CN115522279B - 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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- ZXAKFAMWSBPGHR-UHFFFAOYSA-N CCCN1CCCC1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O Chemical compound CCCN1CCCC1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O ZXAKFAMWSBPGHR-UHFFFAOYSA-N 0.000 claims 1
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- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- 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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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M13/248—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 with compounds containing sulfur
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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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
- D06M13/322—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 nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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 the ionic liquid gel fiber core layer; the components of the ionic liquid gel fiber core layer comprise: 50-90% of ionic liquid, 7-47% of organic polymer and 3-30% of inorganic nano filler with anisotropy; the electron thermoelectric coating comprises an electron thermoelectric material and an ionic liquid. The electronic thermoelectric coating performs thermal-electric conversion by using a temperature gradient to cause temperature fluctuation, and the ionic liquid fiber core layer performs thermoelectric conversion by using the temperature fluctuation so as to improve thermal voltage and thermoelectric power. The invention obtains the composite thermoelectric fiber with excellent thermoelectric property and mechanical property by controlling 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, so that the composite thermoelectric fiber is more suitable for preparing the high-performance wearable thermoelectric material.
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, the principle is that the mutual conversion of heat energy and electric energy is realized through the movement of carriers in the solid, and the thermoelectric material has wide application prospect in the aspects of thermoelectric generation and refrigeration. Conventional thermoelectric materials have poor mechanical properties and cause breakage and deformation when subjected to external pressure, which greatly reduces the service life and range of the materials. Compared with the traditional inorganic thermoelectric material, the organic thermoelectric material has improved mechanical properties and is mainly used in the field of flexible electronic materials; but the electrical properties of the organic thermoelectric material differ too much from those of the inorganic material. Therefore, how to improve the electrical properties of the organic thermoelectric material is of great importance for its application 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 material, 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 tube, 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, and the preparation method is simple, low in cost and good in thermoelectric performance of the thermoelectric fiber; 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 practical application range is limited.
The invention patent (CN 202010176233.2) discloses an organic/inorganic composite thermoelectric fiber, a preparation method and an 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 nanowires Te NWs, and Te NWs are oriented and distributed in the PEDOT: PSS fiber, and the thermoelectric fiber is prepared by adopting wet spinning; the thermoelectric performance of PEDOT: PSS is improved by introducing Te NWs thermoelectric materials, so that the composite fiber has good thermoelectric performance.
Compared with the common organic thermoelectric material, the two thermoelectric fibers have high conductivity, but the Seebeck coefficient of the thermoelectric fibers is far lower than the working voltage of a small wearable electronic device, and the requirements of the application field are difficult to meet.
In view of the foregoing, there is a need for an improved high performance ion-electron composite thermoelectric fiber and method of making the same that addresses the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, wherein an ionic liquid gel fiber and an electron thermoelectric coating are compounded, and the composite thermoelectric fiber with excellent thermoelectric performance and mechanical performance is obtained through controlling the components, the structure of the ionic liquid gel fiber, the structure of the electron thermoelectric coating and the interface combination of the ionic liquid gel fiber and the electron thermoelectric coating. 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 heat 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 the thermoelectric conversion efficiency, and is more suitable for preparing high-performance wearable thermoelectric materials.
In order to achieve the above object, the present invention provides a high performance ion-electron composite thermoelectric fiber, which comprises an ionic liquid gel fiber core layer and an electron thermoelectric coating layer covering the ionic liquid gel fiber core layer; the ionic liquid gel fiber core layer is provided with an organic-inorganic hybrid network structure with an orientation structure, and comprises the following components in percentage by mass: 50-90% of ionic liquid, 7-47% of organic polymer and 3-30% of inorganic nano filler with anisotropy; the electron thermoelectric coating includes an electron 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 a structure with shape anisotropy; the organic polymer is a hydrophilic organic polymer containing polar functional groups.
As a further improvement of the invention, the electronic thermoelectric coating also comprises an ionic liquid, wherein the addition amount of the ionic liquid accounts for 1.0-3.5% of the mass of the total 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 also comprises a modifier to regulate the performance of the electronic thermoelectric coating and promote the interface combination 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, and fully stirring and dispersing to obtain an ionic liquid gel mixed solution;
s3, adopting a spinning method: performing pre-gelatinization treatment on the ionic liquid gel mixed solution in the step S2, wherein the pre-gelatinization treatment time is 0.5-3 h, and the temperature is 25-90 ℃; extruding the fiber core layer into a die by using an extrusion needle, and finally, carrying out gelation treatment to obtain the ionic liquid gel fiber core layer;
or a coating method is adopted: immersing the pretreated fiber substrate in the ionic liquid gel mixed solution in the step S2, so that the ionic liquid gel forms a uniform coating on the surface of the fiber substrate; 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 the step S3, when a spinning method is adopted, the diameter range of the hole of the extrusion needle head is 0.1-2 mm, and the chamfering range of the needle head is 10-60 degrees; when the coating method is adopted, the concentration of the ionic liquid gel mixed solution is 5-20%.
As a further improvement of the present invention, the inorganic nanofiller includes 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 dicyandiamide 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 present invention, the modifier includes one or more of ionic liquid, dimethyl sulfoxide, ethylene glycol, potassium hydroxide, concentrated sulfuric acid, or ionic liquid.
As a further improvement of the invention, the organic 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 includes one of dimethyl sulfoxide, acetone or dimethylformamide; the cross-linking agent comprises one or more of polyethylene glycol, polyethylene glycol diacrylate and formic acid.
The preparation method of the high-performance ion-electron composite thermoelectric fiber comprises the step of uniformly coating an electron 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.
The beneficial effects of the invention are as follows:
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 the ionic liquid gel fiber core layer; the components of the ionic liquid gel fiber core layer comprise: ionic liquid, organic polymer and inorganic nano filler with anisotropy; the electron thermoelectric coating includes an electron thermoelectric material. The components, 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 by compounding the ionic liquid gel fiber and the electronic thermoelectric coating, so that 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 heat 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, and the thermoelectric conversion efficiency is improved by 4-6 times compared with that of the traditional electronic thermoelectric material, so that the composite thermoelectric fiber is more suitable for preparing the high-performance wearable thermoelectric material.
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 performs thermoelectric conversion by utilizing a temperature gradient, the temperature is generally fluctuated, and the ionic liquid fiber core layer performs thermoelectric conversion by utilizing the temperature fluctuation; meanwhile, the temperature change can cause the ion accumulation of the ionic liquid fiber core layer so as to generate higher thermal voltage, and the ion accumulation of the ionic liquid fiber core layer can break the charge balance of the electronic thermoelectric coating, so that the thermoelectric conversion efficiency is further improved. The ionic liquid fiber core layer and the electronic thermoelectric coating are matched in a cooperative manner, so that the thermoelectric voltage and thermoelectric conversion power of the composite thermoelectric fiber are improved.
3. The invention controls the components, structure, fiber core layer components, fiber morphology, section, coating structure, interface combination between the ionic layer and the electronic layer, matching degree of mechanical property and the like of the ion-electronic composite thermoelectric fiber by regulating and controlling the preparation process of the composite thermoelectric fiber, so as to cooperatively improve the mechanical property and the thermoelectric property of the ion-electronic composite thermoelectric fiber, thereby improving the application prospect in the thermoelectric field. In addition, a small amount of ionic liquid is added into the electronic thermoelectric coating, so that the ionic liquid not only can improve the thermoelectric performance of the electronic thermoelectric coating, but also can improve the interface combination of the electronic thermoelectric coating and the ionic liquid to form a capacitance interface transmission signal, so that the inner layer and the outer layer of the ion-electronic composite thermoelectric fiber form a passage, and the thermoelectric performance of the whole composite thermoelectric fiber is improved.
4. The inorganic nano filler in the ionic liquid gel fiber core layer of the invention interacts with organic polymer to form an organic-inorganic hybrid network structure, more crosslinking points and stronger networks can be formed in the gel, the ionic liquid is uniformly dispersed in the networks, the proportion of an amorphous area is increased, and the conversion rate of ions is improved, so that the ionic conductivity is improved; and a hybrid network with an orientation 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 performance 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 showing the internal structure of the high-performance ion-electron composite thermoelectric fiber prepared in example 14 of the present invention.
Reference numerals
1-an inorganic nanofiller; 2-ionic liquid gel fiber core layer; 3-electron thermoelectric coating; 4-fibrous substrate.
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 due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further 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.
The high-performance ion-electron 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 is an organic-inorganic hybrid network structure with an orientation structure, and comprises the following components in percentage by mass: 50-90% of ionic liquid, 7-47% of organic polymer and 3-30% of inorganic nano filler with anisotropy; the electron thermoelectric coating includes an electron thermoelectric material. The ionic liquid is an ionic liquid with thermoelectric performance; the inorganic nano filler is in a structure with shape anisotropy; the organic polymer is a hydrophilic organic polymer containing polar functional groups. 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 mu m; the electronic thermoelectric coating also comprises a modifier to regulate the performance of the electronic thermoelectric coating and promote the interface combination of the electronic thermoelectric coating and the ionic liquid gel fiber core layer.
In particular, the ion-electron composite thermoelectric fiber with good thermoelectric property and mechanical property is prepared by adjusting the components and the content of the ionic liquid gel fiber core layer and the structure of the electron thermoelectric coating. The electronic thermoelectric coating comprises a small amount of ionic liquid and a modifier of an organic 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 transmission signal is formed, and the inner layer and the outer layer of the ion-electronic composite thermoelectric fiber form a passage, so that the overall thermoelectric performance of the composite thermoelectric fiber is improved. The added modifier makes the organic thermoelectric material more easily compound with hydrophilic organic polymer containing polar functional groups in the ionic liquid gel fiber core layer, and the interface combination of the two is promoted by adding the modifier, so that the firmness of combination is increased.
The inorganic nano filler in the ionic liquid gel fiber core layer and the organic polymer interact to form an organic-inorganic hybrid network structure, more crosslinking points and stronger networks can be formed in the gel, the ionic liquid is uniformly dispersed in the networks, the proportion of an amorphous area of the ionic liquid is increased, and the conversion rate of ions is improved, so that the ionic conductivity is improved; and a hybrid network with an orientation 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 performance 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 particular embodiments, 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 dicyandiamide salt, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole bistrifluoro methanesulfonimide salt and N-methyl, N-propyl-N-methylpyrrolidine bistrifluoro methanesulfonimide salt; 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 modifier comprises one or more of ionic liquid, dimethyl sulfoxide, ethylene glycol, potassium hydroxide, concentrated sulfuric acid, or ionic liquid. The organic thermoelectric material comprises 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, the ionic liquid and the cross-linking agent in the step S1, blending, and fully stirring and dispersing to obtain an ionic liquid gel mixed solution;
s3, adopting a spinning method: performing pregelatinization treatment on the ionic liquid gel mixed solution in the step S2, wherein the pregelatinization treatment time is 0.5-3 h, and the temperature is 25-90 ℃; extruding the fiber core layer into a mold by using an extrusion needle, and finally performing gelation treatment to obtain 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 chamfering range of the needle head is 10-60 degrees;
or a coating method is adopted: immersing the pretreated fiber substrate in the ionic liquid gel mixed solution in the step S2, so that the ionic liquid gel forms a uniform coating on the surface of the fiber substrate; 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.
When the spinning method is adopted, the concentration of the spinning solution is controlled in a proper range by controlling the pre-gelatinization temperature and time of the spinning solution in the spinning process, so that the effect of the shearing force field on the induction of the orientation can be improved, the relaxation of the orientation structure is reduced, and the formation of a fiber compact structure is promoted; meanwhile, the weak interactions such as hydrogen bonds, van der Waals force and the like in the gel can be regulated by controlling the temperature, so that the mechanical strength and the thermal stability of the prepared fiber are further improved, and the fiber has excellent thermoelectric property and mechanical property. By controlling the diameter, the circumferential inclination angle and the stretching ratio of the extrusion needle head, the induced orientation effect of the shearing force field on the spinning solution extrusion process is enhanced, so that the prepared fiber has an orientation structure, and the problem of poor conductivity caused by low order of ionic liquid in the organic thermoelectric material is solved.
When a coating method is adopted, elastic fibers with unrecoverable deformation capacity can be selected as the fiber base material, and the inorganic nano filler is an anisotropic structure filler; when the ionic liquid gel fiber core layer is prepared, the fiber soaked in the ionic liquid gel solution for the first time is subjected to stretching treatment, and the inorganic nano filler with an anisotropic structure can generate an orientation effect, and the orientation structure is beneficial to improving the ion conversion rate in the ionic liquid gel coating, so that the ionic conductivity is improved, and the thermal electric performance of the composite fiber is improved; and the fiber matrix can generate irreversible slippage of macromolecular chains, and gaps among molecules are generated, so that organic macromolecules in the ionic liquid gel coating can better interact with a base material, the combination of the coating and the matrix is enhanced, and the mechanical property of the fiber is improved. It should be noted that, the drafting treatment is only performed when the fiber base material is soaked for the first time, and then normal soaking-drying is performed, so that a stronger connection area can be formed between the fiber base material and the ionic liquid gel, thereby improving the strength of the composite fiber, and improving the integrity of the composite fiber, so that 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 substrate can be increased, and the combination of the organic polymer and the fiber substrate is promoted. The fiber base material is subjected to repeated soaking-drying treatment 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 the hydrophilic fiber, and the organic polymer of the ionic liquid gel is also hydrophilic and contains polar functional groups, so that the composite firmness of the ionic liquid gel and the fiber base material is improved through a similar compatibility principle; during the compounding, the polar functional groups in the organic polymer and the polar functional groups in the fiber base material are subjected to bonding reaction, so that 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 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.
A preparation method of a high-performance ion-electron composite thermoelectric fiber comprises the step of uniformly coating an electron 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, 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 performs thermoelectric conversion by utilizing a temperature gradient, the temperature is generally fluctuated, and the ionic liquid fiber core layer can perform thermoelectric conversion by utilizing the temperature fluctuation; meanwhile, the temperature change can cause the ion accumulation of the ionic liquid fiber core layer so as to generate higher thermal voltage, and the ion accumulation of the ionic liquid fiber core layer can break the charge balance of the electronic thermoelectric coating, so that the thermoelectric conversion efficiency is further improved. The ionic liquid fiber core layer and the electronic thermoelectric coating are matched in a cooperative manner, so that the thermal 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 morphology, the section, the structure of the coating, the interface combination between the ion layer and the electronic 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 practical applications of ion-electron composite thermoelectric fibers, ion accumulation occurs in the ionic liquid gel fiber core layer due to thermoionic diffusion (Soret effect); the electron thermoelectric coating has higher electric conductivity and lower thermoelectric voltage than the ionic liquid gel fiber core layer, so that charges in the electron thermoelectric coating can migrate to the interface between the ionic liquid gel fiber core layer and the electron thermoelectric coating to compensate ions accumulated in the ionic liquid gel fiber core layer; thus, a capacitance interface is formed, and an alternating current signal can be transmitted, so that the inner layer and the outer layer of the ion-electron composite thermoelectric fiber form a passage, and the thermoelectric performance of the whole 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 the ionic liquid gel fiber core layer; the ionic liquid gel fiber core layer is an organic-inorganic hybrid network structure with an orientation structure, and comprises the following components in percentage by mass: 80% of 1-ethyl-3-methylimidazole dicyandiamide salt, 15% of polyethylene oxide and 5% of attapulgite filler with anisotropy; the electronic thermoelectric coating comprises PEDOT, PSS, 2% of ionic liquid 1-ethyl-3-methylimidazole dicyandiamide 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, the 1-ethyl-3-methylimidazole dicyandiamide salt and the cross-linking agent polyethylene glycol in the step S11, blending, and fully stirring and dispersing to obtain an ionic liquid gel mixed solution;
s13, adopting a spinning method: performing pre-gelatinization treatment on the ionic liquid gel mixed solution in the step S12, wherein the pre-gelatinization treatment time is 2 hours, and the temperature is 70 ℃; extruding the fiber core layer into a mold by using an extrusion needle, and finally performing gelation treatment to obtain an ionic liquid gel fiber core layer; wherein the diameter of the hole of the extrusion needle head is 1mm, and the chamfer angle is 45 degrees;
s2, uniformly coating an electronic thermoelectric coating containing modifier dimethyl sulfoxide and ionic liquid 1-ethyl-3-methylimidazole dicyan amine salt on the surface of the ionic liquid gel fiber core layer, wherein the thickness of the electronic thermoelectric coating is 2 mu m, and thus the high-performance ion-electronic 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 prepared in this embodiment, and it can be seen from the figure that the inorganic nano-filler 1 in the ionic liquid gel fiber core layer 2 has a good orientation effect, and the electron thermoelectric coating 3 is coated outside.
Examples 2 to 3
Examples 2 to 3 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 thickness of the electron thermoelectric coating layer in the composite thermoelectric fiber is 0.5 μm and 20 μm, respectively; the remainder is substantially the same as that of example 1, and will not be described in detail here.
Example 4
The embodiment provides a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, and compared with the embodiment 1, the fiber is characterized by comprising the following components in percentage by mass: 60% of 1-ethyl-3-methylimidazole dicyandiamide salt, 30% of polyethylene oxide and 10% of nano attapulgite filler with anisotropy; the remainder is substantially the same as that of example 1, and will not be described in detail here.
Example 5
The embodiment provides a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, and compared with the embodiment 1, the fiber is characterized by comprising the following components in percentage by mass: 80% of 1-ethyl-3-methylimidazole dicyandiamide salt, 5% of polyethylene oxide and 15% of nano attapulgite filler with anisotropy; the remainder is substantially the same as that of example 1, and will not be described in detail here.
Comparative example 1
Comparative example 1 improved a composite thermoelectric fiber and method of making the same, except that the fiber was only an ionic liquid gel fiber core layer, not coated with an electronic thermoelectric coating, and the remainder was substantially the same as example 1, and no further description is given here.
Comparative example 2
The comparative example 2 improves a composite thermoelectric fiber and a method for preparing the same, and is different from the example 1 in that no inorganic nano filler is added in the liquid ion nano fiber core layer of the composite thermoelectric fiber, and the rest is substantially the same as the example 1, and no description is repeated here.
Comparative example 3
The difference of the composite thermoelectric fiber and the preparation method thereof in comparative example 3 is that the inorganic nano filler added in the liquid ion nano fiber core layer of the composite thermoelectric fiber is attapulgite particles with uniform shape, and the rest is the same as that in example 1, and is not described here.
Comparative example 4
Comparative example 4 provides a composite thermoelectric fiber and a method for preparing the same, which is different from example 1 in that the ionic liquid 1-ethyl-3-methylimidazole dicyano amine salt is not added to the electronic thermoelectric coating, and the remainder is substantially the same as example 1, and no description is repeated here.
The high performance ion-electron composite thermoelectric fibers prepared in examples 1 to 5 and comparative examples 1 to 4 were tested for thermoelectric performance and mechanical properties, and the results of the respective indexes obtained are shown in the following table.
Table 1 index of composite thermoelectric fibers produced 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. The research shows that the higher the surface electron coverage rate of the composite thermoelectric fiber is, the larger the resistance of the thermoelectric layer is, and the higher the output voltage and the power density of the composite fiber are facilitated. Meanwhile, the thickness of the electronic thermoelectric layer on the surface of the composite thermoelectric fiber also affects the mechanical properties of the composite 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 electron thermoelectric layer is smaller, the complete electron thermoelectric coating can not be formed on the surface of the fiber, so that the coverage rate of the electron thermoelectric coating is affected, and the output voltage and power are affected. However, when the electron thermoelectric thickness is too thick, the resistance of the surface electron layer is reduced, and the output voltage and power are reduced, but the tensile strength of the composite fiber as a whole is improved.
From the above table, it can be seen that decreasing the content of ionic liquid, the seebeck coefficient of the ionic liquid gel fiber decreases, but the tensile strength and elongation at break increase; the content of the anisotropic nano filler is properly increased, the thermoelectric property and the mechanical property of the composite thermoelectric fiber are both increased, but the excessive addition amount can lead to the agglomeration of nano particles, thereby affecting the mechanical property. As is clear from comparative examples 1 to 4 of examples 1 to 5, after the ion thermoelectric material and the electron thermoelectric material are compounded, the thermoelectric performance of the composite thermoelectric fiber is higher than that of the single-component thermoelectric material; the addition of anisotropic nanoparticles in the ionic liquid and the addition of ionic liquid in the electronic thermoelectric material both increase the thermoelectric and mechanical properties of the ion-electronic composite fiber; the halloysite nano particles with uniform shapes are added, and an orientation effect is not generated in the spinning process, so that the thermoelectric performance 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 in step S13, the time and temperature of the pregelatinization treatment, and the parameters of the needle are shown in the following table; the remainder is substantially the same as that of example 1, and will not be described in detail here.
TABLE 2 parameters of the pregelatinization treatments and the showerheads of examples 6 to 13 and comparative examples 5 to 6
The high performance ion-electron composite thermoelectric fibers prepared in examples 6 to 13 were tested for thermoelectric properties and mechanical properties, and the results of the respective indexes obtained are shown in the following table.
Table 3 indicators of composite thermoelectric fibers produced in examples 6 to 13
As is clear from Table 3, the shorter the pregelatinization treatment time, the longer the fiber curing and molding time was, which resulted in the partial unorientation of the nanoparticles, affecting the thermoelectric properties of the ionic liquid gel fibers and thus the thermoelectric properties of the composite thermoelectric fibers, as obtained in examples 6 to 9. The pre-gelation treatment time is too long, so that the curing of the ionic liquid gel can be accelerated, the shearing stress orientation effect is reduced, and meanwhile, the thermoelectric performance of the composite thermoelectric fiber can be influenced. Too low a pregelatinization temperature can result in the ionic liquid gel fibers taking longer to form, thereby resulting in partial unorientation of the nanoparticles, decreasing the degree of orientation, affecting the thermoelectric properties of the ionic liquid gel fibers, and thus affecting the thermoelectric properties of the composite thermoelectric fibers. The high pregelatinization temperature can influence the performance of the high molecular polymer, accelerate the solidification of the ionic liquid gel, reduce the orientation effect of the shearing stress and influence the thermoelectric performance of the composite thermoelectric fiber.
In examples 10 to 11, the smaller the diameter of the ionic liquid gel fiber, the stronger the shearing orientation effect is applied, and thus the orientation of the anisotropic nanoparticles is improved, and the thermoelectric performance and tensile strength of the fiber are increased. In the embodiments 12 to 13, too small inclination angle of the spray nozzle can generate a flowing dead angle, so that the shearing force applied to the spinning solution is uneven, and the shearing orientation effect is reduced, thereby influencing the thermoelectric performance 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 nano particles is reduced, and the thermoelectric and mechanical properties of the fiber are affected. In comparative examples 5 to 6, the pre-gelation treatment temperature was too high or the pre-gelation treatment time was too long, which resulted in a transition of pre-gelation, and the hardness was large, making it difficult to mold the gel fiber later.
Example 14
The embodiment provides a high-performance ion-electron composite thermoelectric fiber and a preparation method thereof, which are different from embodiment 1 in that in step S13 of preparing an ionic liquid gel fiber core layer, a coating method is adopted: immersing the pretreated fiber substrate in the ionic liquid gel mixed solution in the step S2 to form a uniform ionic liquid gel coating on the surface of the fiber substrate, wherein the thickness of the coating is 20 mu m; wherein the concentration of the ionic liquid gel mixed solution is 10%, the fiber base material is elastic fiber with unrecoverable deformation capability, and the fiber base material is subjected to drafting treatment when being soaked in the ionic liquid gel solution for the first time; the remainder is substantially the same as that of example 1, and will not be described in detail here.
Referring to fig. 2, fig. 2 is a schematic diagram of the internal structure of the high-performance ion-electron composite thermoelectric fiber prepared in this embodiment, and it can be seen from the figure that the inorganic nano-filler 1 in the ionic liquid gel coating layer has a good orientation effect, the fiber substrate 4 and the ionic liquid gel coating layer form an ionic liquid gel fiber core layer 2, and the exterior of the ionic liquid gel fiber core layer is coated with an electron thermoelectric coating layer 3.
Example 15
The embodiment provides a high performance ion-electron composite thermoelectric fiber and a preparation method thereof, which is different from embodiment 14 in that in step S13 of preparing an ionic liquid gel fiber core layer, a fiber base material is a common fiber and is not subjected to drafting treatment when the fiber base material is soaked in the ionic liquid gel solution for the first time; the remainder is substantially the same as that of example 1, and will not be described in detail here.
The high performance ion-electron composite thermoelectric fibers prepared in examples 14 to 15 were tested for thermoelectric properties and mechanical properties, and the results of the respective indexes obtained are shown in the following table.
Table 4 index of composite thermoelectric fibers prepared in examples 14 to 15
As can be seen from table 4, ion-electron composite hot spot fibers can also be prepared by applying an ionic liquid gel followed by an electron thermoelectric coating using commercial fibers as a substrate. However, the presence of the non-conductive fibrous base material affects the thermoelectric properties of the composite fiber, and therefore the power density is somewhat reduced. Furthermore, the data of comparative examples 14 and 15 show that, after addition and orientation of anisotropic nanofillers in the ionic liquid gel coating, higher thermoelectric and mechanical properties are obtained.
In summary, the high-performance ion-electron composite thermoelectric fiber and the preparation method thereof provided by the invention comprise an ionic liquid gel fiber core layer and an electron thermoelectric coating the ionic liquid gel fiber core layer; the components of the ionic liquid gel fiber core layer comprise: 50-90% of ionic liquid, 7-47% of organic polymer and 3-30% of inorganic nano filler with anisotropy; the electron thermoelectric coating includes an electron thermoelectric material. The components, 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 by compounding the ionic liquid gel fiber and the electronic thermoelectric coating, so that 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 performs thermal-electric conversion by utilizing a temperature gradient, the temperature is generally fluctuated, and the ionic liquid fiber core layer performs thermoelectric conversion by utilizing temperature fluctuation so as to improve thermal voltage and thermoelectric power; the mechanical property and the thermoelectric property of the ion-electron composite thermoelectric fiber are synergistically improved, so that the ion-electron composite thermoelectric fiber is more suitable for preparing high-performance wearable thermoelectric materials.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The high-performance ion-electron composite thermoelectric fiber is characterized by comprising 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 is provided with an organic-inorganic hybrid network structure with an orientation structure, and comprises the following components in percentage by mass: 50 The inorganic nano-filler comprises (by weight) ionic liquid accounting for 90%, organic polymer accounting for 7% -47%, and inorganic nano-filler accounting for 3% -30% of the inorganic nano-filler; the electron thermoelectric coating comprises an electron thermoelectric material and an ionic liquid, wherein the ionic liquid is used for preparing the electron thermoelectric materialThe addition amount of the catalyst 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; the inorganic nanofiller comprises nano SiO 2 、TiO 2 One or more of halloysite nanotubes, attapulgite, and graphene oxide; the organic thermoelectric material comprises one of polypyrrole and polythiophene organic matters.
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 a structure with shape anisotropy; the organic polymer is a hydrophilic organic polymer containing polar functional groups.
3. The high performance ion-electron composite thermoelectric fiber according to claim 1, wherein the thickness of the electron thermoelectric coating is 0.5-20 μm; the electronic thermoelectric coating also comprises a modifier to regulate the performance of the electronic thermoelectric coating and promote the interface combination of the electronic thermoelectric coating and the ionic liquid gel fiber core layer.
4. 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 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, and fully stirring and dispersing to obtain an ionic liquid gel mixed solution;
s3, adopting a spinning method: performing pre-gelatinization treatment on the ionic liquid gel mixed solution in the step S2, wherein the pre-gelatinization treatment time is 0.5-3 h, and the temperature is 25-90 ℃; extruding the fiber core layer into a die by using an extrusion needle, and finally, carrying out gelation treatment to obtain the ionic liquid gel fiber core layer;
or a coating method is adopted: immersing the pretreated fiber substrate in the ionic liquid gel mixed solution in the step S2, so that the ionic liquid gel forms a uniform coating on the surface of the fiber substrate; 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.
5. The high performance ion-electron composite thermoelectric fiber according to claim 4, wherein in step S3, when the spinning method is adopted, the diameter of the hole of the extrusion needle is in the range of 0.1-2 mm, and the chamfer angle of the needle is in the range of 10-60 °; when the coating method is adopted, the concentration of the ionic liquid gel mixed solution is 5% -20%.
6. The high performance ion-electron composite thermoelectric fiber according to claim 1, wherein the ionic liquid comprises one or more of 1-ethyl-3-methylimidazole dicyano amine salt, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt, N-methyl, propylpyrrolidine bistrifluoromethanesulfonimide salt; the organic polymer comprises one or more of poly (vinylidene fluoride-co-hexafluoropropylene), polyethylene oxide, cellulose, polyvinyl alcohol and polyurethane.
7. The high performance ion-electron composite thermoelectric fiber according to claim 3, wherein the modifier comprises one or more of dimethyl sulfoxide, ethylene glycol, potassium hydroxide, concentrated sulfuric acid.
8. The high performance ion-electron composite thermoelectric fiber according to claim 4, wherein in step S1, the surfactant comprises 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 includes one of dimethyl sulfoxide, acetone or dimethylformamide; the cross-linking agent comprises one or more of polyethylene glycol, polyethylene glycol diacrylate and formic acid.
9. A method for preparing the high-performance ion-electron composite thermoelectric fiber according to any one of claims 1 to 8, which is characterized in that an electron thermoelectric coating containing ionic liquid is uniformly coated on the surface of an ionic liquid gel fiber core layer, so that the high-performance ion-electron composite thermoelectric fiber is obtained.
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