WO2016151634A1 - Élément fonctionnel présentant une structure de série cellulaire d'éléments de conversion thermoélectrique du type π, et procédé de fabrication associé - Google Patents

Élément fonctionnel présentant une structure de série cellulaire d'éléments de conversion thermoélectrique du type π, et procédé de fabrication associé Download PDF

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WO2016151634A1
WO2016151634A1 PCT/JP2015/001704 JP2015001704W WO2016151634A1 WO 2016151634 A1 WO2016151634 A1 WO 2016151634A1 JP 2015001704 W JP2015001704 W JP 2015001704W WO 2016151634 A1 WO2016151634 A1 WO 2016151634A1
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type
spun yarn
functional element
base material
insulating base
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PCT/JP2015/001704
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English (en)
Japanese (ja)
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中村　雅一
光洋 伊藤
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国立大学法人奈良先端科学技術大学院大学
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Priority to PCT/JP2015/001704 priority Critical patent/WO2016151634A1/fr
Priority to JP2017507112A priority patent/JP6529097B2/ja
Publication of WO2016151634A1 publication Critical patent/WO2016151634A1/fr

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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen

Definitions

  • the present invention relates to a functional element that can constitute a flexible thermoelectric device and a manufacturing technique thereof.
  • thermoelectric conversion technology that recovers heat and converts it into electrical energy. This is because about 70% of the total amount of energy used around us is exhausted without being utilized.
  • conventional thermoelectric elements with a high unit area price have so far been limited in use because of the difficulty of obtaining economic benefits. Therefore, the use of large area flexible thermoelectric devices that can be used at a low cost for large areas, can be applied to various shapes of surfaces, and is lightweight has the potential to broaden the application. is there. For example, it can be expected to be used as a distributed self-sustained power source in a sensor network used in a smart building or the like, or a power source for driving a small electric device by body temperature.
  • thermoelectric materials have begun to attract attention as promising thermoelectric materials, and their performance has greatly improved with the development of research.
  • many organic materials have been originally developed with the use of electrodes, transistors, and solar cell materials in mind. Therefore, the use with a thin film is common, and it is not easy to obtain a high-quality thermoelectric conversion material having a sufficient thickness necessary for a thermoelectric device.
  • ⁇ is the Seebeck coefficient
  • ⁇ is the conductivity
  • ⁇ is the thermal conductivity
  • T is the absolute temperature.
  • the power factor PF corresponds to the electric power obtained from the thermoelectric conversion material
  • the dimensionless figure of merit ZT corresponds to the energy conversion efficiency. The larger the value of both, the better the performance as the thermoelectric conversion material.
  • the conversion efficiency of the thermoelectric conversion element is ideally determined only by ZT and does not depend on the device structure.
  • thermoelectric material in a steady state with a temperature difference ⁇ T.
  • ⁇ T is not only a material but also a device structure.
  • ⁇ T increases as the thickness increases. That is, the dimensionless figure of merit ZT is a value that does not depend on the device structure, but the output and efficiency of the actual thermoelectric device greatly depend on the device structure. For example, if a device with a thermal conductivity of 0.1 W / mK is attached to an interface with a temperature difference of 15 ° C. with a body temperature of 37 ° C. and an outside air temperature of 22 ° C., A thickness of about 5 mm is required.
  • the thickness is as small as about 200 ⁇ m, the temperature is only about 1 ° C. Since the efficiency and temperature difference of the thermoelectric device have a substantially linear relationship near room temperature, the relationship between the thickness of the thermoelectric device and the thermoelectric efficiency approaches 15 ° C. as the thickness increases, and the thermoelectric efficiency is saturated. . In order to obtain high thermoelectric efficiency, a sufficient film thickness is necessary for the thermoelectric device.
  • thermoelectromotive force generated by the Seebeck effect is proportional to the temperature difference between the low temperature side and the high temperature side of the device, it is important to give a sufficient temperature difference to the device.
  • thermoelectromotive force generated by the Seebeck effect is proportional to the temperature difference between the low temperature side and the high temperature side of the device.
  • the heat flow from the high temperature side is blocked, and there is almost no temperature difference in the thin film shape (several hundred ⁇ m). is there.
  • thermoelectric device for example, see Non-Patent Document 1
  • a temperature difference is made in the thickness direction of the thermoelectric device by stacking thin films (for example, (Refer nonpatent literature 2).
  • Many use the former that is, the method of creating a temperature difference in the in-plane direction, but this method can be used as a distributed power source for medical monitoring and smart buildings that can be considered as a flexible thermoelectric device application. There is a problem that the usage is limited.
  • thermoelectric devices that form woven structures are known.
  • thermocouple-containing fabric that is used as a fabric for heat-resistant protective clothing such as fire-fighting clothing and that can quantitatively measure the environmental temperature (see Patent Document 1).
  • a thermocouple-containing fabric that is, a thermocouple wire is woven between the woven yarns.
  • thermoelectric structure formed by a network of a plurality of wires substantially facing the weft direction (see Patent Document 2).
  • thermoelectric device of Patent Document 1 since an electrode must be formed and a metal wire is used, there is a problem that the thermoelectric efficiency is greatly reduced.
  • thermoelectric structure of patent document 2 since the use as a thermocouple is assumed and it does not have a type
  • both the thermoelectric device of Patent Document 1 and the thermoelectric structure of Patent Document 2 have a structure in which a temperature difference is applied in the in-plane direction, and are not structures that are provided in the thickness direction.
  • thermoelectromotive force is proportional to the temperature difference between the low temperature side and the high temperature side of the device, so it is important to make a sufficient temperature difference between the devices.
  • the thin film shape of about 100 ⁇ m has a problem that there is almost no temperature difference.
  • the present invention provides a structure for obtaining a flexible thermoelectric device having a sufficient thickness for obtaining a temperature difference, and a yarn composed of a thermoelectric material and having sufficient flexibility and mechanical strength is heated. It is an object of the present invention to provide a functional element having a fabric structure sewn on a flexible insulating base material having a low conductivity and a method for manufacturing the functional element.
  • the functional element of the present invention is an element in which a spun yarn made of a conductive fibrous material is sewn into a sheet-like or strip-like insulating base material, and the spun yarn is insulative.
  • a cell series structure of ⁇ -type thermoelectric conversion elements is formed by sewing so as to alternately penetrate the front surface and the back surface of the base material.
  • the conventional flexible thermoelectric device using a conductive thin film material or a material whose thickness is controlled by stacking thin films has a problem that a sufficient temperature difference cannot be obtained and the efficiency is remarkably lowered.
  • the fibrous substance is sewn so as to alternately penetrate the front and back surfaces of the insulating base material, thereby forming a cell series structure of ⁇ -type thermoelectric conversion elements. Since the thickness of the element can be controlled with respect to the temperature difference direction depending on the thickness of the conductive material, a sufficient temperature difference can be provided between the front and the back, and a flexible thermoelectric conversion element with no reduction in efficiency can be provided.
  • the conductive fibrous material is partially doped, and an insulating base material such as felt having a low thermal conductivity is sewn with one conductive fibrous material.
  • the conductive fibrous substance has P-type characteristics and N-type characteristics that are alternately repeated in the longitudinal direction, and is sewn so as to alternately penetrate the front and back surfaces of the insulating base material. P type and N type are switched when folded back. Thereby, a three-dimensional flexible thermoelectric conversion element is realizable.
  • the spun yarn made of conductive fibrous materials includes carbon nanotubes (CNT), carbon nanofibers (CNF), graphene, graphene nanoribbons, fullerene nano whisker, and inorganic semiconductors. It is possible to use a composite material of one or more conductive nanofibers selected from the group of Whisker and an insulating or conductive flexible polymer.
  • Graphene nanoribbons are described, for example, in the literature (H. Sakaguchi et al., “Width-Controlled Sub-Nanometer Graphene Nanoribbon Films Synthesized by Radical-Polymerized Chemical Vapor Deposition”, Advanced Materials, Volume 26, Issue 24, pp. 4134-4138, 2014) discloses production methods and physical properties.
  • a twisted yarn (hereinafter referred to as “CNT spun yarn”) in which a plurality of fibers made of carbon nanotubes (CNT) having a diameter of 0.1 to 100 ⁇ m are twisted is preferably used. It can.
  • the diameter of one CNT is 1 to 2 nm, and may be up to about 10 nm as the thinnest when CNT is used as a fiber. From the viewpoint of mechanical strength, a CNT spun yarn having a diameter of at least 0.1 ⁇ m or more is used. .
  • CNT spun yarn with a diameter of 100 ⁇ m or more can be realized by twisting many, but it is necessary to sew alternately on the front and back surfaces of the insulating base material. Use.
  • CNT and composite materials thereof can be formed into a thread shape by taking advantage of the flexibility and high aspect ratio of CNT.
  • CNT spun yarn By using CNT spun yarn, a three-dimensional structure device can be produced without using a substrate, and the length of the device with respect to the temperature difference direction can be freely controlled. Furthermore, it is expected that the conductivity and Seebeck coefficient will be improved due to the alignment of the CNTs in the longitudinal direction.
  • shape of the spun yarn a wide range of applications can be expected as a material for textile electronics such as sewing directly on clothes.
  • the cocoon protein is inserted in the joint part of CNT with the fiber which consists of CNT.
  • thermoelectric conversion efficiency can be improved.
  • the insulating base material preferably has flexibility, and specifically, any of cloth, paper, foamed polymer, elastomer, and gel film can be suitably used.
  • the cloth is a product obtained by processing a large number of fibers into a thin and wide plate, and includes woven fabric, knitted fabric (knitted fabric), lace, felt, non-woven fabric, silk fabric, and wool fabric.
  • a method for producing a functional element according to a first aspect of the present invention is a method for producing a functional element that forms a cell series structure of continuous ⁇ -type thermoelectric conversion elements using a spun yarn made of a conductive fibrous material.
  • the spun yarn is cyclically repeated alternately with P-type characteristics and N-type characteristics in the longitudinal direction, and then the spun yarn is made into a sheet-like or strip-like insulating property. Threading is performed so as to alternately penetrate the front and back surfaces of the base material, and a step of sewing is performed so that the P-type and the N-type are switched when folded back in the thickness direction of the insulating base material.
  • Step 1) When the conductive fibrous material has P-type characteristics, the part that leaves the P-type characteristics in the spun yarn at the same time as the process of immersing the spun yarn in the solvent containing the N-type dopant is a solvent that is non-affinity with the solvent.
  • Step 2) In the case where the conductive fibrous material has P-type characteristics, before the treatment of immersing the spun yarn in the solvent containing the N-type doping agent, the portion that leaves the P-type characteristics in the spun yarn is Step 3) If the conductive fibrous material has N-type characteristics, impregnate in a non-affinity solvent and then immerse the spun yarn in the solvent containing N-type doping agent.
  • the portion of the spun yarn that retains the N-type characteristics is impregnated with a solvent that is incompatible with the solvent.
  • a P-type doping agent is contained.
  • the conductive fibrous material is spun into a flexible yarn, and formed so that the P-type semiconductor portion and the N-type semiconductor portion appear alternately after spinning.
  • the manufacturing process of alternately arranging the respective materials and connecting them with electrodes can be omitted.
  • Such an element structure makes it easy to produce flexible thermoelectric devices with sufficient thickness, and applications of flexible thermoelectric devices that tend to be limited to heat dissipation to the atmosphere (such as pasting on the human body or building) ), It is easy to obtain a sufficient temperature difference between both surfaces of the element, and high conversion efficiency can be obtained.
  • the P-type and N-type coating pitches of thermoelectric yarns and the thickness of the base material to be sewn can be selected relatively freely, and the thickness of about 1 mm is suitable for use in clothes, car skins, etc. From a device to a device having a thickness of about 10 cm for use as a heat insulating material for buildings, it can be used for a method for producing a scalable thermoelectric device and for a wide range of applications.
  • a method for producing a functional element according to a second aspect of the present invention is a method for producing a functional element that forms a cell series structure of continuous ⁇ -type thermoelectric conversion elements using a spun yarn made of a conductive fibrous material.
  • the P-type characteristics and the N-type characteristics are alternately and periodically repeated and folded back in the thickness direction of the insulating base material, the P-type characteristics and the N-type characteristics are switched.
  • the dopant solutions are alternately and quickly discharged in order to soak both dopant solutions as soon as possible.
  • a blank solution not containing a doping agent and the other P-type or N-type dopant solution are alternately and quickly discharged in accordance with the stitches after stitching. Impregnating the solution in the thickness direction of the substrate
  • the spun yarn is first sewn so as to alternately penetrate the front and back surfaces of the insulating base material, and then doped according to the stitches after the stitching. Since the processing is performed, the pitch of the seam can be freely changed, and the sewing method and the sewing position can be freely changed.
  • P-type and N-type portions can be alternately produced by performing partial doping on one thread-like conductive fibrous material.
  • the step of sewing the spun yarn so as to alternately penetrate the front surface and the back surface of the insulating base material P is set in accordance with the stitches after the sewing.
  • the P-type dopant solution and the N-type dopant solution and the non-affinity solvent are applied to the front and back surfaces of the insulating base material, and the spun yarn and the insulating property It is preferable to fix the substrate.
  • a method for producing a functional element according to a third aspect of the present invention is a method for producing a functional element that forms a cell series structure of continuous ⁇ -type thermoelectric conversion elements using a spun yarn made of a conductive fibrous material.
  • the following steps a) to c) are provided, and when the spun yarn is periodically repeated with the P-type characteristics and the N-type characteristics alternately in the longitudinal direction and folded back in the thickness direction of the insulating substrate, the P-type And N type are switched.
  • the spun yarn is first sewn so as to alternately penetrate the front and back surfaces of the insulating base material, and then sewn. Since the doping process is performed in accordance with the subsequent seam, the pitch of the seam can be freely changed, and the sewing method and the sewing position can be freely changed.
  • the spun yarn is coated with moisture or gas barrier. It is preferable to further comprise a step of applying an agent. For example, by coating a polymer, passivation can be performed and atmospheric stability can be enhanced.
  • thermoelectric device having a sufficient thickness for obtaining a temperature difference can be provided.
  • FIG. 1 Schematic diagram of functional element of the present invention Image of CNT spun yarn production method Thermoelectric measurement results of the produced CNT spun yarn, (1) is Seebeck measurement, (2) is IV measurement Illustration of ⁇ -type thermoelectric conversion element Correlation graph of immersion time, conductivity and Seebeck coefficient when carrier doping of CNT spun yarn using PEI Characteristics of CNT spun yarn before carrier doping Illustration of carrier doping for CNT spun yarn (1) Characteristics of CNT spun yarn after carrier doping (1) Illustration of carrier doping for CNT spun yarn (2) Characteristics of CNT spun yarn after carrier doping (2) Schematic diagram of functional element Functional device fabrication flow chart (1) Functional device fabrication flow diagram (2) Schematic diagram of manufacturing method of first functional element Manufacturing flow chart of manufacturing method of first functional element Schematic diagram of manufacturing method of second functional element Manufacturing flow chart of manufacturing method of second functional element Schematic diagram of manufacturing method of third functional element Manufacturing flow diagram of third functional element manufacturing method Schematic diagram of fourth functional element fabrication method Manufacturing flow diagram of fourth functional element manufacturing method Schematic diagram of fifth functional element manufacturing method Manufacturing flow diagram of fifth functional element manufacturing
  • FIG. 1 shows a schematic diagram of a functional element of the present invention.
  • a spun yarn of conductive nanofibers is sewn so as to alternately penetrate the front and back surfaces of an insulating substrate 3 such as a nonwoven fabric such as felt.
  • a structure in which the mold yarns 2 appear alternately and repeatedly is formed, thereby forming a cell series structure of ⁇ -type thermoelectric conversion elements.
  • a CNT spun yarn will be described as a spun yarn of conductive nanofibers.
  • FIG. 2 shows an image of a method for producing CNT spun yarn. Stretch spinning was performed hydrodynamically by discharging the dispersion liquid of CNT put in the dispenser to the agglomerated liquid placed on the turntable. As the aggregating liquid, a 5 wt% PVA (Polyvinyl alcohol) aqueous solution was used.
  • SDS sodium Dodecyl Sulfate
  • the rotation speed was about 50 rpm, and the nozzle orientation and position were adjusted to be parallel to the water flow at a distance of about 3 cm from the central axis, and the CNT dispersion was discharged. Thereafter, the solvent was replaced with pure water, and the spun yarn was pulled up from one end and dried in the air to prepare a CNT spun yarn.
  • the diameter of the obtained CNT spun yarn was about 10 to 30 ⁇ m.
  • Thermoelectric measurement was performed on the obtained CNT spun yarn.
  • the measurement results are shown in Table 1 below.
  • Table 1 shows the measurement results of the non-oriented CNT thin film produced under the same dispersion conditions as the CNT spun yarn for comparison. All measurements were performed in the atmosphere.
  • the CNT spun yarn showed a decrease in conductivity compared to the CNT thin film, but the power factor increased 2.9 times compared to the CNT thin film due to an increase in Seebeck coefficient.
  • the conductivity decreased. This is presumed to be due to the decrease in the number of carriers due to the movement of holes to PVA, and the fact that PVA, which is an insulator, entered between the CNTs when forming the spun yarn.
  • the Seebeck coefficient of CNT spun yarn is greatly increased, similarly, there is a possibility that PVA entering between CNTs causes a Seebeck effect at the CNT junction with the movement of holes to PVA. .
  • Carrier doping of CNT spun yarn was performed using PEI (Polyethyleneimine) known as an N-type dopant.
  • the N-type doping was performed by immersing the CNT spun yarn in a 1 wt% PEI aqueous solution (solvent: methanol) for a certain period of time.
  • solvent methanol
  • the relationship between immersion time, electrical conductivity, and Seebeck coefficient is shown in FIG.
  • the Seebeck coefficient is changed to N-type, and it can be seen that PEI functions as a donor.
  • the Seebeck coefficient S is a sum of Seebeck coefficients having the weights of the conductivity of each of electrons and holes, as in the following Equation 1.
  • S e is the electron Seebeck coefficient
  • S h is the Seebeck coefficient of the Hall
  • [delta] e is the electron conductivity
  • the [delta] h is the conductivity of the hole.
  • the change in Seebeck coefficient before and after doping will be described with reference to the graph. While the Seebeck coefficient of the CNT spun yarn before doping was about 38 ( ⁇ V / K) (see FIG. 6), as shown in FIG. 7, only 1 cm of the CNT spun yarn was immersed in PEI and N As a result of the type doping, the Seebeck coefficient on the doped side was ⁇ 26.5 ( ⁇ V / K), and the undoped side was ⁇ 17.8 ( ⁇ V / K) (FIG. 8).
  • the Seebeck coefficient obtained as a whole decreased as ⁇ Vpn (see FIG. 4) canceled out and became a small value of ⁇ 6.2 ( ⁇ V / K).
  • the reason for this is considered that the PEI solution was sucked up by the CNT spun yarn and reached the undoped side.
  • the Seebeck coefficient on the doped side is ⁇ 17.8 ( ⁇ V / K).
  • the side where no doping was performed showed 15.5 ( ⁇ V / K) (see FIG. 10).
  • P-type and N-type respectively, the Seebeck coefficient obtained as a whole is as large as 32.0 ( ⁇ V / K), and a CNT spun yarn having both P-type and N-type characteristics is obtained. It was.
  • 50 CNT spun yarns and a diameter of 25 mm are alternately sewn at an interval of 1 mm on the front and back of felt (0.04 W / mK) having a thickness of 3 mm and a length and width of 10 cm.
  • a structure in which the P-type CNT spun yarn 16 and the N-type CNT spun yarn 17 appear alternately and repeatedly is assumed, and a cell series structure of ⁇ -type thermoelectric conversion elements is assumed, and the obtained output is estimated.
  • a method for manufacturing a functional element will be described.
  • the manufacturing method of the functional element is roughly divided into two methods. First, an outline of these two methods will be described with reference to the flowcharts of FIGS. 12 and 13, and then a specific manufacturing method will be described as another embodiment.
  • a CNT spun yarn is prepared (S01), and after partial doping is performed on the CNT spun yarn, the CNT spun yarn is dyed separately in a P-type N-type stripe shape. (S02), the CNT spun yarn is sewn into the insulating base material so that the front and back are alternately turned out (S03) by matching the dyeing period and the stitch pitch.
  • S04 a cell series structure of ⁇ -type thermoelectric conversion elements is formed
  • a CNT spun yarn is produced (S11), and the CNT spun yarn is sewn into an insulating base material so that the front and back alternately come out (S12). Then, the CNT spun yarn is partially doped while being sewn into the insulating base material (S13).
  • a cell series structure of ⁇ -type thermoelectric conversion elements is formed (S14).
  • FIG. 14 is a schematic diagram of a manufacturing method of the first functional element
  • FIG. 15 is a manufacturing flow diagram of the manufacturing method of the first functional element.
  • the CNT spun yarn 10 is produced (S21).
  • the production method of the CNT spun yarn 10 is performed by the method shown in the above-described Example 1.
  • the above-mentioned partial N-type doping is performed only on the upper part of the CNT spun yarn having a length of about 10 cm wound in a square shape while the lower part is immersed in methanol. .
  • the CNT spun yarn 10 is dyed into P-type N-type stripes alternately with portions for N-type doping and portions immersed in a blank solvent.
  • the P-type CNT spun yarn 11 and the N-type CNT spun yarn 12 appear alternately.
  • the CNT spun yarn 13 in which the P-type and N-type appear alternately It is produced (S22).
  • a functional element is manufactured by sewing on a cloth having a thickness of about 4 mm so that the N-doped portion is positioned in the thickness direction.
  • the CNT spun yarn 13 in which the P-type and the N-type alternately appear is matched with the dyeing cycle and the pitch of the seam so that the yarns come out alternately on the front and back sides.
  • Sewing into the material 15 S23.
  • a cell series structure of ⁇ -type thermoelectric conversion elements is formed (S24). It has been confirmed that a thermoelectromotive force of approximately 2.5 mV is generated by body temperature when the functional element thermoelectric device thus manufactured is touched by hand in the atmosphere (about 21 ° C.).
  • FIG. 16 shows a schematic diagram of a method for manufacturing the second functional element
  • FIG. 17 shows a manufacturing flowchart of the method for manufacturing the second functional element.
  • the CNT spun yarn 10 is produced (S31).
  • the production method of the CNT spun yarn 10 is performed by the method shown in the above-described Example 1.
  • the polymer 21 having a low affinity with the solvent is impregnated into a portion that is not dyed every predetermined pitch (batching dyeing) (S32).
  • the CNT spun yarn is immersed in an N-type doping agent (S33).
  • a CNT spun yarn 13 in which P-type CNT spun yarn 11 and N-type CNT spun yarn 12 appear alternately is obtained (FIG. 16 (4)). Then, as shown in FIG. 16 (5), the CNT spun yarn is sewn into the insulating base material 15 so that the yarn comes out alternately on the front and back sides by matching the dyeing period and the stitch pitch (S34), A cell serial structure of the thermoelectric conversion element is formed (S35).
  • FIG. 18 shows a schematic diagram of a method for manufacturing the third functional element
  • FIG. 19 shows a manufacturing flow diagram of the method for manufacturing the third functional element.
  • the CNT spun yarn 10 is produced by the method shown in the above-described Example 1 (S41), and the insulating base material 15 has the yarn alternately appearing on the front and back sides.
  • the CNT spun yarn 10 is sewn into the insulating base material 15 (S42).
  • the P-type doping agent 30 and the N-type doping agent 31 are discharged in accordance with the stitches (S43).
  • An ink jet method is used for ejection.
  • FIG. 20 shows a schematic diagram of a method for manufacturing the fourth functional element
  • FIG. 21 shows a manufacturing flow diagram of the method for manufacturing the fourth functional element.
  • the CNT spun yarn 10 is produced by the method shown in the above-described Example 1 (S51), and the insulating base material 15 has the yarn alternately appearing on the front and back sides.
  • the CNT spun yarn 10 is sewn into the insulating base material 15 (S52).
  • the polymer 40 having a low affinity with the solvent is discharged in a single manner according to the stitches (S53).
  • An ink jet method is used for ejection. Then, as shown in FIG.
  • FIG. 22 shows a schematic diagram of a fifth functional element manufacturing method
  • FIG. 23 shows a manufacturing flow diagram of the fifth functional element manufacturing method.
  • the CNT spun yarn 10 is produced by the method shown in the above-described Example 1 (S 61), so that the yarn comes out alternately on the front and back of the insulating substrate 15.
  • the CNT spun yarn 10 is sewn into the insulating base material 15 (S62).
  • the front surface 51 and the back surface 52 of the insulating base material 15 are batched using a coating device 50 such as a roller (S63).
  • the batik dyeing is performed in order to prevent unnecessary penetration of the doping agent, fix the base material and the yarn, prevent yarn displacement, and prevent a phase shift. Then, as shown in FIG. 22 (4), the P-type dopant and the N-type dopant are discharged from the gap in accordance with the seam (S64). As a result, a cell series structure of ⁇ -type thermoelectric conversion elements is formed (S65). An image of the formed functional element is shown in FIG.
  • the functional element of the present invention is a distributed power source for forming a sensor matrix for smart houses and smart buildings, and a thermoelectric element for reusing exhaust heat energy in houses, offices and automobiles as energy harvesting elements, It can be used as a power source for sticker-type biological information measuring devices (body temperature, pulse, electrocardiogram monitor, etc.).

Abstract

L'invention vise à fournir : un élément fonctionnel ayant, en tant que structure permettant d'obtenir un dispositif thermoélectrique flexible ayant une épaisseur adéquate pour l'obtention d'une différence de température, une structure tissée dans laquelle un fil composé d'un matériau thermoélectrique est tissé en un matériau de base isolant flexible présentant une faible conductivité thermique ; et un procédé de fabrication dudit élément fonctionnel. Pour ce faire, l'invention concerne un élément fonctionnel dans lequel un fil filé comprenant une substance fibreuse électroconductrice est tissé en un matériau de base isolant qui prend la forme d'une feuille ou d'une bande, le fil filé étant composé d'une substance fibreuse électroconductrice, et étant tissé de manière à passer en alternance à travers les surfaces avant et arrière du matériau de base isolant pour former une structure de série cellulaire d'éléments de conversion thermoélectrique de type π. Dans la substance fibreuse électroconductrice, des caractéristiques de type p et des caractéristiques de type n sont répétées d'une manière alternée dans la direction longitudinale, de sorte que le type p et le type n alternent lorsque le fil filé est tissé de manière alternée dans les surfaces avant et arrière du matériau de base isolant et est replié dans la direction de l'épaisseur du matériau de base.
PCT/JP2015/001704 2015-03-25 2015-03-25 Élément fonctionnel présentant une structure de série cellulaire d'éléments de conversion thermoélectrique du type π, et procédé de fabrication associé WO2016151634A1 (fr)

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PCT/JP2015/001704 WO2016151634A1 (fr) 2015-03-25 2015-03-25 Élément fonctionnel présentant une structure de série cellulaire d'éléments de conversion thermoélectrique du type π, et procédé de fabrication associé
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JP2017034110A (ja) * 2015-08-03 2017-02-09 積水化学工業株式会社 熱電変換素子及びそれを含む熱電変換デバイス
WO2018047882A1 (fr) * 2016-09-06 2018-03-15 国立大学法人奈良先端科学技術大学院大学 ÉLÉMENT FONCTIONNEL AYANT UNE STRUCTURE DE CELLULES EN SÉRIE D'ÉLÉMENTS DE CONVERSION THERMOÉLECTRIQUE DE TYPE π, ET SON PROCÉDÉ DE FABRICATION
JP2018186260A (ja) * 2017-04-25 2018-11-22 国立大学法人横浜国立大学 熱電発電デバイスおよび熱輸送デバイス
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CN109944063A (zh) * 2019-03-04 2019-06-28 东华大学 一种热电转换间隔织物的制备方法
CN112461291A (zh) * 2020-11-11 2021-03-09 大连海事大学 一种模块化拼接式自供能装置及海洋生物传感器***
WO2023127590A1 (fr) * 2021-12-28 2023-07-06 日東電工株式会社 Élément de conversion thermoélectrique et module de capteur
WO2023127592A1 (fr) * 2021-12-28 2023-07-06 日東電工株式会社 Module de conversion thermoélectrique
WO2023127591A1 (fr) * 2021-12-28 2023-07-06 日東電工株式会社 Matériau d'isolation thermique sous vide équipé d'un capteur

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JP2016190982A (ja) * 2015-03-31 2016-11-10 日立造船株式会社 カーボンナノチューブ複合材およびカーボンナノチューブ複合材の製造方法
JP2017034110A (ja) * 2015-08-03 2017-02-09 積水化学工業株式会社 熱電変換素子及びそれを含む熱電変換デバイス
WO2018047882A1 (fr) * 2016-09-06 2018-03-15 国立大学法人奈良先端科学技術大学院大学 ÉLÉMENT FONCTIONNEL AYANT UNE STRUCTURE DE CELLULES EN SÉRIE D'ÉLÉMENTS DE CONVERSION THERMOÉLECTRIQUE DE TYPE π, ET SON PROCÉDÉ DE FABRICATION
JP2018186260A (ja) * 2017-04-25 2018-11-22 国立大学法人横浜国立大学 熱電発電デバイスおよび熱輸送デバイス
CN109524533A (zh) * 2018-12-04 2019-03-26 东华大学 一种线圈状热电单元、织物结构热电器件及其制备和应用
CN109524533B (zh) * 2018-12-04 2020-10-20 东华大学 一种线圈状热电单元、织物结构热电器件及其制备和应用
CN109944063A (zh) * 2019-03-04 2019-06-28 东华大学 一种热电转换间隔织物的制备方法
CN112461291A (zh) * 2020-11-11 2021-03-09 大连海事大学 一种模块化拼接式自供能装置及海洋生物传感器***
WO2023127590A1 (fr) * 2021-12-28 2023-07-06 日東電工株式会社 Élément de conversion thermoélectrique et module de capteur
WO2023127592A1 (fr) * 2021-12-28 2023-07-06 日東電工株式会社 Module de conversion thermoélectrique
WO2023127591A1 (fr) * 2021-12-28 2023-07-06 日東電工株式会社 Matériau d'isolation thermique sous vide équipé d'un capteur

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