compounded to form the ionic-electronic composite thermoelectric fiber, the electronic thermoelectric coating utilizes temperature gradient to carry out thermoelectric conversion, the temperature is usually fluctuated, and the ionic liquid fiber core layer utilizes the temperature fluctuation to carry out thermoelectric conversion; meanwhile, the ion accumulation of the ionic liquid fiber core layer can be caused by the change of the temperature, so that higher thermal voltage is generated, the charge balance of the electronic thermoelectric coating can be broken through the ion accumulation of the ionic liquid fiber core layer, and the thermoelectric conversion efficiency of the electronic thermoelectric coating is further improved. The ionic liquid fiber core layer and the electronic thermoelectric coating layer are cooperatively matched, so that the thermoelectric voltage and the thermoelectric conversion power of the composite thermoelectric fiber are improved.
3. The invention controls the components and the structure of the ion-electron composite thermoelectric fiber, the components of the fiber core layer, the fiber shape, the section, the structure of the coating, the interface combination between the ion layer and the electron layer, the matching degree of the mechanical property and the like by regulating and controlling the preparation process of the composite thermoelectric fiber, so as to synergistically improve the mechanical property and the thermoelectric property of the ion-electron composite thermoelectric fiber and improve the application prospect in the thermoelectric field. In addition, a small amount of ionic liquid is added into the electronic thermoelectric coating, the ionic liquid can improve the thermoelectric performance of the electronic thermoelectric coating, and can also improve the interface combination of the electronic thermoelectric coating and the electronic thermoelectric coating to form a capacitance interface for transmitting signals, so that the inner layer and the outer layer of the ion-electron composite thermoelectric fiber form a passage to improve the overall thermoelectric performance of the composite thermoelectric fiber.
4. The inorganic nano filler in the ionic liquid gel fiber core layer interacts with the organic polymer to form an organic-inorganic hybrid network structure, more cross-linking points and a stronger network can be formed in the gel, the ionic liquid is uniformly dispersed in the network, the amorphous area proportion of the ionic liquid is increased, and the ion conversion rate is improved, so that the ionic conductivity is improved; and a hybrid network with an oriented structure is formed after external force induction, so that the transmission rate of the ionic liquid in the network structure is improved, and the thermoelectric property of the fiber core layer is improved. In addition, the addition of the inorganic nano-filler changes the internal structural characteristics of the ionic liquid gel, improves the mechanical strength of the ionic liquid gel, and further improves the mechanical properties of the finally prepared ionic-electronic composite thermoelectric fiber.
Drawings
Fig. 1 is a schematic structural view of a high-performance ion-electron composite thermoelectric fiber prepared in example 1 of the present invention.
Fig. 2 is a schematic view of the internal structure of a high-performance ion-electron composite thermoelectric fiber prepared in example 14 of the present invention.
Reference numerals
1-an inorganic nanofiller; 2-an ionic liquid gel fiber core layer; 3-an electronic thermoelectric coating; 4-fibrous base material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
A high-performance ion-electron composite thermoelectric fiber comprises an ionic liquid gel fiber core layer and an electron thermoelectric coating for coating the ionic liquid gel fiber core layer; the ionic liquid gel fiber core layer is an organic-inorganic hybrid network structure with an oriented structure, and comprises the following components in percentage by mass: 50 to 90 percent of ionic liquid, 7 to 47 percent of organic polymer and 3 to 30 percent of inorganic nano-filler with anisotropy; the electronic thermoelectric coating includes an organic electronic thermoelectric material. Wherein the ionic liquid is ionic liquid with thermoelectric property; the inorganic nano filler is in an anisotropic structure; the organic polymer is a hydrophilic organic polymer having a polar functional group. The electronic thermoelectric coating also comprises ionic liquid, and the addition amount of the ionic liquid accounts for 1.0-3.5% of the total mass of the electronic thermoelectric coating material. The thickness of the electronic thermoelectric coating is 0.5-20 μm; the electronic thermoelectric coating further comprises a modifier to regulate the performance of the electronic thermoelectric coating and promote interfacial bonding of the electronic thermoelectric coating and the ionic liquid gel fiber core layer.
Particularly, the invention prepares the ion-electron composite thermoelectric fiber with good thermoelectric property and mechanical property by adjusting the components and the content of the ionic liquid gel fiber core layer and the structure of the electronic thermoelectric coating. The electronic thermoelectric coating comprises a small amount of ionic liquid and a modifier of an organic electronic thermoelectric material, wherein the ionic liquid and the ionic liquid in the ionic liquid gel fiber core layer are the same substance; therefore, the thermoelectric performance of the electronic thermoelectric coating can be improved, the interface combination of the electronic thermoelectric coating and the ionic liquid gel fiber core layer can be improved, a capacitance interface is formed to transfer signals, and the inner layer and the outer layer of the ion-electron composite thermoelectric fiber form a channel, so that the overall thermoelectric performance of the composite thermoelectric fiber is improved. The added modifier enables the organic electronic thermoelectric material to be more easily compounded with hydrophilic organic polymers containing polar functional groups in the ionic liquid gel fiber core layer, and the modifier is added to promote the interface combination of the organic electronic thermoelectric material and the hydrophilic organic polymers, so that the combination firmness is improved.
The inorganic nano filler in the ionic liquid gel fiber core layer interacts with the organic polymer to form an organic-inorganic hybrid network structure, more cross-linking points and a stronger network can be formed in the gel, the ionic liquid is uniformly dispersed in the network, the amorphous area proportion of the ionic liquid is increased, and the ion conversion rate is improved, so that the ionic conductivity is improved; and a hybrid network with an oriented structure is formed after external force induction, so that the transmission rate of the ionic liquid in the network structure is improved, and the thermoelectric property of the fiber core layer is improved. In addition, the addition of the inorganic nano-filler changes the internal structural characteristics of the ionic liquid gel, improves the mechanical strength of the ionic liquid gel, and further improves the mechanical properties of the finally prepared ionic-electronic composite thermoelectric fiber.
In some specific embodiments, the inorganic nanofiller comprises nano-SiO 2 、TiO 2 One or more of halloysite nanotubes, attapulgite and graphene oxide; the ionic liquid comprises 1-ethyl-3-methylimidazolium dicyanamide salt, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium bistrifluoromethylsulfimide salt, and N-methylOne or more of N-propyl-N-methylpyrrolidine bistrifluoromethanesulfonylimide salts; the organic polymer comprises one or more of poly (vinylidene fluoride-co-hexafluoropropylene), polyethylene oxide, cellulose, polyvinyl alcohol and polyurethane.
In some specific embodiments, the modifying agent comprises one or more of an ionic liquid, dimethyl sulfoxide, ethylene glycol, potassium hydroxide, concentrated sulfuric acid, or an ionic liquid. The organic electronic thermoelectric material comprises one of PEDOT, PSS, polypyrrole and polythiophene organic matters.
Specifically, the preparation of the ionic liquid gel fiber core layer specifically comprises the following steps:
s1, carrying out surface modification on anisotropic inorganic nano-filler by adopting a surfactant to obtain modified inorganic nano-filler;
s2, dissolving an organic polymer in a solvent, adding the modified inorganic nano filler in the step S1, ionic liquid and a cross-linking agent, blending, and fully stirring and dispersing to obtain an ionic liquid gel mixed solution;
s3, adopting a spinning method: pre-gelling the ionic liquid gel mixed solution obtained in the step S2, wherein the pre-gelling time is 0.5-3 h and the temperature is 25-90 ℃; extruding the fiber into a die by using an extrusion needle, and finally performing gelation treatment to prepare an ionic liquid gel fiber core layer; wherein, the diameter range of the hole of the extrusion needle head is 0.1-2 mm, and the chamfer angle range of the needle head is 10-60 degrees;
or adopting a coating method: soaking the pretreated fiber base material in the ionic liquid gel mixed solution obtained in the step S2 to enable the ionic liquid gel to form a uniform coating on the surface of the fiber base material; after repeated soaking and drying, the ionic liquid gel fiber core layer is obtained; the thickness of the ionic liquid gel coating is 5-100 mu m.
When the spinning method is adopted, the concentration of the spinning solution is controlled within a proper range by controlling the temperature and time of the pre-gelatinization of the spinning solution in the spinning process, so that the effect of inducing orientation by a shearing force field can be improved, and the relaxation of an oriented structure is reduced, thereby promoting the formation of a compact fiber structure; meanwhile, the weak interaction of hydrogen bonds, van der waals force and the like in the gel can be adjusted by controlling the temperature, so that the mechanical strength and the thermal stability of the prepared fiber are further improved, and the prepared fiber has excellent thermoelectric property and mechanical property. The diameter, the circumferential inclination angle and the drawing ratio of the extruding needle head are controlled to enhance the induced orientation effect of the shearing force field on the spinning solution extruding process, so that the prepared fiber has an orientation structure, and the problem of poor conductivity caused by low degree of order of the ionic liquid in the organic thermoelectric material is solved.
When the coating method is adopted, the fiber base material can be elastic fiber with unrecoverable deformation capacity, and the inorganic nano-filler is a filler with an anisotropic structure; when the ionic liquid gel fiber core layer is prepared, the fiber soaked in the ionic liquid gel solution for the first time is stretched, the inorganic nano filler with an anisotropic structure can generate an orientation effect, and the orientation structure is favorable for improving the ion conversion rate in the ionic liquid gel coating, so that the ionic conductivity is improved, and the improvement on the thermoelectric performance of the composite fiber is well influenced; and the fiber matrix can generate irreversible slippage of macromolecular chains, and gaps among molecules are generated, so that organic polymers in the ionic liquid gel coating can better interact with the base material, the combination of the coating and the matrix is enhanced, and the mechanical property of the fiber is improved. The fiber base material is only subjected to drawing treatment during first soaking, and then is subjected to normal soaking-drying, so that a strong connecting area can be formed between the fiber base material and the ionic liquid gel, the strength of the composite fiber is improved, the integrity of the composite fiber is improved, and the composite fiber has excellent thermoelectric performance; the temperature of the ionic liquid gel during soaking is further controlled, so that the contact between the organic polymer in the ionic liquid gel and the fiber base material can be increased, and the combination of the organic polymer and the fiber base material is promoted. The fiber base material is repeatedly soaked and dried for many times, so that the uniformity of the coating can be improved, and the overall thermoelectric performance of the composite thermoelectric fiber is improved.
The fiber base material is preferably hydrophilic fiber containing polar functional groups or yarn constructed by hydrophilic fiber, the organic polymer of the ionic liquid gel also contains polar functional groups and has hydrophilicity, and the aim is to increase the composite firmness of the ionic liquid gel and the fiber base material by the principle of similar intermiscibility; when the ionic liquid gel and the fiber base material are compounded, a bonding reaction occurs between the polar functional group in the organic polymer and the polar functional group in the fiber base material, and the compounding of the ionic liquid gel and the fiber base material is promoted.
As a further improvement of the present invention, in step S1, the surfactant includes one of a silane coupling agent or sodium dodecyl sulfate to improve the dispersibility of the inorganic nano-filler and its interaction with the organic polymer; in step S2, the solvent comprises one of dimethyl sulfoxide, acetone or dimethylformamide; the cross-linking agent comprises one or more of polyethylene glycol, polyethylene glycol diacrylate and formic acid.
A preparation method of a high-performance ion-electron composite thermoelectric fiber comprises the step of uniformly coating an electronic thermoelectric coating containing a modifier on the surface of an ionic liquid gel fiber core layer to obtain the high-performance ion-electron composite thermoelectric fiber.
In particular, an ionic liquid gel fiber core layer and an electronic thermoelectric coating layer are compounded to form the ionic-electronic composite thermoelectric fiber, the electronic thermoelectric coating layer utilizes temperature gradient to perform thermoelectric conversion, the temperature is usually fluctuant, and the ionic liquid fiber core layer can utilize the temperature fluctuation to perform thermoelectric conversion; meanwhile, the ion accumulation of the ionic liquid fiber core layer can be caused by the change of the temperature, so that higher thermal voltage is generated, the charge balance of the electronic thermoelectric coating can be broken through the ion accumulation of the ionic liquid fiber core layer, and the thermoelectric conversion efficiency of the electronic thermoelectric coating is further improved. The ionic liquid fiber core layer and the electronic thermoelectric coating layer are cooperatively matched, so that the thermoelectric voltage and the thermoelectric power are improved.
The invention synergistically improves the mechanical property and the thermoelectric property of the ion-electron composite thermoelectric fiber by regulating and controlling the structure of the composite thermoelectric fiber, the components of the fiber core layer, the fiber shape, the section, the structure of the coating, the interface combination between the ion layer and the electron layer, the matching degree of the mechanical property and the like, so as to improve the application prospect of the ion-electron composite thermoelectric fiber in the thermoelectric field.
In the practical application of the ion-electron composite thermoelectric fiber, due to thermionic diffusion (Soret effect), ion accumulation occurs in the core layer of the ionic liquid gel fiber; the electronic thermoelectric coating has higher electrical conductivity and lower thermoelectric voltage than the ionic liquid gel fiber core layer, so that charges in the electronic thermoelectric coating can migrate to an interface between the ionic liquid gel fiber core layer and the electronic thermoelectric coating to compensate ions accumulated in the ionic liquid gel fiber core layer; thus, a capacitance interface is formed, alternating current signals can be transmitted, and the inner layer and the outer layer of the ion-electron composite thermoelectric fiber form a passage, so that the overall thermoelectric performance of the composite thermoelectric fiber is improved.
Example 1
The embodiment provides a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, wherein the composite thermoelectric fiber comprises an ionic liquid gel fiber core layer and an electron thermoelectric coating layer for coating the ionic liquid gel fiber core layer; the ionic liquid gel fiber core layer is an organic-inorganic hybrid network structure with an oriented structure, and comprises the following components in percentage by mass: 80% of 1-ethyl-3-methylimidazolium dicyanamide salt, 15% of polyethylene oxide and 5% of attapulgite filler with anisotropy; the electronic thermoelectric coating comprises PEDOT, PSS, 2 percent of ionic liquid 1-ethyl-3-methylimidazole dicyanamide salt and modifier dimethyl sulfoxide; the preparation method specifically comprises the following steps:
s1, preparation of ionic liquid gel fiber core layer
S11, carrying out surface modification on the anisotropic attapulgite filler by adopting a surfactant to obtain a modified inorganic nano attapulgite filler;
s12, dissolving polyethylene oxide in a solvent, adding the modified inorganic nano attapulgite filler in the step S11, 1-ethyl-3-methylimidazole dicyanamide salt and a cross-linking agent polyethylene glycol, mixing, fully stirring and dispersing to obtain an ionic liquid gel mixed solution;
s13, adopting a spinning method: pre-gelling the ionic liquid gel mixed solution obtained in the step S12 for 2 hours at the temperature of 70 ℃; extruding the fiber into a mould by using an extrusion needle, and finally performing gelation treatment to prepare an ionic liquid gel fiber core layer; wherein, the diameter of the hole of the extrusion needle is 1mm, and the chamfer angle is 45 degrees;
s2, uniformly coating the electronic thermoelectric coating containing the modifier dimethyl sulfoxide and the ionic liquid 1-ethyl-3-methylimidazolium dicyanamide on the surface of the ionic liquid gel fiber core layer, wherein the thickness of the electronic thermoelectric coating is 2 microns, and thus the high-performance ion-electron composite thermoelectric fiber is obtained.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a high-performance ion-electron composite thermoelectric fiber manufactured in this embodiment, and it can be seen from the diagram that an inorganic nano filler 1 in an ionic liquid gel fiber core layer 2 has a good orientation effect, and an electronic thermoelectric coating 3 is coated outside the ionic liquid gel fiber core layer.
Examples 2 to 3
Example 4
The embodiment provides a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, and compared with embodiment 1, the difference is that the fiber comprises the following components in percentage by mass: 60% of 1-ethyl-3-methylimidazolium dicyanamide salt, 30% of polyethylene oxide and 10% of nano attapulgite filler with anisotropy; the rest is substantially the same as embodiment 1, and the description thereof is omitted.
Example 5
The embodiment provides a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, and compared with embodiment 1, the difference is that the fiber comprises the following components in percentage by mass: 80% of 1-ethyl-3-methylimidazole dicyanamide salt, 5% of polyethylene oxide and 15% of nano attapulgite filler with anisotropy; the rest is substantially the same as that of embodiment 1, and the description thereof is omitted.
Comparative example 1
Comparative example 1 is a composite thermoelectric fiber and a preparation method thereof, and compared with example 1, the difference is that the fiber is only an ionic liquid gel fiber core layer, and is not coated with an electronic thermoelectric coating, and the rest is substantially the same as example 1, and is not described herein again.
Comparative example 2
Comparative example 2 is a composite thermoelectric fiber and a method for preparing the same, and compared with example 1, the difference is that inorganic nanofillers are not added to a liquid ion nanofiber core layer of the composite thermoelectric fiber, and the rest is substantially the same as example 1, and the details are not repeated.
Comparative example 3
Comparative example 3 is a composite thermoelectric fiber and a method for preparing the same, and compared with example 1, the difference is that the inorganic nanofiller added to the liquid ion nanofiber core layer of the composite thermoelectric fiber is attapulgite particles with a uniform shape, and the rest is substantially the same as example 1, and is not repeated herein.
Comparative example 4
Comparative example 4 is a composite thermoelectric fiber and a method for preparing the same, and compared with example 1, the difference is that the ionic liquid 1-ethyl-3-methylimidazole dicyanamide salt is not added to the electronic thermoelectric coating, and the rest is substantially the same as example 1, and will not be described again.
The results of the thermoelectric properties and mechanical properties of the high-performance ion-electron composite thermoelectric fibers obtained in examples 1 to 5 and comparative examples 1 to 4 are shown in the following table.
TABLE 1 indexes of composite thermoelectric fibers obtained in examples 1 to 5 and comparative examples 1 to 4
As can be seen from table 1, the data of examples 1 to 3 and comparative example 1 show that changing the structure of the surface electron thermoelectric layer affects the coverage and conductivity of the surface electron thermoelectric layer. Research shows that the higher the electron coverage rate of the surface of the composite thermoelectric fiber is, the higher the resistance of the thermoelectric layer is, and the more beneficial the output voltage and power density of the composite fiber are. Meanwhile, the mechanical properties of the composite fiber can be influenced by the thickness of the electronic thermoelectric layer on the surface of the composite thermoelectric fiber, and the larger the thickness is, the higher the tensile strength is, but the elongation at break is basically kept unchanged. When the thickness of the electronic thermoelectric layer is smaller, the complete electronic thermoelectric coating cannot be formed on the surface of the fiber, and the coverage rate of the electronic thermoelectric coating is influenced, so that the output voltage and the power are influenced. However, when the electron thermoelectric thickness is too large, the electric resistance of the surface electron layer is rather decreased, and the output voltage and power are both decreased, but the tensile strength of the entire composite fiber is improved.
As can be seen from the above table, when the content of the ionic liquid is reduced, the seebeck coefficient of the ionic liquid gel fiber is reduced, but the tensile strength and the elongation at break are improved; when the content of the anisotropic nano filler is properly increased, the thermoelectric property and the mechanical property of the composite thermoelectric fiber are increased, but the nano particles are agglomerated due to excessive addition amount, so that the mechanical property is influenced. As can be seen from examples 1 to 5 and comparative examples 1 to 4, the thermoelectric performance of the composite thermoelectric fiber is higher than that of a single-component thermoelectric material after the ionic thermoelectric material and the electronic thermoelectric material are compounded; the thermoelectric property and the mechanical property of the ion-electron composite fiber can be improved by adding the anisotropic nano particles into the ionic liquid and adding the ionic liquid into the electronic thermoelectric material; the halloysite nanoparticles with uniform shapes are added, so that the orientation effect cannot be generated in the spinning process, and the thermoelectric property and the tensile strength of the prepared composite thermoelectric fiber are reduced.
Examples 6 to 13 and comparative examples 5 to 6
Examples 6 to 13 and comparative examples 5 to 6 provide a high-performance ion-electron composite thermoelectric fiber and a method for preparing the same, which are different from example 1 in that the time and temperature of the pregelatinization treatment and the parameters of the needle in step S13 are shown in the following table; the rest is substantially the same as embodiment 1, and will not be described again.
TABLE 2 pregelatinization treatments and showerhead parameters for examples 6-13 and comparative examples 5-6
The results of the thermoelectric properties and mechanical properties of the high-performance ion-electron composite thermoelectric fibers obtained in examples 6 to 13 are shown in the following table.
TABLE 3 indexes of the composite thermoelectric fibers obtained in examples 6 to 13
As is clear from table 3, it is found from examples 6 to 9 that the shorter the pre-gelation treatment time, the longer the time required for the fiber to be cured and molded, the partially de-oriented nanoparticles are caused, and the thermoelectric performance of the ionic liquid gel fiber is affected, and the thermoelectric performance of the composite thermoelectric fiber is affected. And the long pre-gelation treatment time can accelerate the solidification of the ionic liquid gel, reduce the shear stress orientation effect and influence the thermoelectric performance of the composite thermoelectric fiber. The pre-gelation treatment temperature is too low, so that the ionic liquid gel fiber needs longer time for forming, the nano particles are partially de-oriented, the orientation degree is reduced, the thermoelectric property of the ionic liquid gel fiber is influenced, and the thermoelectric property of the composite thermoelectric fiber is influenced. The performance of the high molecular polymer can be influenced by overhigh pre-gelation treatment temperature, the solidification of the ionic liquid gel is accelerated, the shear stress orientation effect is reduced, and the thermoelectric performance of the composite thermoelectric fiber is influenced.
In examples 10 to 11, the smaller the diameter of the ionic liquid gel fiber, the stronger the shear orientation effect, and thus the orientation of the anisotropic nanoparticles was improved, and the thermoelectric properties and tensile strength of the fiber were increased. In examples 12 to 13, when the inclination angle of the nozzle is too small, a flow dead angle is generated, so that the shearing force applied to the spinning solution is not uniform, and the shearing orientation effect is reduced, thereby affecting the thermoelectric property of the ionic liquid gel fiber core layer; the larger the inclination angle is, the smaller the shearing force applied to the spinning solution is, the orientation of the anisotropic nanoparticles is reduced, and the thermoelectric and mechanical properties of the fiber are affected. In comparative examples 5 to 6, since the temperature of the pregelatinization treatment was too high or the pregelatinization treatment time was too long, pregelatinization was excessive and the hardness was large, and the subsequent molding of the gel fiber was difficult.
Example 14
The embodiment provides a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, and compared with embodiment 1, the difference is that in step S13 of preparing an ionic liquid gel fiber core layer, a coating method is adopted: soaking the pretreated fiber base material in the ionic liquid gel mixed solution obtained in the step S2 to form a uniform ionic liquid gel coating on the surface of the fiber base material, wherein the thickness of the coating is 20 microns; wherein the concentration of the ionic liquid gel mixed solution is 10%, the fiber base material is elastic fiber with unrecoverable deformation capacity, and the fiber base material is subjected to drafting treatment when the fiber base material is soaked in the ionic liquid gel solution for the first time; the rest is substantially the same as embodiment 1, and will not be described again.
Referring to fig. 2, fig. 2 is a schematic diagram of an internal structure of the high-performance ion-electron composite thermoelectric fiber prepared in this embodiment, and it can be seen from the diagram that the inorganic nanofiller 1 in the ionic liquid gel coating has a good orientation effect, the fiber substrate 4 and the ionic liquid gel coating form an ionic liquid gel fiber core layer 2, and an electronic thermoelectric coating 3 is coated outside the ionic liquid gel fiber core layer.
Example 15
Compared with the embodiment 14, the difference is that in the step S13 of preparing the ionic liquid gel fiber core layer, the fiber base material is a common fiber, and the fiber base material is not subjected to drawing treatment when the ionic liquid gel fiber core layer is soaked in the ionic liquid gel solution for the first time; the rest is substantially the same as embodiment 1, and the description thereof is omitted.
The results of the thermoelectric properties and mechanical properties of the high-performance ion-electron composite thermoelectric fibers obtained in examples 14 to 15 are shown in the following table.
TABLE 4 indexes of the composite thermoelectric fibers obtained in examples 14 to 15
As can be seen from table 4, the ion-electron composite hot spot fiber can also be prepared by using a commercial fiber as a substrate, and applying an ionic liquid gel and an electronic thermoelectric coating in sequence. However, the presence of the non-conductive fiber base material affects the thermoelectric performance of the composite fiber, and therefore the power density is slightly lowered. Furthermore, comparing the data of examples 14 and 15, it can be seen that higher thermoelectric and mechanical properties are obtained after adding anisotropic nanofillers and orientation in the ionic liquid gel coating.
In summary, according to the high-performance ion-electron composite thermoelectric fiber and the preparation method thereof provided by the invention, the composite thermoelectric fiber comprises an ionic liquid gel fiber core layer and an electron thermoelectric coating layer coating the ionic liquid gel fiber core layer; the ionic liquid gel fiber core layer comprises the following components: 50 to 90 percent of ionic liquid, 7 to 47 percent of organic polymer and 3 to 30 percent of inorganic nano-filler with anisotropy; the electronic thermoelectric coating includes an organic electronic thermoelectric material. The ionic liquid gel fiber and the electronic thermoelectric coating are compounded, so that the components and the structure of the ionic liquid gel fiber, the structure of the electronic thermoelectric coating and the interface combination of the ionic liquid gel fiber and the electronic thermoelectric coating are controlled, and the composite thermoelectric fiber with excellent thermoelectric performance and mechanical performance is obtained. The ionic liquid gel fiber core layer and the electronic thermoelectric coating are compounded to form the ionic-electronic composite thermoelectric fiber, the electronic thermoelectric coating utilizes temperature gradient to perform thermoelectric conversion, the temperature generally fluctuates, and the ionic liquid fiber core layer utilizes temperature fluctuation to perform thermoelectric conversion so as to improve the thermoelectric voltage and the thermoelectric power; the ionic-electronic composite thermoelectric fiber and the preparation method thereof can synergistically improve the mechanical property and the thermoelectric property of the ionic-electronic composite thermoelectric fiber, so that the ionic-electronic composite thermoelectric fiber is more suitable for preparing high-performance wearable thermoelectric materials.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A high-performance ion-electron composite thermoelectric fiber is characterized in that the composite thermoelectric fiber comprises an ionic liquid gel fiber core layer and an electronic thermoelectric coating layer wrapping the ionic liquid gel fiber core layer; the ionic liquid gel fiber core layer has an organic-inorganic hybrid network structure with an oriented structure, and comprises the following components in percentage by mass: 50 to 90 percent of ionic liquid, 7 to 47 percent of organic polymer and 3 to 30 percent of inorganic nano-filler with anisotropy; the electronic thermoelectric coating includes an organic electronic thermoelectric material.
2. The high performance ion-electron composite thermoelectric fiber according to claim 1, wherein the ionic liquid is an ionic liquid having thermoelectric properties; the inorganic nano filler is in an anisotropic shape structure; the organic polymer is a hydrophilic organic polymer containing a polar functional group.
3. The high-performance ion-electron composite thermoelectric fiber according to claim 1, wherein the electron thermoelectric coating further comprises an ionic liquid, and the amount of the ionic liquid added is 1.0-3.5% of the total mass of the electron thermoelectric coating material; the ionic liquid of the electronic thermoelectric coating and the ionic liquid in the ionic liquid gel fiber core layer are the same substance.
4. The high-performance ion-electron composite thermoelectric fiber according to claim 1, wherein the thickness of the electron thermoelectric coating layer is 0.5 to 20 μm; the electronic thermoelectric coating further comprises a modifier to regulate the performance of the electronic thermoelectric coating and promote the interfacial bonding of the electronic thermoelectric coating and the ionic liquid gel fiber core layer.
5. The high-performance ion-electron composite thermoelectric fiber according to claim 1, wherein the preparation of the ionic liquid gel fiber core layer specifically comprises the following steps:
s1, carrying out surface modification on anisotropic inorganic nano-filler by adopting a surfactant to obtain modified inorganic nano-filler;
s2, dissolving organic polymer in a solvent, adding the modified inorganic nano filler, the ionic liquid and the cross-linking agent in the step S1, blending, fully stirring and dispersing to prepare an ionic liquid gel mixed solution;
s3, adopting a spinning method: pre-gelling the ionic liquid gel mixed solution obtained in the step S2, wherein the pre-gelling time is 0.5-3 h and the temperature is 25-90 ℃; extruding the fiber into a die by using an extrusion needle, and finally performing gelation treatment to prepare the ionic liquid gel fiber core layer;
or adopting a coating method: soaking the pretreated fiber base material in the ionic liquid gel mixed solution obtained in the step S2 to enable the ionic liquid gel to form a uniform coating on the surface of the fiber base material; repeatedly soaking and drying to obtain the ionic liquid gel fiber core layer; the thickness of the ionic liquid gel coating is 5-100 mu m.
6. The high-performance ion-electron composite thermoelectric fiber according to claim 5, wherein in step S3, when a spinning method is employed, the hole diameter of the extrusion needle is in the range of 0.1 to 2mm, and the chamfer angle of the needle is in the range of 10 to 60 °; when the coating method is adopted, the concentration of the ionic liquid gel mixed solution is 5-20%.
7. The high performance ion-electron composite thermoelectric fiber of claim 2, wherein the inorganic nanofiller comprises nano-SiO 2 、TiO 2 One or more of halloysite nanotubes, attapulgite and graphene oxide; the ionic liquid comprises 1-ethyl-3-methylimidazole dicyanamide salt, 1-ethyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylOne or more of a imidazolylbis (trifluoromethanesulfonylimide salt), an N-methyl, N-propyl-N-methylpyrrolidine bistrifluoromethylsulfonylimide salt; the organic polymer comprises one or more of poly (vinylidene fluoride-co-hexafluoropropylene), polyethylene oxide, cellulose, polyvinyl alcohol and polyurethane.
8. The high performance ion-electron composite thermoelectric fiber according to claim 4, wherein the modifier comprises one or more of an ionic liquid, dimethyl sulfoxide, ethylene glycol, potassium hydroxide, concentrated sulfuric acid; the organic electronic thermoelectric material comprises one of PEDOT, PSS, polypyrrole and polythiophene organic matters.
9. The high-performance ion-electron composite thermoelectric fiber according to claim 5, wherein in step S1, the surfactant comprises one of a silane coupling agent or sodium dodecyl sulfate to improve the dispersibility of the inorganic nano-filler and its interaction with the organic macromolecule; in step S2, the solvent comprises one of dimethyl sulfoxide, acetone, or dimethylformamide; the cross-linking agent comprises one or more of polyethylene glycol, polyethylene glycol diacrylate and formic acid.
10. The preparation method of the high-performance ion-electron composite thermoelectric fiber according to any one of claims 1 to 9, wherein the high-performance ion-electron composite thermoelectric fiber is obtained by uniformly coating an electronic thermoelectric coating containing a modifier on the surface of an ionic liquid gel fiber core layer.
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