WO2018047882A1 - ÉLÉMENT FONCTIONNEL AYANT UNE STRUCTURE DE CELLULES EN SÉRIE D'ÉLÉMENTS DE CONVERSION THERMOÉLECTRIQUE DE TYPE π, ET SON PROCÉDÉ DE FABRICATION - Google Patents

ÉLÉMENT FONCTIONNEL AYANT UNE STRUCTURE DE CELLULES EN SÉRIE D'ÉLÉMENTS DE CONVERSION THERMOÉLECTRIQUE DE TYPE π, ET SON PROCÉDÉ DE FABRICATION Download PDF

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WO2018047882A1
WO2018047882A1 PCT/JP2017/032179 JP2017032179W WO2018047882A1 WO 2018047882 A1 WO2018047882 A1 WO 2018047882A1 JP 2017032179 W JP2017032179 W JP 2017032179W WO 2018047882 A1 WO2018047882 A1 WO 2018047882A1
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spun yarn
type
functional element
base material
insulating base
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PCT/JP2017/032179
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English (en)
Japanese (ja)
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中村　雅一
光洋 伊藤
拓也 小泉
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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 JP2018538450A priority Critical patent/JP6974854B2/ja
Publication of WO2018047882A1 publication Critical patent/WO2018047882A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • 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
    • 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
    • H10N10/856—Thermoelectric active materials comprising organic compositions

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.
  • the conventional thermoelectric conversion element with a high unit area price has so far been limited in use because it is difficult to obtain economic merit. 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 and the thermal conductivity decreases. 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).
  • two kinds of metal fibers X and metal fibers Y forming a thermocouple are alternately woven into the warp made of insulating fibers as wefts. As a whole, the wefts are composed of the metal fibers X and the metal fibers Y.
  • line which becomes is known (refer patent document 3).
  • thermoelectric device of Patent Document 1 an electrode has to be formed, and the problem is that the thermoelectric efficiency is greatly reduced because a metal wire is used. Moreover, in the case of the thermoelectric structure of patent document 2, the use as a thermocouple is assumed and since it does not have a pi-type structure, it is a problem that thermoelectric efficiency is bad. Furthermore, the thermoelectric device of Patent Document 1, the thermoelectric structure of Patent Document 2, and the thermoelectric conversion material of Patent Document 3 all have a structure in which the temperature difference is applied in the in-plane direction, and the structure is provided in the thickness direction. Not.
  • 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. It is another object of the present invention to provide a functional element in which output characteristics are unlikely to deteriorate with respect to disconnection and a manufacturing method thereof.
  • a functional element is used to mean an element capable of exhibiting various functions such as an element for power generation, an element for cooling / heating, and an element for temperature sensing.
  • a plurality of series structures of ⁇ -type thermoelectric conversion cells using a temperature difference in the thickness direction of the insulating base material are arranged in parallel, and p-type and n-type are switched.
  • This element is a device having a topology in which the stages having the same potential during power generation are electrically connected.
  • the insulating base material is in the form of a sheet or a strip having heat insulating properties and flexibility, and has a base material strength capable of maintaining the shape of the base material alone in the use environment.
  • n-type spun yarn and p-type spun yarn made of conductive fibrous material having heat insulation properties are sewn alternately and in parallel to the insulating base material, and the front and back surfaces of the insulating base material are alternately placed. Are electrically connected to each other when penetrating them. Then, the insulating base material and the spun yarn are loosely bonded to each other, and the ⁇ -type thermoelectric conversion cell is connected in a vertical and horizontal form as an electric circuit in both series connection and parallel connection, increasing the resistance of the element to disconnection. .
  • the functional element of the present invention has a structure that is extremely resistant to disconnection, in which ⁇ -type thermoelectric conversion cells are connected vertically and horizontally in a mesh shape in both series connection and parallel connection.
  • the network structure in which the insulating base material and the spun yarn are loosely coupled to each other can provide an effect of suppressing a decrease in output due to the spun yarn being cut.
  • the n-type spun yarn and the p-type spun yarn made of the conductive fibrous substance are sewn so as to alternately penetrate the front surface and the back surface of the insulating base material.
  • a cell series structure of type thermoelectric conversion elements is formed, and the thickness of the element can be controlled with respect to the direction of temperature difference depending on the thickness of the insulating material.
  • a flexible thermoelectric conversion element can be provided. It is preferable that the thermal conductivity in the longitudinal direction of the conductive fibrous substance in the functional element of the present invention is suppressed to less than 10 W / mK.
  • the thermal conductivity in the longitudinal direction of the conductive fibrous substance is suppressed to less than 1 W / mK, and more preferably less than 0.1 W / mK.
  • the functional element of the present invention has heat insulation.
  • the thickness of the element is controlled in the temperature difference direction according to the thickness of the insulating material, and a sufficient temperature difference is provided between the front and back of the insulating material. Since the conductive fibrous substance penetrates between the front and back of the insulating material, the thermal conductivity in the longitudinal direction is suppressed rather than the radial direction (transverse direction) of the conductive fibrous substance.
  • the heat insulation of the functional element of the present invention is improved.
  • the entire flexible thermoelectric device of the functional element can be made heat insulating, and by improving the heat insulating properties of the conductive fibrous material, the overall heat insulating performance can be improved.
  • the flexible thermoelectric device using the functional element of the present invention assumes a use temperature (high temperature side) of about 35 (body temperature) to about 100 ° C., it can cope with natural air cooling as cooling on the low temperature side. is there. It is assumed that the thermal conductivity is markedly higher in the longitudinal direction than in the direction crossing the conductive fibrous material. In particular, in the case of carbon nanotubes (CNT), it can be inferred that the ratio reaches several tens to several hundred times.
  • CNT carbon nanotubes
  • the yarns are crossed and twisted and joined at least once. Is preferred.
  • the functional element of the present invention is such that when the n-type spun yarn and the p-type spun yarn pass through the front and back surfaces of the insulating base material alternately, the yarn is crossed, and the electrical connection by the conductive paste is made at the intersection It is preferable that the reinforcement is provided.
  • the yarn crosses or is brought into contact with each other, and the intersection or contact is adhered. It is preferable.
  • the n-type spun yarn and the p-type spun yarn penetrate obliquely with respect to the thickness direction of the insulating base material, and increase or decrease the portions exposed on the front and back surfaces of the insulating base material, respectively. It is preferable to have made it.
  • the n-type spun yarn and the p-type spun yarn are band-shaped, or the cross-section of the n-type spun yarn and the p-type spun yarn is polygonal or elliptical in order to reduce the thermal resistance at the exposed portion.
  • the shape is preferred. By making the cross section of the spun yarn a shape having a large specific surface area such as a rectangle, an ellipse, or a star, for example, the thermal resistance at the exposed portion can be reduced.
  • the insulating base material preferably has flexibility and heat insulating properties, specifically, cloth or paper, or foamed polymer, elastomer, cotton-like aggregate and gel-like aggregate. Any of those obtained by processing a material selected from the above into a plate shape or a sheet shape 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.
  • the insulating base material is sewn, and it is preferable that the n-type spun yarn and the p-type spun yarn are sewn at the same time, and more preferably, That is, sewing was performed using warp and weft having substantially the same diameter as the thickness of the ⁇ -type thermoelectric conversion cell.
  • the spun yarn made of conductive fibrous materials includes carbon nanotubes (CNT), carbon nanofibers (CNF), graphene, graphene nanoribbons, fullerene nano whisker, and inorganic semiconductors.
  • CNT carbon nanotubes
  • CNF carbon nanofibers
  • a material made of a composite material of 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.
  • Fullerene nanowhiskers for example, have been disclosed in the literature (Junichi Miyazawa, “Synthesis and Properties of Fullerene Nanowhiskers”, Surface Science Vol. 28, No. 1, pp. 34-39, 2007) and their physical properties. Yes.
  • 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. .
  • a CNT spun yarn having a diameter of 100 ⁇ m or more can be realized by twisting many times, but since a workability when sewing alternately on the front surface and the back surface of the insulating base material is required, a diameter of 100 ⁇ m or less is required. CNT spun yarn is used.
  • CNT and composite materials thereof can be formed into a thread shape by taking advantage of the flexibility and high aspect ratio of CNT.
  • the CNT spun yarn By using the CNT spun yarn, a three-dimensional structure device can be manufactured without using a substrate processed into a complicated shape, 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.
  • the 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 further improved by combining with a heat insulating base material. Furthermore, by encapsulating inorganic semiconductor particles in the basket-like protein, electrons or holes can be selectively tunnel-transported at the junction, and the conductivity and Seebeck coefficient can be improved.
  • the functional element manufacturing method of the present invention is the above-described functional element manufacturing method, and a current path is formed in a direction orthogonal to the direction of wave stitching by repeating the following steps 1) and 2).
  • a ⁇ -type structure series connection is formed along the current path.
  • Step 2 When the second spun yarn is wave-sewn adjacent to the first spun yarn that has been wave-stitched in parallel with the insulating base material, The portions exposed on the first surface of the first spun yarn that has been sewn are crossed, twisted at least once, and then sewn.
  • Step 2 Next, when the first spun yarn is wave-sewn adjacently in parallel with the second spun yarn that has been wave-stitched, the second surface is exposed to the second surface of the second spun yarn that has been sewn one step before. After crossing, twist at least once and sew.
  • thermoelectric conversion cells By simply sewing each n-type spun yarn and p-type spun yarn into an electrically and thermally insulating cloth-like substrate, not only a single thermoelectric conversion cell, but many thermoelectric conversion cells A structure for serial connection can be easily formed.
  • 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, building on buildings, etc.) ), It is easy to obtain a sufficient temperature difference between both surfaces of the element, and high conversion efficiency can be obtained.
  • thermoelectric device It is a method for producing a thermoelectric device that can be used in a scalable manner from an element having a thickness of about 1 mm suitable for use in the skin of clothes or a car seat to an element having a thickness of about 10 cm for use as a heat insulating material for buildings. Can be used in a wide range of applications.
  • the functional element of the present invention has an effect that it is possible to provide a heat-insulating flexible thermoelectric device having a sufficient thickness to obtain a temperature difference.
  • FIG. 3 is a diagram illustrating a method for manufacturing a functional element.
  • Correlation graph of immersion time, conductivity and Seebeck coefficient when carrier doping of CNT spun yarn using PEI Thermoelectric characteristics graph of functional elements
  • Flow chart of functional element manufacturing method Explanatory diagram about the effect of partial disconnection of functional elements
  • Schematic diagram of functional device of Example 3 Thermoelectric output characteristic graph of the functional element of Example 3
  • Equivalent circuit model of functional element used for simulation The graph which shows the change of the output of the functional element of Example 3 accompanying the change of a cutting probability.
  • thermoelectric conversion cell A series structure of ⁇ -type thermoelectric conversion cells using a temperature difference in the thickness direction will be described with reference to FIG.
  • the metal wiring connecting the n-type semiconductor portion and the p-type semiconductor portion which is often used in conventional thermoelectric conversion elements, is omitted for the sake of simplicity.
  • the ⁇ -type structured thermoelectric conversion cell is composed of a p-type semiconductor portion and an n-type semiconductor portion, and each cell is connected in series to become a thermoelectric conversion element.
  • an electromotive force is generated due to the Seebeck effect when a temperature difference occurs between the front surface and the back surface of the thermoelectric conversion element. Therefore, the thermoelectric conversion element heats one side (high temperature side) and cools the other side (low temperature side) to generate a temperature difference in the thermoelectric conversion element.
  • FIG. 2 (1) shows a connection topology of a series structure of five ⁇ -type thermoelectric conversion cells ( ⁇ -type thermocouples 1 to 5). Electrodes 1 and 2 are formed at both ends of the series structure, respectively. As shown in FIG. 1, each of the ⁇ -type thermocouples 1 to 5 generates power using a temperature difference in the thickness direction. Due to the electromotive force generated in the ⁇ -type thermocouple 1, the potential at the end of the ⁇ -type thermocouple 1 becomes V 1 from the potential (V 0 ) of the electrode 1. Similarly, due to the electromotive force generated in the ⁇ -type thermocouple 2, the potential at the end of the ⁇ -type thermocouple 2 becomes V2.
  • FIG. 2 (2) shows a connection topology in which five blocks are connected in parallel with a series structure of five ⁇ -type thermoelectric conversion cells as one block.
  • FIG. 3 shows the connection topology of the functional element of the present invention.
  • the functional element of the present invention has a topology in which stages at the same potential are connected at a portion where p-type and n-type are switched.
  • FIG. 3 when only the dotted line portion is viewed, only n-type or p-type is connected in the path.
  • FIGS. A structure equivalent to the connection topology shown in FIG. 3 is shown in FIGS.
  • ⁇ -type thermoelectric conversion cells are connected in series along a current path from the electrode 1 to the electrode 2. Further, the half-cells of the ⁇ -type thermoelectric conversion cells are connected in parallel. As a result, the ⁇ -type thermoelectric conversion cells are connected vertically and horizontally in a mesh pattern in both series connection and parallel connection.
  • each dotted line portion forms one ⁇ -type thermoelectric conversion cell.
  • each dotted line portion indicates one ⁇ -type thermoelectric conversion cell. 3 and 4 or 5 are equivalent in terms of topology.
  • FIG. 6 shows a case where a thin line for showing an electrical connection is removed from the connection described with reference to FIG. 4 or 5, and instead a p-type spun yarn or an n-type spun yarn is assumed and they are meandered and connected.
  • FIG. 6 when the three-dimensional structure is formed so that the portion indicated by the solid line is on the front side and the portion indicated by the dotted line is on the back side, each of the portions surrounded by the rectangle is one ⁇ -type thermoelectric conversion cell. It has become. That is, the topology is equivalent from FIG. 3 to FIG. The rectangle drawn in FIG.
  • 6 and symbols A to C are for showing examples of current paths that can be regarded as cell series connection in this element.
  • the area indicated by the symbol A is drawn when a combination of a p-type spun yarn side and an n-type spun yarn side that linearly connects one intersection of the p-type spun yarn and the n-type spun yarn is regarded as one ⁇ -type cell. ing. If the path is followed from the bottom to the upper left by two cells and then to the upper right by one cell, it can be regarded as a series connection of three cells.
  • four types of ⁇ -type cells can be defined by any combination of two p-type spun yarn sides and two n-type spun yarn sides.
  • a number of arbitrary series connection paths can be taken.
  • FIG. 7 shows a schematic diagram of the functional element of this example.
  • the functional element of the present invention is a p-type spun yarn 1 in which a p-type spun yarn 1 and a n-type spun yarn 2 of conductive nanofibers are sewn into a sheet-like insulating substrate 3 such as a nonwoven fabric.
  • the n-type spun yarn 2 is sewn so as to be joined to each other when the front and back surfaces of the insulating base material 3 are wave-sewn and alternately penetrate the front and back surfaces.
  • four p-type spun yarns 1 and three n-type spun yarns 2 are alternately twisted once when the yarns cross each other when passing through the front and back surfaces of the insulating base material alternately. Are joined together.
  • Each of the p-type spun yarn 1 and the n-type spun yarn 2 is provided with six seams.
  • a structure is formed in which ⁇ -type thermoelectric conversion cells are connected vertically and horizontally in a mesh pattern in both series connection and parallel connection.
  • the network structure shown in FIG. 7 can be called a structure having 3.5 units in series and 12 units in parallel.
  • the number of mesh structure elements in series means that the number of units of the ⁇ -type thermoelectric conversion cell is counted in the connection direction of the voltage drop connecting the potentials of the counter electrodes
  • the number of nodes in parallel means that the nodal points of thermoelectric yarns are counted in the connection direction connecting the equipotentials, and twice the number of nodal points of the row with the smallest number of nodal points.
  • thermoelectric yarn not connected to the next stage at both ends it is defined as reducing it.
  • a copper wire 4 having a lower electrical resistance than that of the conductive nanofiber spun yarn is used, which is a current harvesting wiring.
  • the copper wire 4 is sewn so as to alternately pass through the front surface and the back surface of the insulating base material 3, and is engaged with the p-type spun yarn on the front surface and the back surface of the insulating base material 3.
  • the copper wire is connected only to both ends of the p-type spun yarn, but may be connected to each seam.
  • a silver paste 5 is applied to a portion where the p-type spun yarn 1, the n-type spun yarn 2 and the copper wire 4 are engaged to reinforce the electrical connection at the intersection.
  • it is not restricted to a silver paste, Various conductive pastes, such as a carbon paste, may be sufficient.
  • a CNT spun yarn will be described as a spun yarn of conductive nanofibers.
  • NanoIntegris manufactured by HiPCO method (a method of growing iron monoxide as a catalyst and carbon monoxide as a carbon source) was used. Ultrasonically dispersed and dispersed in a 3% by weight aqueous solution of SDS (Sodium Dodecyl Sulfate). With reference to FIG. 8, a method for producing CNT spun yarn will be described. First, the CNT dispersant 11 placed in the dispenser 12 was ejected to the agglomerate 15 in the container 14 placed on the turntable 13, thereby performing hydrodynamic stretching spinning. The aggregating liquid 15 was a 5 wt% PVA (Polyvinyl alcohol) aqueous solution.
  • PVA Polyvinyl alcohol
  • Spinning CNT16 is produced by adjusting the direction and position of the nozzle of the dispenser 12 so that the rotation speed is approximately 50 rpm and parallel to the water flow at a distance of about 3 cm from the central axis, and discharging the CNT dispersant 11. did. Thereafter, the solvent was replaced with pure water, and the spun CNT 16 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, the possibility that PVA that has entered between CNTs has enhanced the Seebeck effect at the CNT junction as well as the movement of holes to PVA. There is.
  • thermoelectric performance it is possible to control the CNT carrier and interface by selecting an appropriate flocculant, and there is a possibility of further improving thermoelectric performance by selecting an appropriate flocculant. . Further, the thermoelectric performance can be improved by optimizing the carrier density by carrier doping described later.
  • 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% by weight PEI aqueous solution (solvent: methanol) for a predetermined time.
  • FIG. 12 shows the relationship between the immersion time, the conductivity, and the Seebeck coefficient. When the CNT spun yarn is immersed in PEI and doped for a sufficient time, the Seebeck coefficient changes 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.
  • FIG. 9 shows a state in which one p-type CNT spun yarn is wave-sewn on the insulating base material 3.
  • the p-type CNT spun yarn 1a is sewn by wave stitching in a straight line so as to alternately penetrate the front surface and the back surface of the insulating base material 3. .
  • FIG. 10 shows a state in which p-type CNT spun yarn and n-type CNT spun yarn are sewn one by one in parallel.
  • the n-type CNT spun yarn 2a is sewn in parallel to the p-type CNT spun yarn 1a in a state where the p-type CNT spun yarn 1a is sewn into the insulating base material 3.
  • FIG. 4 when the n-type CNT spun yarn 2a is sewn, it is sewn so as to alternately penetrate the front and back surfaces of the insulating base material 3 in the same manner as when the p-type CNT spun yarn 1a is sewn. It is rare.
  • the p-type CNT spun yarn 1a and the n-type CNT spun yarn 2a are joined by being twisted once and engaged by joining the portions exposed on the surface of the insulating base material 3. .
  • silver paste is applied to the engaged intersections to reinforce the electrical connection.
  • FIG. 11 shows a state in which four p-type CNT spun yarns and four n-type CNT spun yarns are sewn.
  • the p-type CNT spun yarn 1b is sewn into the insulating base material 3, as shown in FIG. 11, the front and back surfaces of the insulating base material 3 are alternated in the same manner as when the p-type CNT spun yarn 1a is sewn. It is sewn so as to penetrate through. Then, the p-type CNT spun yarn 1b and the n-type CNT spun yarn 2a are engaged by twisting once, with the portions exposed on the back surface of the insulating base material 3 intersecting each other. Although not shown here, silver paste is applied to the engaged intersections to reinforce the electrical connection.
  • the n-type CNT spun yarn 2b is sewn.
  • the method for sewing the n-type CNT spun yarn 2b is the same as the method for sewing the n-type CNT spun yarn 2a.
  • the method for weaving the p-type CNT spun yarn 1b and the n-type CNT spun yarn 2b is the same as the method for weaving the p-type CNT spun yarn 1a and the n-type CNT spun yarn 2a.
  • the p-type CNT spun yarn 1c is sewn.
  • the method for sewing the p-type CNT spun yarn 1c is the same as the method for sewing the p-type CNT spun yarn 1b.
  • the method for weaving the n-type CNT spun yarn 2b and the p-type CNT spun yarn 1c is the same as the method for weaving the n-type CNT spun yarn 2a and the p-type CNT spun yarn 1b.
  • the n-type CNT spun yarn 2c is sewn.
  • the method for sewing the n-type CNT spun yarn 2c is the same as the method for sewing the n-type CNT spun yarn (2a, 2b).
  • the p-type CNT spun yarn 1c and the n-type CNT spun yarn 2c are knitted in the p-type CNT spun yarn 1a and the n-type CNT spun yarn 2a, or the p-type CNT spun yarn 1b and the n-type CNT spun yarn 2b. This is the same as the weaving method.
  • the p-type CNT spun yarn 1d is sewn.
  • the method for sewing the p-type CNT spun yarn 1d is the same as the method for sewing the p-type CNT spun yarn (1b, 1c).
  • the n-type CNT spun yarn 2c and the p-type CNT spun yarn 1d are knitted by the n-type CNT spun yarn 2a and the p-type CNT spun yarn 1b or the n-type CNT spun yarn 2b and the p-type CNT spun yarn 1c. This is the same as the weaving method.
  • the adjacent n-type CNT spun yarn 2 before one step is knitted on the back surface, and when the n-type CNT spun yarn 2 is sewn, it is adjacent.
  • the p-type CNT spun yarn 1 before one step is knitted into the insulating base material 3 so as to be knitted on the back surface.
  • FIG. 14 shows a flowchart of a method for manufacturing a functional element of the present invention.
  • the p-type spun yarn is wave-stitched linearly on the insulating base material (step S01).
  • step S01 the n-type spun yarn is wave-sewn adjacent to the wave-sewn p-type spun yarn in parallel, the portion exposed on the surface of the p-type spun yarn sewed one step before on the surface intersects. And sew after twisting once (step S02).
  • step S02 sew after twisting once
  • step S03 After being twisted, sewing is performed (step S03). Steps 2 and 3 are repeated as many times as necessary (step S04).
  • step S01 good conductor thin wires are used instead of p-type spun yarn, and the final step S03 is repeated.
  • a good conductor fine wire instead of using the p-type spun yarn, a good conductor fine wire may be used.
  • the direction perpendicular to the direction of wave stitching is a current path, and a ⁇ -type structure series connection is formed along the current path. In other words, the equipotential points are laterally connected in parallel.
  • FIG. 15 (1) shows a conventional thermoelectric conversion element based on a ⁇ -type structure series structure in which three sets of series connection units are juxtaposed in order to obtain a sufficient amount of generated power by increasing the area. Yes. These three sets of series connection units are connected in parallel outside the element.
  • this element let us consider a case in which a break occurs in the current path at the location indicated by the cross in the figure. As a result of this disconnection at one place, one set of series connection units painted in gray completely stops the power generation operation.
  • a large-area element in which 10 sets of 10 ⁇ -type cells connected in series are juxtaposed and connected externally in parallel. In this large-area element, if the spun yarn breaks at one place, the total electric conductance becomes 90% (that is, the electric resistance is about 110%), and the maximum power generation amount is also reduced to 90%. That is, a 10% reduction in generated power occurs.
  • FIG. 15 (2) shows a thermoelectric conversion element having a network structure of functional elements of the present invention.
  • a case is considered in which a disconnection occurs in the current path at a location indicated by a cross in the figure. Due to this disconnection at one location, the ⁇ -type half-cells painted in gray cease to generate electricity, but since the topology of the current path is a network structure, they are considered to belong to the same ⁇ -type structure cell. Since current paths are secured in all cells including adjacent half-cells capable of generating power, the power generation operation other than the disconnected seam portion is not affected. For example, consider a large-area device having a network structure of ⁇ -type cells 10 ⁇ 10 units.
  • the total number of cells is the same as that of the large-area element by the conventional series connection described above.
  • the total electric conductance is about 99% (that is, the electric resistance is about 101%), and the maximum power generation amount is about 99%. That is, the decrease in generated power is suppressed to 1%.
  • thermoelectric characteristics of the functional element of the present invention The p-type spun yarn obtained by spinning the CNT composite material by the method shown in FIG. 8 and the n-type spun yarn doped by the method shown in FIG. Thus, the thermoelectric characteristics of the functional element having the network structure shown in FIG. 7 were evaluated.
  • a thermoelectric output characteristic graph of the functional element is shown in FIG. From Table 2, it can be seen that the open-circuit voltage increases in proportion to the temperature difference between the front surface and the back surface. Further, as shown in FIG. 13, the output characteristics are also characteristics as shown in the theory that the output power draws a parabola with respect to the voltage according to the load resistance.
  • This functional element has sufficient flexibility, and it was confirmed that the element resistance did not change with respect to bending, twisting, and pulling of about several percent. In addition, it is confirmed that an output corresponding to a temperature difference of 5 to 10 ° C can be obtained by simply touching one side with the hand in the atmosphere because of the use of a heat insulating base material and a CNT composite material spun yarn having low thermal conductivity. It was.
  • a functional element having the same structure as that of Embodiments 1 and 2 and having higher performance will be described.
  • the structure of the functional element of this example is the same as the schematic diagram of the functional element shown in FIG. That is, in the functional element of this example, as shown in FIG. 7, the p-type spun yarn 1 and the n-type spun yarn 2 of conductive nanofibers are sewn into a sheet-like insulating substrate 3 such as a nonwoven fabric.
  • the p-type spun yarn 1 and the n-type spun yarn 2 are sewn so that the front and back surfaces of the insulating base material 3 are corrugated and joined together when alternately penetrating the front and back surfaces. It is rare.
  • FIG. 7 the schematic diagram of FIG.
  • the p-type spun yarn 1 and the n-type spun yarn 2 are each provided with six stitches so that the ⁇ -type thermoelectric conversion cells can be connected vertically and horizontally in both a series connection and a parallel connection.
  • three p-type spun yarns 1 and 2 are formed.
  • the n-type spun yarn 2 passes through the front and back surfaces of the insulating base material alternately, the yarns are crossed, twisted once, engaged and joined, and the p-type spun yarn 1 and the n-type spun yarn are joined.
  • Each thread 2 is provided with seven seams, so that the ⁇ -type thermoelectric conversion cells are vertically connected in a mesh shape in both series connection and parallel connection.
  • a horizontally connected structure (2.5 units in series, 14 units in parallel) is formed.
  • the copper wire 4 is connected only to both ends of the p-type spun yarn, that is, only to the end of the series structure of the ⁇ -type thermoelectric conversion cell. It was set as the structure where a copper wire is connected for every. That is, the copper wire 4 is sewn so as to alternately penetrate the front surface and the back surface of the insulating base material 3, and on the front surface and the back surface of the insulating base material 3, it intersects with the p-type spun yarn for each stitch. And connected to a ⁇ -type thermoelectric conversion cell for each stitch.
  • copper wire, p-type spun yarn, n-type spun yarn, p-type spun yarn, n-type spun yarn, p-type spun yarn, copper wire are sewn in this order, and the copper wire and p-type spun yarn intersect at each stitch. It has been made to.
  • a silver paste 5 was applied to the portion where the p-type spun yarn 1, the n-type spun yarn 2 and the copper wire 4 were engaged in order to reinforce the electrical connection at the intersection.
  • the method for producing the CNT spun yarn is the same as in Example 1, but the CNTs used and the aggregating liquid are different, and the diameter of the produced CNT spun yarn is different. Similar to the first embodiment, description will be made with reference to FIG. CNT used what was made using eDIPS method (enhanced Direct Injection Pyrolytic Synthesis method). Ultrasonically dispersed, dispersed in a 3% by weight aqueous solution of SDS (Sodium Dodecyl Sulfate), and further 0.01% by weight of polyethylene glycol was added as a binder. As shown in FIG.
  • SDS sodium Dodecyl Sulfate
  • the CNT dispersant 11 placed in the dispenser 12 was ejected to the agglomerate 15 in the container 14 placed on the turntable 13, thereby hydrodynamically drawing and spinning.
  • pure methanol was used as the aggregating liquid 15.
  • Spinning CNT16 is produced by adjusting the direction and position of the nozzle of the dispenser 12 so that the rotation speed is approximately 50 rpm and parallel to the water flow at a distance of about 3 cm from the central axis, and discharging the CNT dispersant 11. did. Thereafter, the solvent was replaced with pure water, and the spun CNT 16 was pulled up from one end and dried in the air to prepare a CNT spun yarn.
  • the obtained CNT spun yarn had a diameter of about 30 to 50 ⁇ m, and a spun yarn thicker than the CNT spun yarn of Example 1 (diameter of about 10 to 30 ⁇ m) could be produced.
  • [BMIM] PF 6 known as an ionic liquid was used for n-type doping of CNT spun yarn.
  • DMSO Dimethyl sulfoxide
  • the CNT spun yarn was immersed for 24 hours for doping.
  • DMSO has a role to help [BMIM] PF 6 penetrate into the CNT spun yarn.
  • the ionic liquid adhering to the CNT spun yarn after immersion was wiped off with an experimental cotton cloth.
  • thermoelectric properties of functional elements The thermoelectric characteristics of the functional element of this example were evaluated.
  • a thermoelectric output characteristic graph of the functional element of this example is shown in FIG. Due to improvements in the CNT spun yarn production method and doping method, an equivalent output voltage was obtained despite the fact that the number of series was smaller compared to FIG. 13 (in the case of FIG. 13, the number of series is 3.5 units). In contrast, in the case of FIG. 17, the number of series is 2.5 units), and the output power is increased. In addition, the output power has a theoretical characteristic that draws a parabola with respect to the voltage according to the load resistance.
  • the functional element of this example had sufficient flexibility, and it was confirmed that the element resistance did not change with respect to bending, twisting, and pulling of about several percent.
  • thermoelectric characteristics before and after the disconnection of the functional element of this example will be described. As shown in FIG. 18, the thermoelectric characteristics after cutting only one of the disconnection points 8 were evaluated. Table 4 below shows the maximum power generation amount before and after cutting at one place in the functional element of this example. From Table 4 below, it can be seen that the maximum power generation amount is increased in proportion to the square of the temperature difference between the front surface and the back surface. The element resistance was 239 ⁇ before cutting and 262 ⁇ after cutting.
  • this functional element In evaluating the influence of the disconnection of the maximum power generation amount, this functional element is rich in flexibility and stretchability, so it is difficult to make the applied temperature difference and the distribution in the element strictly constant. There are challenges. As a result, variations in measurement values and fluctuations due to time occur, and the influence is reduced by taking the average of the relative values of the generated power at each temperature in Table 4.
  • the average value of the amount of generated power at each temperature in Table 4 is 0.994, and it is determined that the decrease in maximum output is only about 0.6% due to disconnection at one location. This is slightly better than the theoretically predicted 2.5%, but it is judged to be a reasonable value considering the above error factors.
  • the element conductance is 0.912 times, and it is determined that the decrease due to disconnection at one place is about 8.8%. This is slightly larger than the theoretically predicted value of 4.8%, but is estimated to be an error due to variation in the resistance value of each cell.
  • FIG. 19 shows an equivalent circuit model of the functional element used in the simulation.
  • the equivalent circuit model of FIG. 19 is a model in which an equivalent circuit from a node point to a node point in a p-type or n-type thermoelectric yarn is represented by a voltage source as indicated by reference numeral 21.
  • each voltage source can provide a thermoelectromotive force of V p or V n , and a resistor R is connected in series inside the voltage source (not shown).
  • the value of the resistance R of each voltage source (V1 to V60) is set so large that it can be regarded as infinite with a given cutting probability, and the others are set to 100 ⁇ , and the voltage and current generated in the circuit was calculated.
  • voltage sources (V61, V62) are voltage sources used for obtaining the current-voltage characteristics of the element, and these have an internal resistance of 0 (zero).
  • a triangular mark indicated by reference numeral 22 represents a reference potential (0 V).
  • FIG. 20 shows the change in the output of the functional element as a result of changing the cutting probability of the CNT spun yarn constituting the stitch from 0 to 50% and trying 100 times each.
  • the vertical axis of the graph shown in FIG. 20 represents the maximum output power of the functional element normalized by the output when there is no disconnection, the error bar represents the maximum and minimum of the 100 trial results, “O” represents the average.
  • the output expected for the functional element decreases almost linearly as the cutting probability increases. However, even if the cutting probability is 50%, the output of the functional element still remains. It has been shown that the output is likely to remain.
  • the functional element of the present invention is a distributed power source for forming a sensor matrix for a smart house or smart building, or a thermoelectric conversion element for reusing exhaust heat energy in a house, office, or automobile as an energy harvesting element It can be used as a power source for sticker-type biological information measuring instruments (body temperature, pulse, electrocardiogram monitor, etc.).
  • the thermoelectric conversion element has the same structure as the thermocouple, the functional element of the present invention is a highly versatile planar high-sensitivity internal / external temperature difference sensor, automobile seat, office chair or carpet.
  • the functional element of the present invention is a cloth-like Peltier cooling used for seats and backrests of automobiles, trains, airplanes, etc. It can also be used for devices and clothing with heating and cooling functions.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Woven Fabrics (AREA)

Abstract

L'invention concerne un élément fonctionnel résistant à la déconnexion, comprenant une structure pour l'obtention d'un dispositif thermoélectrique flexible dont l'épaisseur est suffisante à l'obtention d'une différence de températures, la structure ayant une structure textile dans laquelle des fils constitués de matériau thermoélectrique sont cousus dans un matériau de base isolant flexible ayant une faible conductivité thermique. Dans une structure d'élément, une pluralité de structures en série de cellules de conversion thermoélectrique de type π qui utilisent une différence de températures dans la direction de l'épaisseur d'un matériau de base isolant sont agencées en parallèle, la structure d'élément ayant une topologie dans laquelle, dans des parties où le type p et le type n sont commutés, des étages qui ont le même potentiel pendant la génération de puissance électrique sont connectés électriquement, les cellules de conversion thermoélectrique de type π étant connectées en tant que circuits électriques aussi bien dans le sens de la longueur que dans le sens de la largeur en un maillage par connexion en série et connexion en parallèle. De cette manière, un élément fonctionnel qui n'est pas susceptible de détérioration de ses caractéristiques de sortie en raison de déconnexions peut être réalisé. Plus précisément, un fil torsadé de type n et un fil torsadé de type p comprenant une substance fibreuse électriquement conductrice sont cousus alternativement et en parallèle dans un drap de matériau de base isolant, le fil torsadé de type n et le fil torsadé de type p étant connectés électriquement lorsqu'ils pénètrent respectivement alternativement à travers une surface avant et une surface arrière du matériau de base isolant.
PCT/JP2017/032179 2016-09-06 2017-09-06 ÉLÉMENT FONCTIONNEL AYANT UNE STRUCTURE DE CELLULES EN SÉRIE D'ÉLÉMENTS DE CONVERSION THERMOÉLECTRIQUE DE TYPE π, ET SON PROCÉDÉ DE FABRICATION WO2018047882A1 (fr)

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JP2021027149A (ja) * 2019-08-05 2021-02-22 国立大学法人横浜国立大学 フラーレンナノウィスカーを含む複合材およびその作製方法と同複合材を使用した半導体デバイス
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系统
RU2778010C1 (ru) * 2021-06-17 2022-08-12 Розалия Альбертовна Габдуллина Способ изготовления термоэлектрического генератора на основе композиционных материалов
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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
WO2023127590A1 (fr) * 2021-12-28 2023-07-06 日東電工株式会社 Élément de conversion thermoélectrique et module de capteur

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JP7402485B2 (ja) 2019-08-05 2023-12-21 国立大学法人横浜国立大学 フラーレンナノウィスカーを含む複合材の作製方法
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RU2778010C1 (ru) * 2021-06-17 2022-08-12 Розалия Альбертовна Габдуллина Способ изготовления термоэлектрического генератора на основе композиционных материалов
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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
WO2023127590A1 (fr) * 2021-12-28 2023-07-06 日東電工株式会社 Élément de conversion thermoélectrique et module de capteur

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