CN117750866A - Three-layer carbon nanotube thermoelectric yarn and preparation method and application thereof - Google Patents
Three-layer carbon nanotube thermoelectric yarn and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 114
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 46
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- 238000001035 drying Methods 0.000 claims abstract description 28
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- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 229920005570 flexible polymer Polymers 0.000 claims abstract description 14
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- 238000012986 modification Methods 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 229920002635 polyurethane Polymers 0.000 claims description 34
- 239000004814 polyurethane Substances 0.000 claims description 34
- 239000004065 semiconductor Substances 0.000 claims description 28
- 229910052797 bismuth Inorganic materials 0.000 claims description 27
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 27
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229920002873 Polyethylenimine Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims description 2
- MFIWAIVSOUGHLI-UHFFFAOYSA-N selenium;tin Chemical compound [Sn]=[Se] MFIWAIVSOUGHLI-UHFFFAOYSA-N 0.000 claims description 2
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 2
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- 239000011241 protective layer Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000009941 weaving Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
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- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009954 braiding Methods 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 239000002079 double walled nanotube Substances 0.000 description 1
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- 238000004134 energy conservation Methods 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Abstract
The invention relates to a three-layer carbon nanotube thermoelectric yarn and a preparation method and application thereof, and belongs to the technical field of spinning. S1, carrying out sectional N-type thermoelectric modification on a carbon nano tube yarn through a modified polymer to obtain a modified carbon nano tube yarn; s2, coating the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid on the modified carbon nano tube yarn of the S1 to form P-type and N-type alternating thermoelectric units, coating conductive silver paste on the alternating nodes to form electrode nodes, and drying to obtain the double-layer carbon nano tube thermoelectric yarn; s3, dipping the double-layer carbon nano tube thermoelectric yarn of the S2 into a flexible polymer solution, and drying to obtain the carbon nano tube thermoelectric yarn with a three-layer structure. The air permeability, the stretchability and the comfort of the obtained elastic thermoelectric fabric are obviously improved compared with those of the thermoelectric fabric prepared by depositing, coating and spraying thermoelectric materials on the fabric at present.
Description
Technical Field
The invention belongs to the technical field of textile, and particularly relates to a carbon nano tube thermoelectric yarn with a three-layer structure, and a preparation method and application thereof.
Background
With the rapid development of flexible electronic technology, wearable intelligent electronic products are increasingly penetrating into daily life, and energy harvesting techniques are widely studied. The thermoelectric material is a material capable of converting heat energy into electric energy or converting electric energy into heat energy, and is one of important materials for realizing energy conversion, energy conservation and environmental protection, so that the thermoelectric material is prepared into thermoelectric fibers and fabrics, and can directly utilize the heat of a human body to provide a new solution for power supply of wearable electronic products.
In the field of thermoelectric materials, the preparation of thermoelectric yarns using CNT fibers has become a research hotspot in the thermoelectric field due to the excellent thermoelectric properties of Carbon Nanotube (CNT) materials, particularly CNT fibers, due to their high conductivity, flexibility, light weight and expandability. At present, certain progress has been made in the preparation technology of CNT thermoelectric yarns by means of wet spinning, electrostatic spinning and the like. Meanwhile, another semiconductor thermoelectric material is a popular research field of thermoelectric materials because of its commercial mass production and outstanding thermoelectric performance at room temperature. Therefore, the CNT fiber and the semiconductor thermoelectric material are compounded to prepare the flexible thermoelectric yarn, and then the flexible thermoelectric yarn is further combined with the elastic yarn to develop the comfortable, breathable and stretchable thermoelectric fabric, so that the flexible thermoelectric yarn has important significance in flexible energy supply.
Patent CN 216650023U discloses a p-type and n-type integrated wearable thermoelectric device, which is composed of a p-type carbon nanotube fiber substrate, n-type thermoelectric units and a fabric body, wherein the n-type thermoelectric units are arranged on the p-type carbon nanotube fiber substrate at equal intervals to form p-type and n-type alternately existing integrated thermoelectric fibers, and the p-type and n-type alternately existing integrated thermoelectric fibers are vertically woven in the fiber direction of the fabric body to form the p-type and n-type integrated wearable thermoelectric device. However, the thermoelectric performance is not further improved by using the carbon nanotube fiber itself as the P-type; in addition, the carbon nano tube fiber is modified into the N-type thermoelectric yarn by polyethyleneimine, so that the stability in air can not be ensured, and the whole fabric has no elasticity.
PCT/US2016/055062 discloses a semiconductor wire braided low heat flux flexible thermoelectric generator. The thermoelectric string has a repeating structure of (metal) - (p-type semiconductor) - (metal) - (n-type semiconductor) material and is formulated with a continuous structure forming a module. In this woven structure, the thermoelectric strings are warp yarns and the insulating strings are weft yarns. The p-type and n-type stripes are aligned to the same size. The metal terminals at the ends of the strings are connected in series in a serpentine pattern to provide electrical connection. Two layers of electrically insulating film laminated on top and bottom of such a woven structure conduct surface heat to the metal junctions of the hot and cold sides. However, the upper and lower surfaces of the device are integrally covered with a layer of insulating film, the whole device is a sheet type thermoelectric device, and the device has a non-woven structure and poor air permeability and comfort; bismuth telluride materials wrapped on the inner core fibers have low flexibility and are easy to fall off after being dried, and the stability of the overall thermoelectric performance is insufficient.
Other development technologies related to thermoelectric fibers are mainly to mix carbon nanotube powder with thermoelectric powder materials, and prepare the thermoelectric fibers by using a spinning technology, so that the operation is complex, the output is small, and wider application is difficult to realize; or spraying and dipping a solvent prepared by using a thermoelectric powder material on a nanofiber membrane prepared by electrostatic spinning, and loading the thermoelectric material on the surface of the fiber, wherein the thermoelectric fabric prepared by the method is not a traditional fabric structure, but a thermoelectric membrane obtained by unordered arrangement of nanofibers has certain challenges in weaving, wearing and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a three-layer carbon nanotube thermoelectric yarn and a preparation method and application thereof. The carbon nano tube thermoelectric yarn with the three-layer structure takes carbon nano tube fibers as an inner core; the outer layer is wrapped with a P-type and N-type composite thermoelectric material with high thermoelectric performance, and the P-type and N-type composite thermoelectric material has excellent flexibility, braiding property and thermoelectric performance; and a thin protective film is prepared on the surface so as to improve the stability of the appearance and ensure the overall performance of the yarn. And then the carbon nano tube thermoelectric yarn with a three-layer structure and the elastic yarn are mixed and woven, so that the air permeability, the stretchability and the comfort of the obtained elastic thermoelectric fabric are obviously improved compared with those of the thermoelectric fabric prepared by depositing, coating and spraying thermoelectric materials on the fabric at present.
The first object of the present invention is to provide a method for preparing a three-layer carbon nanotube thermoelectric yarn, comprising the steps of,
s1, performing segmented N-type thermoelectric modification on a carbon nano tube yarn through a modified polymer to obtain a modified carbon nano tube yarn; the modified polymer is selected from one or more of polyethylenimine, poly (vinyl pyrrolidone) and poly (vinyl chloride);
s2, coating the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid on the modified carbon nano tube yarn in the S1 to form P-type and N-type alternating thermoelectric units, coating conductive silver paste on the alternating nodes to form electrode nodes, and drying to obtain the double-layer carbon nano tube thermoelectric yarn; the P-type composite thermoelectric precursor liquid comprises 70-90% of P-type semiconductor thermoelectric material, 2.5-8% of carbon nano tube and 7-23% of flexible polymer solution by mass fraction; the N-type composite thermoelectric precursor liquid comprises 70-95% of N-type semiconductor thermoelectric material and 5-30% of flexible polymer solution by mass fraction;
s3, dipping the double-layer carbon nano tube thermoelectric yarn in the flexible polymer solution, and drying to obtain the carbon nano tube thermoelectric yarn with a three-layer structure;
wherein the flexible polymer solution comprises a polymer and a solvent; the polymer is selected from the group consisting of polyurethanes.
In one embodiment of the present invention, in S2, the P-type semiconductor thermoelectric material and the N-type semiconductor thermoelectric material are independently selected from one or more of bismuth telluride, lead telluride, silicon germanium, tin selenide, and copper selenide.
In one embodiment of the present invention, in S2, the particle sizes of the P-type semiconductor thermoelectric material and the N-type semiconductor thermoelectric material are independently 350 mesh to 400 mesh.
In one embodiment of the present invention, in S2, the P-type thermoelectric unit and the N-type thermoelectric unit have a length of 6mm to 20mm and the electrode node has a length of 3mm to 10mm.
In one embodiment of the present invention, in S2, the drying is performed at a temperature of 50 ℃ to 80 ℃ for a time of 1h to 3h.
In one embodiment of the present invention, in S3, the temperature of the drying is 60 ℃ to 80 ℃ for 3h to 4h.
In one embodiment of the invention, the concentration of the flexible polymer solution is 5wt% to 15wt%.
In one embodiment of the invention, the solvent is selected from dimethylformamide.
The second object of the invention is to provide a carbon nano tube thermoelectric yarn with a three-layer structure prepared by the preparation method.
The third object of the present invention is to provide an elastic thermoelectric fabric prepared from the carbon nanotube thermoelectric yarn of the three-layer structure.
In one embodiment of the present invention, the elastic thermoelectric fabric uses the carbon nanotube thermoelectric yarn with the three-layer structure as a weft yarn and the elastic yarn as a warp yarn.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The CNT adopted by the three-layer-structure carbon nano tube thermoelectric yarn has excellent conductivity; the semiconductor thermoelectric material has excellent thermoelectric performance at room temperature; the preparation process of the outer flexible protective layer is simple, and the wearing performance of the yarn is greatly improved. Based on the three important material components, the final thermoelectric yarn has good synergistic effect among conductivity, thermoelectric property and serviceability.
(2) According to the preparation method, the CNT yarn is used as a substrate, and the CNT yarn can be subjected to P/N modification through a simple process; then compounding the semiconductor thermoelectric material and the flexible polymer material on the CNT yarns through a coating process, and improving the flexibility of the semiconductor material and ensuring good adhesion of the semiconductor thermoelectric material and the CNT yarns by utilizing the flexible polymer material; furthermore, the flexible protective layer is sprayed on the outer layer of the yarn to prevent the semiconductor thermoelectric material from falling off and improve the overall wear resistance, insulation safety and braiding performance of the thermoelectric yarn; finally, the elastic thermoelectric fabric with comfort and high practicability can be obtained through a simple plain weaving process, and the further development of thermoelectric technology in the field of wearable power supply is promoted.
(3) The thermoelectric fabric disclosed by the invention has strong operability, combines a carbon material and a semiconductor thermoelectric material, has good thermoelectric performance, can more efficiently utilize the temperature difference between human skin and the external environment in the wearing process, converts heat energy into electric energy, and has wide application prospects in the environment-friendly fields of waste heat recovery, human latent heat reutilization and the like.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a schematic diagram of a three-layer carbon nanotube thermoelectric yarn according to the present invention;
FIG. 2 is a schematic plan view of an elastic thermoelectric fabric of the present invention;
FIG. 3 shows the electrical resistance of the double-layered carbon nanotube thermoelectric fiber of examples 1-4 of the present invention;
FIG. 4 shows the electrical resistance of the double-layered carbon nanotube thermoelectric fiber of example 4, comparative examples 1-2 of the present invention;
FIG. 5 is a surface morphology of the double-layer carbon nanotube thermoelectric fiber of examples 1-4 of the present invention; wherein, the upper left is example 1, the upper right is example 2, the lower left is example 3, and the lower right is example 4;
FIG. 6 is a cross-sectional morphology of a double-walled carbon nanotube thermoelectric fiber of example 4 of the present invention;
reference numerals illustrate: 1-elastic yarn, 2-P type thermoelectric unit, 3-N type thermoelectric unit, 4-electrode node, 5-carbon nanotube yarn, 6-composite thermoelectric material and 7-flexible protective layer.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In the present invention, the polyurethane solution used in the examples is a polyurethane solution having a concentration of 10wt% obtained by dissolving the TPU elastomeric polymer in Dimethylformamide (DMF), unless otherwise specified.
Example 1
Referring to fig. 1-2, the preparation of the carbon nanotube thermoelectric yarn and the elastic thermoelectric fabric with the three-layer structure of the present invention specifically comprises the following steps:
s1, mixing P-type 400-mesh bismuth telluride powder, carbon nanotubes and polyurethane solution to obtain P-type composite thermoelectric precursor liquid; wherein, the concentration of bismuth telluride is 75wt%, the concentration of carbon nano tube is 6wt%, and the concentration of polyurethane solution is 19wt%;
s2, mixing N-type 400-mesh bismuth telluride powder and polyurethane solution to obtain N-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 75wt% and the concentration of polyurethane solution is 25wt%;
s3, coating and drying the carbon nano tube yarns 5 in a modified area by using a polyethyleneimine ethanol solution with the concentration of 10 weight percent to prevent redundant modification positions; coating P-type composite thermoelectric precursor liquid and N-type composite thermoelectric precursor liquid (composite thermoelectric material 6) on a modified region of the carbon nanotube yarn 5 to form equidistant P-type and N-type alternating thermoelectric units, coating conductive silver paste on the alternating nodes to form electrode nodes 4, and drying for 1h at 50 ℃ in a blast oven to obtain double-layer carbon nanotube thermoelectric yarn; the lengths of the P-type thermoelectric unit 2 and the N-type thermoelectric unit 3 are 6mm, and the length of the electrode node 4 is 3mm; the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid are coated for 3 times;
s4, soaking the double-layer carbon nano tube thermoelectric yarn in polyurethane solution to form a flexible protective layer 7, and drying the flexible protective layer at 80 ℃ for 3 hours in an oven to obtain the carbon nano tube thermoelectric yarn with a three-layer structure;
s5, weaving the carbon nano tube thermoelectric yarn with the three-layer structure serving as weft yarns and the elastic yarn 1 serving as warp yarns to finally obtain the elastic thermoelectric fabric with stable form and good performance.
Example 2
The invention relates to preparation of a three-layer-structured carbon nanotube thermoelectric yarn and an elastic thermoelectric fabric, which specifically comprises the following steps:
s1, mixing P-type 400-mesh bismuth telluride powder, carbon nanotubes and polyurethane solution to obtain P-type composite thermoelectric precursor liquid; wherein, the concentration of bismuth telluride is 80wt%, the concentration of carbon nano tube is 5wt%, and the concentration of polyurethane solution is 15wt%;
s2, mixing N-type 400-mesh bismuth telluride powder and polyurethane solution to obtain N-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 80wt%, and the concentration of polyurethane solution is 20wt%;
s3, coating and drying the carbon nano tube yarns in a modified area by using a polyethyleneimine ethanol solution with the concentration of 10wt%, so as to prevent redundant modification positions; coating the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid on a modified region of the carbon nanotube yarn to form equidistant P-type and N-type alternating thermoelectric units, coating conductive silver paste on the alternating nodes to form electrode nodes, and drying for 1h at 50 ℃ in a blast oven to obtain the double-layer carbon nanotube thermoelectric yarn; the length of the P-type thermoelectric unit and the N-type thermoelectric unit is 6mm, and the length of the electrode node is 3mm; the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid are coated for 3 times;
s4, soaking the double-layer carbon nano tube thermoelectric yarn in polyurethane solution to form a flexible protective layer, and drying the flexible protective layer at 80 ℃ for 3 hours in an oven to obtain the carbon nano tube thermoelectric yarn with a three-layer structure;
s5, weaving the carbon nano tube thermoelectric yarns with the three-layer structure serving as weft yarns and the elastic yarns serving as warp yarns, and finally obtaining the elastic thermoelectric fabric with stable form and good performance.
Example 3
The invention relates to preparation of a three-layer-structured carbon nanotube thermoelectric yarn and an elastic thermoelectric fabric, which specifically comprises the following steps:
s1, mixing P-type 400-mesh bismuth telluride powder, carbon nanotubes and polyurethane solution to obtain P-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 85wt%, the concentration of carbon nano tube is 4wt%, and the concentration of polyurethane solution is 11wt%;
s2, mixing N-type 400-mesh bismuth telluride powder and polyurethane solution to obtain N-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 85wt%, and the concentration of polyurethane solution is 15wt%;
s3, coating and drying the carbon nano tube yarns in a modified area by using a polyethyleneimine ethanol solution with the concentration of 10wt%, so as to prevent redundant modification positions; coating the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid on a modified region of the carbon nanotube yarn to form equidistant P-type and N-type alternating thermoelectric units, coating conductive silver paste on the alternating nodes to form electrode nodes, and drying for 1h at 50 ℃ in a blast oven to obtain the double-layer carbon nanotube thermoelectric yarn; the length of the P-type thermoelectric unit and the N-type thermoelectric unit is 6mm, and the length of the electrode node is 3mm; the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid are coated for 3 times;
s4, soaking the double-layer carbon nano tube thermoelectric yarn in polyurethane solution to form a flexible protective layer, and drying the flexible protective layer at 80 ℃ for 3 hours in an oven to obtain the carbon nano tube thermoelectric yarn with a three-layer structure;
s5, weaving the carbon nano tube thermoelectric yarns with the three-layer structure serving as weft yarns and the elastic yarns serving as warp yarns, and finally obtaining the elastic thermoelectric fabric with stable form and good performance.
Example 4
The invention relates to preparation of a three-layer-structured carbon nanotube thermoelectric yarn and an elastic thermoelectric fabric, which specifically comprises the following steps:
s1, mixing P-type 400-mesh bismuth telluride powder, carbon nanotubes and polyurethane solution to obtain P-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 90wt%, the concentration of carbon nano tube is 2.5wt%, and the concentration of polyurethane solution is 7.5wt%;
s2, mixing N-type 400-mesh bismuth telluride powder and polyurethane solution to obtain N-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 90wt%, and the concentration of polyurethane solution is 10wt%;
s3, coating and drying the carbon nano tube yarns in a modified area by using a polyethyleneimine ethanol solution with the concentration of 10wt%, so as to prevent redundant modification positions; coating the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid on a modified region of the carbon nanotube yarn to form equidistant P-type and N-type alternating thermoelectric units, coating conductive silver paste on the alternating nodes to form electrode nodes, and drying for 1h at 50 ℃ in a blast oven to obtain the double-layer carbon nanotube thermoelectric yarn; the length of the P-type thermoelectric unit and the N-type thermoelectric unit is 6mm, and the length of the electrode node is 3mm; the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid are coated for 3 times;
s4, soaking the double-layer carbon nano tube thermoelectric yarn in polyurethane solution to form a flexible protective layer, and drying the flexible protective layer at 80 ℃ for 3 hours in an oven to obtain the carbon nano tube thermoelectric yarn with a three-layer structure;
s5, weaving the carbon nano tube thermoelectric yarns with the three-layer structure serving as weft yarns and the elastic yarns serving as warp yarns, and finally obtaining the elastic thermoelectric fabric with stable form and good performance.
Comparative example 1
The invention relates to preparation of a three-layer-structured carbon nanotube thermoelectric yarn and an elastic thermoelectric fabric, which specifically comprises the following steps:
s1, mixing P-type 200-mesh bismuth telluride powder, carbon nanotubes and polyurethane solution to obtain P-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 90wt%, the concentration of carbon nano tube is 2.5wt%, and the concentration of polyurethane solution is 7.5wt%;
s2, mixing N-type 200-mesh bismuth telluride powder and polyurethane solution to obtain N-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 90wt%, and the concentration of polyurethane solution is 10wt%;
s3, coating and drying the carbon nano tube yarns in a modified area by using a polyethyleneimine ethanol solution with the concentration of 10wt%, so as to prevent redundant modification positions; coating the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid on a modified region of the carbon nanotube yarn to form equidistant P-type and N-type alternating thermoelectric units, coating conductive silver paste on the alternating nodes to form electrode nodes, and drying for 1h at 50 ℃ in a blast oven to obtain the double-layer carbon nanotube thermoelectric yarn; the length of the P-type thermoelectric unit and the N-type thermoelectric unit is 6mm, and the length of the electrode node is 3mm; the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid are coated for 3 times;
s4, soaking the double-layer carbon nano tube thermoelectric yarn in polyurethane solution to form a flexible protective layer, and drying the flexible protective layer at 80 ℃ for 3 hours in an oven to obtain the carbon nano tube thermoelectric yarn with a three-layer structure;
s5, weaving the carbon nano tube thermoelectric yarns with the three-layer structure serving as weft yarns and the elastic yarns serving as warp yarns, and finally obtaining the elastic thermoelectric fabric with stable form and good performance.
Comparative example 2
The invention relates to preparation of a three-layer-structured carbon nanotube thermoelectric yarn and an elastic thermoelectric fabric, which specifically comprises the following steps:
s1, mixing P-type 100-mesh bismuth telluride powder, carbon nanotubes and polyurethane solution to obtain P-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 90wt%, the concentration of carbon nano tube is 2.5wt%, and the concentration of polyurethane solution is 7.5wt%;
s2, mixing N-type 100-mesh bismuth telluride powder and polyurethane solution to obtain N-type composite thermoelectric precursor liquid; wherein the concentration of bismuth telluride is 90wt%, and the concentration of polyurethane solution is 10wt%;
s3, coating and drying the carbon nano tube yarns in a modified area by using a polyethyleneimine ethanol solution with the concentration of 10wt%, so as to prevent redundant modification positions; coating the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid on a modified region of the carbon nanotube yarn to form equidistant P-type and N-type alternating thermoelectric units, coating conductive silver paste on the alternating nodes to form electrode nodes, and drying for 1h at 50 ℃ in a blast oven to obtain the double-layer carbon nanotube thermoelectric yarn; the length of the P-type thermoelectric unit and the N-type thermoelectric unit is 6mm, and the length of the electrode node is 3mm; the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid are coated for 3 times;
s4, soaking the double-layer carbon nano tube thermoelectric yarn in polyurethane solution to form a flexible protective layer, and drying the flexible protective layer at 80 ℃ for 3 hours in an oven to obtain the carbon nano tube thermoelectric yarn with a three-layer structure;
s5, weaving the carbon nano tube thermoelectric yarns with the three-layer structure serving as weft yarns and the elastic yarns serving as warp yarns, and finally obtaining the elastic thermoelectric fabric with stable form and good performance.
Test example 1
Based on examples 1-4 and comparative examples 1-2, the double layer carbon nanotube thermoelectric yarn was subjected to resistance test, and the results are shown in fig. 3-4. As can be seen from fig. 3, as the semiconductor thermoelectric material increases, the resistance of the yarn decreases and the conductivity increases, because the increase in the ratio of the semiconductor thermoelectric material results in a decrease in the composition of the insulating flexible polymer, and thus the conductivity is improved. As can be seen from fig. 4, as the particle size of the semiconductor thermoelectric material increases, the resistance of the composite material increases, because the larger particle size powder material increases the voids within the composite material, and the effective conductive coupling path decreases, and thus the resistance increases.
Test example 2
Based on examples 1-4, electron microscopy characterization was performed on double layer carbon nanotube thermoelectric yarns, and the results are shown in fig. 5-6. As can be seen from fig. 5, as the semiconductor thermoelectric material increases, the thermoelectric material loading and density of the fiber surface also increases, and thus the conductivity is also improved. As can be seen from fig. 6, the semiconductor thermoelectric material is uniformly combined with the carbon nanotube yarn, increasing the thermoelectric performance of the yarn.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the carbon nano tube thermoelectric yarn with the three-layer structure is characterized by comprising the following steps of,
s1, performing segmented N-type thermoelectric modification on a carbon nano tube yarn through a modified polymer to obtain a modified carbon nano tube yarn; the modified polymer is selected from one or more of polyethylenimine, poly (vinyl pyrrolidone) and poly (vinyl chloride);
s2, coating the P-type composite thermoelectric precursor liquid and the N-type composite thermoelectric precursor liquid on the modified carbon nano tube yarn in the S1 to form P-type and N-type alternating thermoelectric units, coating conductive silver paste on the alternating nodes to form electrode nodes, and drying to obtain the double-layer carbon nano tube thermoelectric yarn; the P-type composite thermoelectric precursor liquid comprises 70-90% of P-type semiconductor thermoelectric material, 2.5-8% of carbon nano tube and 7-23% of flexible polymer solution by mass fraction; the N-type composite thermoelectric precursor liquid comprises 70-95% of N-type semiconductor thermoelectric material and 5-30% of flexible polymer solution by mass fraction;
s3, dipping the double-layer carbon nano tube thermoelectric yarn in the flexible polymer solution, and drying to obtain the carbon nano tube thermoelectric yarn with a three-layer structure;
wherein the flexible polymer solution comprises a polymer and a solvent; the polymer is selected from the group consisting of polyurethanes.
2. The method of claim 1, wherein in S2, the P-type semiconductor thermoelectric material and the N-type semiconductor thermoelectric material are independently selected from one or more of bismuth telluride, lead telluride, silicon germanium, tin selenide, and copper selenide.
3. The method of manufacturing a three-layered carbon nanotube thermoelectric yarn according to claim 1, wherein in S2, the particle sizes of the P-type semiconductor thermoelectric material and the N-type semiconductor thermoelectric material are independently 350 mesh to 400 mesh.
4. The method of manufacturing a three-layered carbon nanotube thermoelectric yarn according to claim 1, wherein in S2, the P-type thermoelectric unit and the N-type thermoelectric unit have a length of 6mm to 20mm and the electrode node has a length of 3mm to 10mm.
5. The method for preparing a three-layer carbon nanotube thermoelectric yarn according to claim 1, wherein in S2, the drying temperature is 50 ℃ to 80 ℃ for 1h to 3h.
6. The method for preparing a three-layer carbon nanotube thermoelectric yarn according to claim 1, wherein in S3, the drying temperature is 60 ℃ to 80 ℃ and the time is 3h to 4h.
7. The method for producing a three-layer carbon nanotube thermoelectric yarn according to claim 1, wherein the concentration of the flexible polymer solution is 5wt% to 15wt%.
8. The method for producing a three-layer carbon nanotube thermoelectric yarn according to claim 1, wherein the solvent is selected from dimethylformamide.
9. A carbon nanotube thermoelectric yarn of three-layer structure produced by the production method of any one of claims 1 to 8.
10. An elastic thermoelectric fabric, wherein the elastic thermoelectric fabric is prepared from the carbon nanotube thermoelectric yarn with the three-layer structure according to claim 9.
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