WO2013114854A1 - Élément générateur de puissance thermoélectrique organique et son procédé de production - Google Patents

Élément générateur de puissance thermoélectrique organique et son procédé de production Download PDF

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Publication number
WO2013114854A1
WO2013114854A1 PCT/JP2013/000450 JP2013000450W WO2013114854A1 WO 2013114854 A1 WO2013114854 A1 WO 2013114854A1 JP 2013000450 W JP2013000450 W JP 2013000450W WO 2013114854 A1 WO2013114854 A1 WO 2013114854A1
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Prior art keywords
thermoelectric conversion
thermoelectric
conversion layer
power generation
generation element
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PCT/JP2013/000450
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English (en)
Japanese (ja)
Inventor
久保　雅洋
俊亘 小勝
雅芳 角野
渋谷　明信
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日本電気株式会社
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Publication of WO2013114854A1 publication Critical patent/WO2013114854A1/fr

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    • 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
    • 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

Definitions

  • the present invention relates to an organic thermoelectric power generation element using an organic conductive polymer material and a method for manufacturing the same.
  • thermoelectric power generation elements are elements that can convert heat energy and electrical energy to each other. By installing the thermoelectric generator in an environment where a temperature difference occurs between both ends of the thermoelectric generator, electric power can be taken out. By applying this phenomenon, waste heat generated from factories and automobiles is expected to be applied to power generation. In recent years, it is expected that power generated by thermoelectric power generation elements is generated using heat generated from office electronic devices such as servers and PCs, and that power is used as a power source for electronic devices such as sensors.
  • Waste heat generated by electronic devices or the like is often scattered not only on a flat surface but also on a surface including a curved surface portion and an uneven portion.
  • the thermoelectric power generation element be flexible as well as improving the power generation efficiency of the thermoelectric power generation element.
  • Patent Document 1 uses a thin film of a thermoelectric conversion material made of an organic conductive polymer (hereinafter referred to as a conductive polymer) formed on a flexible substrate.
  • a thermoelectric conversion material made of an organic conductive polymer (hereinafter referred to as a conductive polymer) formed on a flexible substrate.
  • a conductive polymer organic conductive polymer
  • Patent Document 2 has a corrugated shape in which peaks and troughs are alternately repeated, thereby increasing the arrangement ratio of thermoelectric conversion element pairs per unit area as compared to a planar shape.
  • a thermoelectric conversion module with improved power generation efficiency is disclosed.
  • thermoelectric power generation elements In order to generate power by thermoelectric power generation elements using waste heat generated by equipment such as air conditioners, lighting equipment, PCs, servers, etc., or human body temperature, the temperature difference within the surface scattered on curved surfaces and irregularities In addition, it is necessary to efficiently recover the temperature difference in the direction perpendicular to the installation surface as heat. For this purpose, thermoelectric conversion elements are required to have flexibility, reliability associated therewith, high power generation efficiency, and ease of manufacture that enables product variations that are expected to be used in many situations.
  • Patent Document 1 discloses a flexible thermoelectric element using a flexible substrate and a thin film of a thermoelectric conversion material made of a conductive polymer.
  • the conductive polymer thin film has an elongated shape.
  • the temperature difference is increased by ensuring a large distance between the hot junction and the cold junction, and the power generation efficiency is improved. Therefore, this thermoelectric element requires a large area and restricts the installation location.
  • thermoelectric elements In order to improve the degree of freedom of installation of thermoelectric elements, elements that can utilize the temperature difference in the vertical direction of the installation surface are effective.
  • the conductive polymer of Patent Document 1 is a thin film formed by vapor deposition and the substrate is flat, it is difficult to obtain a temperature difference in the direction perpendicular to the installation surface.
  • the linear expansion coefficient of the organic film as the substrate material is 10 times or more larger than the linear expansion coefficient of the inorganic material such as metal. Therefore, a structure in which a metal wiring or the like is formed on an organic film having a large linear expansion causes peeling due to mismatch of the linear expansion coefficient in view of the fact that thermoelectric elements are repeatedly used at high temperatures, and has a high reliability. There was a problem of causing a drop.
  • Patent Document 2 has a corrugated shape in which peaks and troughs are alternately repeated, thereby increasing the arrangement ratio of thermoelectric conversion element pairs per unit area as compared with a planar shape.
  • a thermoelectric conversion module with improved power generation efficiency is disclosed.
  • This thermoelectric conversion module is a rigid module using copper or constantan metal as a thermoelectric conversion material and ceramic such as alumina as an insulating material. Therefore, the degree of freedom of installation of the thermoelectric conversion module is greatly limited, and is limited to a flat heat source. Furthermore, since a plurality of materials are used for the thermoelectric conversion material, the manufacturing process is complicated, resulting in a decrease in manufacturing yield.
  • the present invention has been made in view of the above problems, has a flexible element structure, is excellent in reliability and manufacturability, and sufficiently secures the temperature difference between the heat absorbing portion and the heat radiating portion.
  • an organic thermoelectric power generation device capable of The thermoelectric power generation element of the present invention is suitable for generating power by efficiently recovering a temperature difference scattered over a wide range including a curved surface and a concavo-convex surface, eliminating restrictions on the installation of a conventional thermoelectric power generation element, A new thermoelectric generator is provided.
  • thermoelectric power generation element in which a plurality of thermoelectric conversion layers are connected in series, wherein the thermoelectric power generation element includes a base material having a wave shape structure in which a bottom portion and a top portion are alternately repeated, and the thermoelectric conversion layer includes the top portion and the top portion A first thermoelectric conversion layer along a first slope between the first bottom connected to the top and the second between the top and the second bottom connected to the top.
  • the first thermoelectric conversion layer and the second thermoelectric conversion layer have the same type, and the first thermoelectric conversion layer has the top side and On the first bottom side, the second thermoelectric conversion layer has connection points with wirings on the top side and the second bottom side, respectively.
  • connection between the first thermoelectric conversion layers is connected at the connection point on the top side of the first thermoelectric conversion layer, along the second slope, at the second bottom, It is a connection to be connected at a connection point on the bottom side of the first thermoelectric conversion layer adjacent to the first thermoelectric conversion layer, and the connection between the second thermoelectric conversion layers is the top of the second thermoelectric conversion layer.
  • the wiring connected at the connection point on the side is connected at the connection point on the bottom side of the second thermoelectric conversion layer adjacent to the second thermoelectric conversion layer at the first bottom along the first slope. It is a connection.
  • connection between the first thermoelectric conversion layer and the second thermoelectric conversion layer is connected at the connection point on the top side of the first thermoelectric conversion layer, along the second slope, Connection connected at the connection point on the bottom side of the second thermoelectric conversion layer, or wiring connected at the connection point on the top side of the second thermoelectric conversion layer, along the first slope,
  • the connection is made at a connection point on the bottom side of the first thermoelectric conversion layer, and both ends of the series connection are open electrodes.
  • thermoelectric power generation element having flexibility, excellent reliability and manufacturability, and capable of sufficiently ensuring a temperature difference between a heat absorption part and a heat dissipation part by the thermoelectric power generation element and the manufacturing method thereof according to the present invention.
  • Can do. Eliminates installation restrictions that were problems with conventional thermoelectric generators, and realizes thermoelectric generators suitable for generating power by efficiently recovering the temperature difference due to waste heat scattered widely in electronic equipment as heat To do.
  • thermoelectric power generation element of 1st embodiment of this invention It is a figure which shows the cross-section of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the planar structure of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the cross-section of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the planar structure of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the cross-section of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the planar structure of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the cross-section of the thermoelectric power generation element of 1st embodiment of this invention.
  • thermoelectric power generation element of 1st embodiment of this invention It is a figure which shows the cross-section of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the cross-section of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the cross-section of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the cross-section of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the planar structure of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the manufacturing method of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the manufacturing method of the thermoelectric power generation element of 1st embodiment of this invention.
  • thermoelectric power generation element of 1st embodiment of this invention It is a figure which shows the manufacturing method of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the manufacturing method of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the manufacturing method of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the manufacturing method of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the manufacturing method of the thermoelectric power generation element of 1st embodiment of this invention. It is a figure which shows the cross-section of a well-known thermoelectric power generation element. It is a figure which shows the cross-section of the thermoelectric power generation element of 2nd embodiment of this invention.
  • thermoelectric power generation element of 2nd embodiment of this invention It is a figure which shows the planar structure of the thermoelectric power generation element of 2nd embodiment of this invention. It is a figure which shows the cross-section of the thermoelectric power generation element of 2nd embodiment of this invention. It is a figure which shows the planar structure of the thermoelectric power generation element of 2nd embodiment of this invention. It is a 1st figure which shows the manufacturing method of the thermoelectric power generation element of 2nd embodiment of this invention. It is a 2nd figure which shows the manufacturing method of the thermoelectric power generation element of 2nd embodiment of this invention. It is a 3rd figure which shows the manufacturing method of the thermoelectric power generation element of 2nd embodiment of this invention. It is a 4th figure which shows the manufacturing method of the thermoelectric power generation element of 2nd embodiment of this invention.
  • thermoelectric power generation element of 2nd embodiment of this invention It is a 5th figure which shows the manufacturing method of the thermoelectric power generation element of 2nd embodiment of this invention. It is a schematic diagram of the cross section of the thermoelectric power generation element of 2nd embodiment of this invention. It is a schematic diagram of the cross section in which the bending of the cross section of the thermoelectric power generation element of 2nd embodiment of this invention eased. It is a figure which shows the pad electrode thickness d dependence of the yield Y1 and relative power generation efficiency (eta) of the thermoelectric power generation element of 2nd embodiment of this invention. It is a figure which shows the occupancy ratio X dependency of the pad electrode of the yield Y2 of the waveform of the thermoelectric power generation element of 2nd embodiment of this invention, and the yield Y3 of adhesive protrusion.
  • thermoelectric power generation element of 2nd embodiment of this invention It is a figure which shows the L1 / L2 ratio dependence of the wiring contact yield Y4 of the thermoelectric power generation element of 2nd embodiment of this invention, and the electric power generation amount per unit area. It is a figure which shows the cross-section of the thermoelectric power generation element of 2nd embodiment of this invention. It is a figure which shows the planar structure of the thermoelectric power generation element of 2nd embodiment of this invention. It is a plane structure figure of the thermoelectric power generation element of 2nd embodiment of this invention. It is a structural diagram of the pad electrode and wiring of the thermoelectric power generation element of the second embodiment of the present invention. It is an external view of the thermoelectric power generation element of 2nd embodiment of this invention.
  • thermoelectric power generation element according to a first embodiment of the present invention will be described with reference to FIGS. 1 and 2.
  • FIG. 1 shows a cross-sectional view of a thermoelectric generator according to a first embodiment of the present invention.
  • FIG. 2 shows a plan view of the thermoelectric generator of the first embodiment of the present invention.
  • a cross section taken along line AA 'in FIG. 2 corresponds to FIG.
  • the wiring 11 is not limited to this, and is described in FIG. 1 as necessary to explain the structure of the element.
  • thermoelectric power generation element 1 in which a plurality of thermoelectric conversion layers are connected in series.
  • the base material 2 of the thermoelectric generator 1 has a corrugated structure composed of a bottom and a top.
  • the thermoelectric conversion layer has a first thermoelectric conversion layer 8 along a first slope 6 between the top 3 and the first bottom 4 connected to the top 3, and further includes a first thermoelectric conversion layer 8 connected to the top 3 and the top 3.
  • 2 has a second thermoelectric conversion layer 9 along the second slope 7 between the bottom 5 of the two.
  • the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 have the same type. That is, if the first thermoelectric conversion layer 8 is P-type, the second thermoelectric conversion layer 9 is also P-type.
  • thermoelectric conversion layer of the present embodiment A conductive polymer material can be used for the thermoelectric conversion layer of the present embodiment.
  • a conductive polymer having P-type semiconductor characteristics can be used.
  • the first thermoelectric conversion layer 8 is provided on the top 3 side and the first bottom 4 side
  • the second thermoelectric conversion layer 9 is provided on the top 3 side and the second bottom 5 side.
  • the connection between the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 is along the second inclined surface 7.
  • the connection is made at the connection portion 10 on the bottom 5 side of the second thermoelectric conversion layer 9. Furthermore, both ends of the series connection of the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 are open electrodes.
  • the wiring 11 connected at the connection portion 10 on the top 3 side of the second thermoelectric conversion layer 9 is along the first slope 6.
  • the connection may be made at the connection portion 10 on the bottom 4 side of the first thermoelectric conversion layer 8. Also at this time, both ends of the series connection of the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 are open electrodes.
  • thermoelectric generator 1 the bottom is the heat absorption side and the top is the heat dissipation side. Power generation is performed by the temperature difference between the bottom side and the top side, and power can be taken out by the open electrode.
  • the base material has a wave shape, it is possible to secure the distance from the heat source to the bottom part that is the heat absorption side that is in contact with the heating element that is the heat source and the top part that is the heat radiation side. A sufficient temperature difference can be secured.
  • thermoelectric conversion layer can be comprised with the same type of single material, manufacture is made easy.
  • FIG. 3 shows a cross-sectional view of the thermoelectric generator of this embodiment.
  • FIG. 4 shows a plan view of the thermoelectric generator of the present embodiment.
  • a cross section taken along line B-B 'of FIG. 4 corresponds to FIG.
  • the wiring 11 is not limited to this, and is illustrated in FIG. 3 as necessary to explain the configuration of the element.
  • thermoelectric power generation element 30 in which a plurality of thermoelectric conversion layers are connected in series.
  • the base material 2 of the thermoelectric power generation element 30 has a wave shape structure in which a bottom portion and a top portion are alternately repeated.
  • the thermoelectric conversion layer has a first thermoelectric conversion layer 8 along a first slope 6 between the top 3 and the first bottom 4 connected to the top 3, and further includes a first thermoelectric conversion layer 8 connected to the top 3 and the top 3.
  • 2 has a second thermoelectric conversion layer 9 along the second slope 7 between the bottom 5 of the two.
  • the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 have the same type. That is, if the first thermoelectric conversion layer 8 is P-type, the second thermoelectric conversion layer 9 is also P-type.
  • thermoelectric conversion layer of the present embodiment A conductive polymer material can be used for the thermoelectric conversion layer of the present embodiment.
  • a conductive polymer having P-type semiconductor characteristics can be used.
  • the first thermoelectric conversion layer 8 is provided on the top 3 side and the first bottom 4 side
  • the second thermoelectric conversion layer 9 is provided on the top 3 side and the second bottom 5 side. Have.
  • connection between the first thermoelectric conversion layers 8 is such that the wiring 11 connected at the connection portion 10 on the top 3 side of the first thermoelectric conversion layer 8 is along the second inclined surface 7 and at the second bottom portion 5.
  • the connection is made at the connection portion 10 on the first bottom portion 4 side of the first thermoelectric conversion layer 8 adjacent to the one thermoelectric conversion layer 8.
  • the connection between the second thermoelectric conversion layers 9 is such that the wiring 11 connected at the connection portion 10 on the top 3 side of the second thermoelectric conversion layer 9 is along the first inclined surface 6 and at the second bottom portion 5.
  • the connection is made at the connection portion 10 on the first bottom portion 4 side of the second thermoelectric conversion layer 9 adjacent to the second thermoelectric conversion layer 9.
  • the wiring 11 connected at the connection portion 10 on the top 3 side of the first thermoelectric conversion layer 8 is along the second inclined surface 7.
  • the connection is made at the connection portion 10 on the bottom 5 side of the second thermoelectric conversion layer 9. Furthermore, both ends of the series connection of the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 are open electrodes.
  • the wiring 11 connected at the connection portion 10 on the top 3 side of the second thermoelectric conversion layer 9 is along the first slope 6.
  • the connection may be made at the connection portion 10 on the bottom 4 side of the first thermoelectric conversion layer 8. Also at this time, both ends of the series connection of the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 are open electrodes.
  • thermoelectric generator 30 the bottom is the heat absorption side and the top is the heat dissipation side. Power generation is performed by the temperature difference between the bottom side and the top side, and power can be taken out by the open electrode.
  • the base material has a wave shape, it is possible to secure the distance from the heat source to the bottom part that is the heat absorption side that is in contact with the heating element that is the heat source and the top part that is the heat radiation side. A sufficient temperature difference can be secured.
  • thermoelectric conversion layer can be comprised with the same type of single material, manufacture is made easy.
  • thermoelectric generator of this embodiment will be described with reference to FIGS.
  • FIG. 5 shows a cross-sectional view of the thermoelectric generator of this embodiment.
  • FIG. 6 shows a plan view of the thermoelectric generator of the present embodiment.
  • a cross section taken along line C-C 'in FIG. 6 corresponds to FIG.
  • the wiring 11 is not limited to this, and is described in FIG. 5 as necessary to explain the configuration of the element.
  • 5 and 6 is a thermoelectric power generation element 50 in which more thermoelectric conversion layers are connected in series than the thermoelectric power generation elements 30 in FIGS. 3 and 4.
  • the base material 2 of the thermoelectric power generation element 50 has a wave shape structure in which a bottom portion and a top portion are alternately repeated.
  • the thermoelectric conversion layer has a first thermoelectric conversion layer 8 along a first slope 6 between the top 3 and the first bottom 4 connected to the top 3, and further includes a first thermoelectric conversion layer 8 connected to the top 3 and the top 3.
  • 2 has a second thermoelectric conversion layer 9 along the second slope 7 between the bottom 5 of the two.
  • the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 have the same type. That is, if the first thermoelectric conversion layer 8 is P-type, the second thermoelectric conversion layer 9 is also P-type.
  • thermoelectric conversion layer of the present embodiment A conductive polymer material can be used for the thermoelectric conversion layer of the present embodiment.
  • a conductive polymer having P-type semiconductor characteristics can be used.
  • the first thermoelectric conversion layer 8 is provided on the top 3 side and the first bottom 4 side
  • the second thermoelectric conversion layer 9 is provided on the top 3 side and the second bottom 5 side. Have.
  • connection between the first thermoelectric conversion layers 8 is such that the wiring 11 connected at the connection portion 10 on the top 3 side of the first thermoelectric conversion layer 8 is along the second inclined surface 7 and at the second bottom portion 5.
  • the connection is made at the connection portion 10 on the first bottom portion 4 side of the first thermoelectric conversion layer 8 adjacent to the one thermoelectric conversion layer 8.
  • the connection between the second thermoelectric conversion layers 9 is such that the wiring 11 connected at the connection portion 10 on the top 3 side of the second thermoelectric conversion layer 9 is along the first inclined surface 6 and at the second bottom portion 5.
  • the connection is made at the connection portion 10 on the first bottom portion 4 side of the second thermoelectric conversion layer 9 adjacent to the second thermoelectric conversion layer 9.
  • the wiring 11 connected at the connection portion 10 on the top 3 side of the first thermoelectric conversion layer 8 is along the second inclined surface 7.
  • the connection is made at the connection portion 10 on the bottom 5 side of the second thermoelectric conversion layer 9.
  • the series connection of the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 is performed by connecting the wiring 11 connected at the connection portion 10 on the top 3 side of the second thermoelectric conversion layer 9 to the first slope 6.
  • both ends of the series connection of the first thermoelectric conversion layer 8 and the second thermoelectric conversion layer 9 are open electrodes.
  • thermoelectric generator 50 the bottom is the heat absorption side and the top is the heat dissipation side. Power generation is performed by the temperature difference between the bottom side and the top side, and power can be taken out by the open electrode.
  • the base material has a wave shape, it is possible to secure the distance from the heat source to the bottom part that is the heat absorption side that is in contact with the heating element that is the heat source and the top part that is the heat radiation side. A sufficient temperature difference can be secured.
  • thermoelectric conversion layer can be comprised with the same type of single material, manufacture is made easy.
  • thermoelectric generator of this embodiment will be described with reference to FIG. FIG. 7 shows a cross-sectional view of the thermoelectric generator 70 of the present embodiment.
  • the feature of the thermoelectric power generation element 70 is that the base material 2 has the reinforcing material 12.
  • the structure of the thermoelectric power generation element 70 is the same as that of the thermoelectric power generation element 50 except for the reinforcing material 12.
  • thermoelectric generator of this embodiment will be described with reference to FIG. FIG. 8 shows a cross-sectional view of the thermoelectric generator 80 of the present embodiment.
  • a feature of the thermoelectric power generation element 80 is that it includes the protective layer 13.
  • the structure of the thermoelectric generation element 80 is the same as that of the thermoelectric generation element 50 except for the protective layer 13.
  • thermoelectric generator of this embodiment will be described with reference to FIG. FIG. 9 shows a cross-sectional view of the thermoelectric generator 90 of this embodiment.
  • a feature of the thermoelectric power generation element 90 is a thermoelectric power generation element 90 in which a plurality of stacked thermoelectric power generation elements are connected in series.
  • a protective layer 13 may be inserted between the stacked thermoelectric generators.
  • the structure of the thermoelectric power generation element 90 is the same as that of the thermoelectric power generation element 50 except that the thermoelectric power generation element 90 includes a plurality of stacked thermoelectric power generation elements.
  • thermoelectric generator of this embodiment will be described with reference to FIG. FIG. 10 shows a cross-sectional view of the thermoelectric generator 100 of this embodiment.
  • the feature of the thermoelectric power generation element 100 is that it has a thermoelectric conversion layer and wiring on both surfaces of the substrate 2 and is connected in series.
  • the structure of the thermoelectric power generation element 100 is the same as that of the thermoelectric power generation element 50 except that the thermoelectric conversion layer and the wiring are provided on both surfaces of the substrate 2.
  • FIG. 14 shows a cross-sectional structure of a thermoelectric conversion element using a conventional inorganic material.
  • a P-type semiconductor material 16 and an N-type semiconductor material 17 made of an inorganic crystal such as bismuth tellurium are mounted on a ceramic substrate 20 through an electrode 18 and a wiring 19 so as to correspond to the heat absorption 21 side and the heat dissipation 22 side. Yes.
  • Power generation is performed by the temperature difference 23 generated between the heat absorption 21 side and the heat dissipation 22 side. Since conventional inorganic thermoelectric power generation elements are not flexible, they cannot cope with curved shapes. Further, the use of a plurality of thermoelectric conversion materials of the P-type semiconductor material 16 and the N-type semiconductor material 17 causes a decrease in manufacturability.
  • the base material 2 used for the thermoelectric generator of this embodiment is made of a flexible material. This material is required to have electrical insulation and not deteriorate due to the manufacturing process of the thermoelectric power generation element, the environmental temperature during use, the humidity, or the like.
  • the required heat resistance varies depending on the application. For example, when the thermoelectric power generation element of the present embodiment is used for power generation using the waste heat of lighting equipment as a heat source, it is exposed to a temperature of about 100 ° C. Heat resistance against this temperature is required.
  • the corrugated structure base material 2 used in the present embodiment has a sufficient temperature difference in a substantially vertical direction with respect to the installation surface of the thermoelectric power generation element generated between the heat absorption side at the bottom and the heat dissipation side at the top. It must be low in thermal conductivity so that it can be increased. Furthermore, it is necessary that the material is easy to mold into a wave-shaped structure.
  • resins such as polyimide, polyethylene naphthalate, polyethylene terephthalate, polycarbonate, epoxy resin, aramid resin, silicone resin, ABS resin, and various rubber elastic resins such as silicone rubber and polybutadiene rubber Can be used.
  • the substrate has a thickness of 10 microns or more.
  • the thickness is 2 mm or less as a thickness for facilitating the transfer of the temperature of the heat source to the thermoelectric generator element part without impairing flexibility. If it is 2 mm or less, it can follow also when the installation surface of a thermoelectric power generation element has a fixed curvature.
  • the layer for reducing the thermal resistance with a heat source part may be apply
  • the flexibility of the base material can contribute to increasing the efficiency at the time of heat recovery from the heat source part, and is effective in improving the thermoelectric power generation performance.
  • the base material used here needs to have electrical insulation, it does not necessarily need to be formed with a single organic material.
  • the organic material may contain an inorganic filler or an inorganic fiber. Silicon filler or glass fiber can be used to reduce the linear expansion coefficient.
  • thermoelectric generator of this embodiment can use a conductive polymer material.
  • conductive polymer materials having P-type semiconductor characteristics applicable to this embodiment include polymers having thiophene and its derivatives as a skeleton, polymers having phenylene vinylene and its derivatives as a skeleton, and polymers having aniline and its derivatives as a skeleton.
  • Oligomers and polymers having pyrrole and its derivatives in the backbone Oligomers and polymers having acetylene and its derivatives in the backbone, polymers having heptadiene and its derivatives in the backbone, phthalocyanines and their derivatives, diamines, phenyldiamines and their Derivatives, pentacene and its derivatives, porphyrin and its derivatives, cyanine, quinone, naphthoquinone, and other small molecules.
  • Polythiophene and its derivatives can be used particularly advantageously from the standpoints of manufacturability, stability in the atmosphere, charge mobility and the like.
  • the thermal conductivity of the conductive polymer is about 1/10 to 1/100 that of the inorganic thermoelectric material, the heat conducted from the heat absorbing portion to the heat radiating portion can be greatly reduced. That is, the temperature difference between the heat absorption part and the heat radiation part can be maintained sufficiently large.
  • the film thickness of the conductive polymer used in this embodiment can be 0.01 mm or more and 2 mm or less.
  • the required flexibility can be imparted to the thermoelectric element by setting the film thickness of the conductive polymer to 2 mm or less.
  • the current amount required in order to take out a voltage as a thermoelectric power generation element can be ensured by setting it as 0.01 mm or more.
  • a conductive polymer having P-type semiconductor characteristics can be used.
  • the cross-sectional area perpendicular to the heat flow direction of the wiring straddling the heat absorption side at the bottom and the heat dissipation side at the top is the cross-sectional area perpendicular to the heat flow direction of the conductive polymer. It is desirable that it is small compared. This is because, when the cross-sectional area of the wiring part is large, heat is easily conducted through the wiring part in the direction of reducing the temperature difference between the heat absorbing part and the heat radiating part, so that it is difficult to ensure the temperature difference.
  • the cross-sectional area of the wiring part is small, sufficient current cannot be taken out, and reliability may be impaired due to insufficient physical strength.
  • polyaniline thermal conductivity 0.2 W / mK
  • copper thermal conductivity 372 W / mK
  • the wiring is maintained while maintaining the temperature difference between the heat absorption side and the heat dissipation side.
  • the ratio of the cross-sectional area of the copper wiring to the cross-sectional area of the polyaniline element needs to be 1/10 or less. More preferably, 1/30 or less is desirable.
  • the linear expansion coefficient of the conductive polymer is about 10 times larger than that of the conductive material used for the wiring part. Therefore, the reliability is lowered due to the mismatch of the linear expansion coefficients.
  • the temperature of the heat source varies depending on the operation status of the CPU of the PC or server. In such applications, cracks occur in the wiring portion or the contact portion between the conductive polymer and the wiring, and the reliability of the element is impaired.
  • a large-area thermoelectric conversion element is required. At this time, for example, when a square thermoelectric conversion element is used, the influence of the mismatch of the linear expansion coefficient is particularly noticeable particularly at the outer corner.
  • the metal material has high thermal conductivity. Therefore, in the wiring portion extending between the heat absorbing portion and the heat radiating portion, heat is generated in a direction that reduces the temperature difference. Flow and power generation performance will be reduced. Therefore, in order to maintain the temperature difference, it is necessary to reduce the cross-sectional area of the wiring part as much as possible. On the other hand, by reducing the cross-sectional area, the physical strength is lowered and the reliability is lowered when a thermal load is generated.
  • the thermoelectric conversion element of this embodiment can use a structure having elasticity in the wiring portion.
  • the wiring portion 11 is formed when expansion / contraction occurs such as a loop-like slack shape, a bellows shape (FIG. 9), a lattice shape (FIG. 10), or the like. Can relieve stress and make it hard to break. In this way, even when using a base material that reversibly expands and contracts by 10% or more, it is possible to use it while ensuring reliability.
  • FIG. 11 shows a plan view of the thermoelectric generator 110 of the present embodiment.
  • a feature of the thermoelectric generator 110 is that the wiring has a bellows structure wiring 14.
  • Other elements constituting the thermoelectric power generation element 110 are the same as those of the thermoelectric power generation element 30.
  • FIG. 12 is a plan view of the thermoelectric generator 120 of the present embodiment.
  • a feature of the thermoelectric power generation element 120 is that the wiring has a lattice structure wiring 15.
  • Other elements constituting the thermoelectric power generation element 120 are the same as those of the thermoelectric power generation element 30.
  • the material of the wiring part having elasticity is not only a metal such as a gold wire or an aluminum wire, but also a rubber material kneaded with a conductive fiber such as a carbon nanotube, or a liquid metal in the channel structure. It is possible to fill it with a conductor.
  • the liquid metal include a gallium indium alloy (for example, Ga75.5In24.5 has a melting point of about 15 ° C.).
  • thermoelectric conversion layer and the wiring with the conductive polymer of this embodiment an electrode made of a metal thin film layer having good conductivity is provided, and the thermoelectric conversion layer and the wiring are connected via this electrode. Can do. Thereby, the contact resistance between a thermoelectric conversion layer and wiring can be reduced, and the performance enhancement of an element can be achieved.
  • a suitable ratio of the wiring cross-sectional area of the wiring part having elasticity of the present embodiment and the cross-sectional area perpendicular to the heat flow direction of the thermoelectric conversion layer by the conductive polymer is the conductivity or thermal conductivity of the material used for the wiring part. by.
  • the ratio of the cross-sectional area of the wiring to the cross-sectional area of the conductive polymer element is 1 / 30 or less. More preferably, 1/100 or less is desirable. This is because if the ratio of the cross-sectional area exceeds 1/30, the wiring structure relaxes the temperature difference between the heat absorbing portion and the heat radiating portion.
  • the length in the heat flow direction of the thermoelectric conversion layer by the conductive polymer of the present embodiment can be 0.5 mm or more and 10 mm or less. By setting it as the range of this length, it is excellent in a softness
  • the element can be covered with a material having high thermal conductivity as a protective layer for protecting the thermoelectric conversion layer and wiring.
  • This protective layer is effective for mechanical protection of the thermoelectric conversion layer surface, improvement of moisture resistance, ensuring insulation, and the like. This also makes it possible to reduce contact resistance with the heat source and improve heat dissipation.
  • thermoelectric generator of this embodiment is a method for manufacturing a thermoelectric generator of the present invention.
  • a moldable and flexible base material to be the base material 2 of the thermoelectric power generation element is prepared, and after cleaning with a solvent such as alcohol, surface treatment such as plasma treatment is performed.
  • thermoelectric conversion layer 8 is formed.
  • the thermoelectric conversion layer is a method of printing and pasting a paste in which a conductive polymer is dissolved in a solvent, drying it into a film, and pasting it on a substrate, cutting a bulk material of a conductive polymer into a film, and pasting it. Is possible.
  • thermoelectric conversion material As a printing method of the paste-like thermoelectric conversion material, methods such as bar coating, screen printing, and spin coating are possible after performing masking as necessary. Or the method of apply
  • a paste of a thermoelectric conversion material can be applied and dried to form a conductive polymer film. In order to obtain a conductive polymer film having a high electron mobility, it is effective to print while orienting the conductive polymer monomer dispersed in the ink.
  • thermoelectric conversion layer can be formed by attaching a conductive polymer film to the adhesive and curing the adhesive.
  • connection portions 10 for fixing the wiring are provided at both ends of the obtained thermoelectric conversion layer.
  • an electrode can be formed by providing a metal layer in a connection part.
  • a surface treatment such as plasma treatment may be performed on the surface of the thermoelectric conversion layer in advance.
  • the electrode As a means for forming the electrode, a method such as a method of printing a conductive paste using a mask or a gas layer growth method such as vapor deposition or sputtering is possible.
  • the electrode material can be gold, silver, platinum, copper, aluminum, rhodium, or the like. Gold can be suitably used in that it is less affected by oxidation and improves the production yield and can easily reduce the contact resistance with the organic conductive polymer. In order to reduce the contact resistance between the thermoelectric conversion layer and the wiring, it is effective to form a fine unevenness on the surface of the connection part or the electrode by a nanoimprint method or the like to increase the surface area.
  • the wiring 11 is formed in the connection portion. It is desirable that the wiring has a structure that is not easily stressed in order to prevent breakage caused by mismatching of the linear expansion coefficients of the base material and the thermoelectric conversion layer due to a rise and fall in temperature when the thermoelectric power generation element is used.
  • a wire such as gold or copper is connected to the connecting portion, or, when an electrode is formed, the wire and the electrode are connected by a conductive paste. At this time, the wire is allowed to have slack.
  • the wire can also have a bellows structure or a lattice structure.
  • Wiring can also be formed by a printing method. For example, by applying a paste in which carbon nanotubes are dispersed in silicone rubber, it is possible to form a wiring corresponding to a stress when the heat load is high. Also, when gold or copper is used, wiring corresponding to stress can be formed by using a bellows structure or a lattice structure.
  • the base material on which the thermoelectric conversion layer and the wiring are formed is formed into a corrugated structure.
  • a hot embossing method can be used. That is, two molds having a wave shape are prepared, and the bent portion and the wave shape of the mold are aligned. Thereafter, the substrate on which the thermoelectric conversion layer and the wiring are formed is sandwiched between heated molds and held for an appropriate time, whereby the wave shape can be transferred to the substrate and molded.
  • the reinforcing material 12 is formed on the base material in the step of FIG. 13F.
  • the reinforcing material 12 can be obtained by applying and embedding a flexible resin material on the back surface of the substrate 2.
  • the protective layer 13 is formed in the process of FIG. 13G as needed.
  • the protective layer is formed by attaching a film-like sheet having insulating properties.
  • the electrode and the like can be exposed by a photolithography method after the protective layer is formed.
  • a thermoelectric power generation element can be electrically connected with an external circuit.
  • the electrode can be exposed by laser processing and desmear processing after laser processing, and can be electrically connected to an external circuit.
  • Example 1 A PET (polyethylene terephthalate) base material having a thickness of 0.1 mm was prepared, degreased and washed with ethanol, and subjected to surface treatment with oxygen plasma for 1 minute. Subsequently, in order to fix the film-like conductive polymer to the substrate, a silicone resin adhesive was applied to the substrate surface by a screen printing method.
  • thermoelectric conversion layer was formed on the PET substrate.
  • connection terminal portion with the external circuit was formed by etching the electrode pad portion with a UV-YAG laser, performing plasma treatment at 150 ° C. to remove the residue after laser processing, and exposing the electrode pad.
  • thermoelectric conversion layers were connected in series in an array on a 200 mm square PET substrate.
  • a fluorescent lamp with a temperature of about 65 ° C. was used on the heat absorption side of the obtained element and the atmosphere at 24 ° C. was used on the heat dissipation side, a power generation amount of about 0.1 mW was obtained.
  • thermoelectric power generation elements Two types were produced in which the length of the wiring connecting the thermoelectric conversion layers made of the conductive polymer in series was 8 mm and 5 mm.
  • the obtained thermoelectric power generation element was subjected to a thermal shock test in which a cycle of holding at ⁇ 40 ° C. for 15 minutes, holding at 25 ° C. for 5 minutes, and holding at 125 ° C. for 15 minutes was one cycle.
  • the thermoelectric power generation element with a wiring length of 8 mm has a long number of cycles and has a long-term reliability as compared with a thermoelectric power generation element with a wiring length of 5 mm.
  • the length of the wiring is 10% or more longer than the length between adjacent thermoelectric conversion layers, long-term reliability can be secured.
  • thermoelectric generator with high long-term reliability can be realized.
  • a PEN (polyethylene naphthalate) substrate having a thickness of 0.1 mm was prepared and subjected to oxygen plasma treatment for 1 minute. Subsequently, in order to fix the film-like conductive polymer to the substrate, a silicone resin adhesive was applied to the substrate surface by a screen printing method.
  • a PEN semiconductor material (trade name: PH1000) monomer aqueous solution is applied onto a PDMS substrate and dried under reduced pressure overnight at 10 mbar at room temperature.
  • a conductive polymer film was produced on the substrate.
  • the obtained substrate was stretched while being heated to 70 ° C., cut out into dimensions of 5 mm in length ⁇ 2 mm in width ⁇ 0.05 mm in thickness, and then bonded to the aforementioned silicone resin adhesive, and 2 at 70 ° C.
  • the silicone resin adhesive was cured by heat treatment for a period of time.
  • a thermoelectric conversion layer was formed on the PEN substrate.
  • the obtained base material with the conductive polymer layer is subjected to oxygen plasma treatment for 1 minute, and a metal mask patterned so that the end of the conductive polymer layer is opened is placed on the base material.
  • An electrode having a thickness of about 100 nm was formed by sputtering.
  • a conductive paste is printed and heat-treated using a screen printing method so that a bellows structure is formed. did. (See Figure 11)
  • molding and protective layer formation were performed in the same process as in Example 1 to obtain a thermoelectric power generation element.
  • thermoelectric conversion layers were connected in series in an array on a 200 mm square PEN substrate.
  • a fluorescent lamp with a temperature of about 65 ° C. was used on the heat absorption side of the obtained element and the atmosphere at 24 ° C. was used on the heat dissipation side, a power generation amount of about 0.1 mW was obtained.
  • thermoelectric power generation elements were produced by the above process, when the wiring connecting the conductive polymer layers in series had a bellows structure and a straight structure.
  • the obtained thermoelectric power generation element was subjected to a thermal shock test in which a cycle of holding at ⁇ 40 ° C. for 15 minutes, holding at 25 ° C. for 5 minutes, and holding at 125 ° C. for 15 minutes was one cycle.
  • a thermal shock test in which a cycle of holding at ⁇ 40 ° C. for 15 minutes, holding at 25 ° C. for 5 minutes, and holding at 125 ° C. for 15 minutes was one cycle.
  • the thermoelectric power generation element with the bellows-structured wiring has a longer number of cycles and the long-term reliability than the thermoelectric power generation element with the linear structure wiring.
  • thermoelectric generator with high long-term reliability can be realized.
  • Example 3 A polyimide base material having a thickness of 0.1 mm was prepared, and oxygen plasma treatment was performed for 1 minute. Subsequently, in order to fix the thermoelectric conversion film, a silicone resin adhesive was applied by a screen printing method. The above process was performed on both sides of the substrate.
  • the obtained base material with a conductive polymer layer is subjected to oxygen plasma treatment for 1 minute, and a metal mask patterned so as to open the ends of the conductive polymer layer is placed on the substrate. Electrodes having a thickness of about 100 nm were formed on the front and back surfaces of the substrate by sputtering, and electrodes were formed at the ends of the conductive polymer layer formed on both sides of the substrate. Thereafter, molding and protective layer formation were performed by the same process as in Example 1 to obtain a thermoelectric power generation element (see FIG. 10).
  • thermoelectric conversion layers were connected in series in an array on a 200 mm square polyimide substrate.
  • a fluorescent lamp with a temperature of about 65 ° C. was used on the heat absorption side of the obtained element and the atmosphere at 24 ° C. was used on the heat radiation side, a power generation amount of about 0.2 mW was obtained.
  • thermoelectric conversion elements Two types were manufactured by the above process, in which the wiring connecting the conductive polymer layers in series had a bellows structure and a linear structure.
  • the obtained thermoelectric power generation element was subjected to a thermal shock test in which a cycle of holding at ⁇ 40 ° C. for 15 minutes, holding at 25 ° C. for 5 minutes, and holding at 125 ° C. for 15 minutes was one cycle.
  • a thermal shock test in which a cycle of holding at ⁇ 40 ° C. for 15 minutes, holding at 25 ° C. for 5 minutes, and holding at 125 ° C. for 15 minutes was one cycle.
  • the thermoelectric power generation element with the bellows-structured wiring has a longer number of cycles and the long-term reliability than the thermoelectric power generation element with the linear structure wiring.
  • FIG. 15 is a diagram showing a cross-sectional structure of a thermoelectric power generation element representing the second embodiment of the present invention.
  • FIG. 16 is a diagram showing a planar structure of a thermoelectric power generation element representing the embodiment of the present invention.
  • FIG. 15 shows a cross-sectional structure taken along line AA ′ of FIG.
  • the thermoelectric power generating element includes a base material 32, a top portion 33, a first bottom portion 34, a second bottom portion 35, a first slope 36, a second slope 37, a first thermoelectric conversion layer 38, and a second thermoelectric conversion.
  • the layer 39, the pad electrode part 40, the fine wiring part 41, the first electrode 42, and the second electrode 43 are included.
  • an output is obtained from the first electrode 42 and the second electrode 43 by providing a temperature difference between the bottom 34 and the top 33.
  • thermoelectric power generation element has a pad electrode portion 40 for connecting the first thermoelectric conversion layer 38 or the second thermoelectric conversion layer 39 and the fine wiring portion 41.
  • the pad electrode and the fine wiring are made of rolled copper, and the surface of the rolled copper is silver-plated to prevent oxidation.
  • Silver plating has the advantage of lowering the electrical contact resistance when the thermoelectric conversion layer 38 is bonded to the pad electrode portion 40 with a silver paste.
  • the substrate 32 is a polyimide film having a thickness of 50 ⁇ m.
  • a substrate having heat resistance at 150 ° C. such as a polyimide film is suitable for this embodiment.
  • the pad electrode and the fine wiring were formed by adhering a rolled copper thin film on the substrate 32 and then removing unnecessary copper by etching using a photolithography method.
  • the present embodiment is characterized in that the pad electrode portion 40 and the fine wiring portion 41 are in contact with the base material 32.
  • the fine wiring portion 41 has a thickness of 18 ⁇ m and a line width of 50 ⁇ m. In order to maintain the temperature difference between the top 33 and the bottom 34, it is desirable that the width of the fine wiring is narrow. On the other hand, if the width of the fine wiring is narrowed, the yield of the element is lowered. Therefore, the width of the fine wiring is suitably 15 ⁇ m to 60 ⁇ m.
  • the thickness of the pad electrode part 40 is 18 ⁇ m, the dimension of the pad electrode part 40 is 3 mm ⁇ 4 mm, and the width of the gap between adjacent pad electrodes 40 in the plan view is 2 mm.
  • the ratio of the two electrode pads having a width of 4 mm in the length 12 mm of the top broken line (B-B ′ in FIG. 16) is 66%.
  • the interval between the bottoms of the corrugated base material is 3 mm.
  • the first thermoelectric conversion layer 38 and the second thermoelectric conversion layer 39 are made of poly 3,4-ethylenedioxythiophene / polystyrene sulfonate (poly (3,4-ethylenedioxythiophene) / poly (styreneenesulfonate) as a conductive polymer material film. ), Hereinafter referred to as PEDOT / PSS.)
  • the film has a width of 4 mm, a length of 15 mm, and a thickness of 40 ⁇ m.
  • both ends of the conductive organic film were bonded to the two pad electrodes. After bonding, the bonded portion was cured by heating at 150 ° C. for 30 minutes. The electrical resistance between the pad electrodes connected by one thermoelectric conversion layer after curing was 1 ⁇ . When gold plating was applied to the pad electrode surface, the electrical resistance was 0.8 ⁇ . This is because the contact resistance is reduced because gold is equal to the work function of PEDOT / PSS.
  • thermoelectric power generation element avoids bending at the fine wiring portion and bends at the pad electrode portion 40 to form the top portion and the bottom portion.
  • the first advantage of the present embodiment is that the fine metal wiring portion does not break during bending because the pad electrodes are formed on the folded top and bottom. As a result, the yield is improved and the reliability is improved. Wiring using rolled copper is resistant to breakage.
  • the second advantage is that since the folded top and bottom are pad electrodes having a certain thickness, a high-density corrugated structure folded at an acute angle can be stably maintained. Thereby, it can prevent that a bending angle increases by the elasticity of a base film, and a wiring part and a thermoelectric conversion layer contact-short-circuit.
  • the third advantage is that since both ends of the thermoelectric conversion part connect the top and bottom of the wave-shaped structure, a large temperature difference is created between both ends of the thermoelectric conversion layer, and a high power generation amount is obtained.
  • thermoelectric power generation element has higher reliability and mass productivity than wiring formed of bonding wires because the wiring is formed of rolled copper.
  • the base film does not deteriorate due to bonding, and the connection strength is not lowered due to a low bonding temperature, so that there is no disconnection. Further, there is an advantage that it does not take time and effort to form a great number of bonding wires.
  • FIG. 17 is a diagram showing a cross-sectional structure of a thermoelectric power generation element representing this embodiment.
  • FIG. 18 is a diagram showing a planar structure of a thermoelectric power generation element representing this embodiment.
  • FIG. 17 shows a cross-sectional structure taken along CC ′ in FIG.
  • This thermoelectric power generation element is a thermoelectric power generation element in which the number of thermoelectric conversion parts of the thermoelectric power generation elements in FIGS. 15 and 16 is quadrupled.
  • the support base material 31 the base material 32, the top 33, the first bottom 34, the second bottom 35, the first slope 36, the second slope 37, the first thermoelectric conversion layer 38, the first 2 thermoelectric conversion layers 39, pad electrode portions 40, fine wiring portions 41, first electrodes 42, and second electrodes 43.
  • the base material 32 is a polyimide film, and the thickness of the base material 32 is 40 ⁇ m to 80 ⁇ m, which is suitable for keeping the folded and corrugated shape.
  • thermoelectric power generation element has a structure in which eight thermoelectric conversion layers are wired in series using pad electrodes and fine wiring, bent into a wave shape, and bonded to the support substrate 31.
  • the dimensions of the thermoelectric conversion layer 38, the pad electrode portion 44, and the fine wiring portion 41 are the same as those in FIGS.
  • the ratio of the four electrode pads on the broken line to the length of the broken line is 70%.
  • the length between the top and the bottom is 15 mm and the gap between the bottoms of the corrugated structure is 3 mm.
  • the dimensions of the outer shape after bending are 26 mm in length, 14 mm in width, and 14 mm in height.
  • thermoelectric power generation element an output is obtained from the first electrode 42 and the second electrode 43 by providing a temperature difference between the bottom portions 34 and 35 and the top portion 33. 17 and 18, an output four times that of the thermoelectric generators shown in FIGS. 15 and 16 can be obtained.
  • FIG. 19 shows a first diagram showing a method for manufacturing the thermoelectric generator of this embodiment.
  • a rectangular pad electrode portion 40, a fine wiring portion 41 connecting the pad electrode portion 40, a first electrode 42, and a second electrode 43 are formed on the base material 32 using rolled copper by photolithography and etching.
  • FIG. 20 shows a second diagram illustrating the method for manufacturing the thermoelectric generator of this embodiment.
  • a conductive adhesive 81 such as silver paste is applied to the end of the opposing pad electrode.
  • the conductive adhesive 81 is dropped onto the end of the pad electrode using a dispenser or the like, and an amount necessary for adhesion is applied.
  • FIG. 21 shows a third diagram showing the method for manufacturing the thermoelectric generator of this embodiment. Eight strips with a width of 4 mm and a length of 15 mm are cut out from a PEDOT / PSS film having a thickness of 40 ⁇ m, and 8 places are pasted so as to connect the pad electrodes. Pad electrode part 40, first thermoelectric conversion layer 38, pad electrode part 40, fine wiring 41, pad electrode part 40, first thermoelectric conversion layer 38, fine wiring 41 and the like from first electrode 42 through fine wiring Connect in series. Further, the fine wiring 41 is folded back in the opposite direction at the right end of FIG. 21, and the pad electrode portion 40, the second thermoelectric conversion layer 39, the pad electrode portion 40, the fine wiring 41, the pad electrode portion 40, and the second thermoelectric conversion layer 39.
  • the pad electrode part 40 and the fine wiring 41 are connected in series and folded at the left end. In this manner, the eight thermoelectric conversion layers from the first electrode 42 are connected in series with the pad electrode portion and the fine wiring to be connected to the second electrode 43.
  • the film to which the thermoelectric conversion layer was connected was sintered in an oven at 150 ° C. for 15 minutes, and the pad electrode portion 40 and the thermoelectric conversion layers 38 and 39 were electrically connected.
  • FIG. 22 shows a fourth diagram illustrating the method for manufacturing the thermoelectric generator of this embodiment.
  • the base material 32 is bent by alternately repeating a mountain fold and a valley fold along a line passing through the pad electrode. When folding in a straight line, it is effective to attach a straight mold. It is also effective to raise the temperature of the substrate when bending.
  • FIG. 23 shows a fifth diagram illustrating the method of manufacturing the thermoelectric generator of this embodiment.
  • FIG. 23 shows a cross-sectional structure taken along the line C-C ′ of FIG.
  • the first bottom portion 34 and the second bottom portion 35 are bent into a periodic corrugated shape so that the distance between them is constant.
  • the support base 31 is fixed with an adhesive.
  • the support base 31 is a resin such as polyethylene, an adhesive containing a silylated urethane resin is used and fixed and bonded for at least 30 minutes.
  • thermoelectric power generation element of this embodiment is shown.
  • the interval between the bottoms is referred to as a pitch length L1
  • the slope length is referred to as a slope length L2.
  • FIG. 25 shows a schematic diagram of a cross section of a thermoelectric power generation element in which the bending of the top and bottom is relaxed. This is a case where the bending is insufficient or the base material is relaxed after the bending, and the acute angle bending is changed to an obtuse angle bending.
  • the first cause of bending is when the pad electrode is thin.
  • the second cause of bending is when the occupancy of the pad electrode portion is small.
  • the occupation rate of the pad electrode portion is the length of the pad electrode portion in the length of the bent portion.
  • thermoelectric power generation elements decreases. Even if the bending is somewhat relaxed, it does not come into contact when the pitch length L1 is sufficiently larger than the slope length L2, but comes into contact when the pitch length L1 is smaller than the slope length L2. That is, when L1 / L2, which is the ratio between L1 and L2, is small, the yield decreases.
  • FIG. 26 shows the pad electrode thickness d dependency of the yield Y1 and the relative power generation efficiency ⁇ in the present embodiment.
  • the yield was obtained by producing 100 thermoelectric generators. The same tendency was shown when the thickness of the substrate was 40 ⁇ m to 80 ⁇ m.
  • Yield Y1 decreases due to bending relaxation. That is, when the pad electrode is thinned, bending becomes easy to relax, thereby reducing the output and reducing the yield.
  • the thickness d of the pad electrode is preferably 10 ⁇ m or more, and in order to obtain a yield of 90% or more, the thickness d of the pad electrode is preferably 15 ⁇ m or more.
  • the thickness of the fine wiring is the same as the thickness of the pad electrode. Since the fine wiring easily conducts heat, when the thickness of the fine wiring is increased, the temperature difference between the bottom and the top of the base material is reduced, and the relative power generation efficiency is lowered. Considering relative power generation efficiency, the thickness d of the pad electrode is preferably 40 ⁇ m or less, and more preferably 35 ⁇ m or less.
  • the thickness d of the pad electrode is desirably 10 ⁇ m to 40 ⁇ m, and more desirably 15 ⁇ m to 35 ⁇ m.
  • the thickness d of the pad electrode was set to 18 ⁇ m in order to increase the power generation efficiency. As a result, a yield of 92% and a relatively high power generation efficiency were obtained.
  • FIG. 27 shows the pad electrode occupancy ratio X dependency of the corrugated yield Y2 and the adhesive protrusion yield Y3 in the thermoelectric generator of this embodiment.
  • the pad electrode occupation ratio X is the ratio of the width of the pad electrode section 40 to the width in the direction of the top D-D 'in FIG. Y2 is 70% or more because the pad electrode occupation ratio X is 52% or more.
  • the reason why the waveform yield Y2 is 90% or more is that the pad electrode occupation ratio X in the broken line portion is 65% or more.
  • Silver paste adhesive protrudes from the pad electrode when a thermoelectric conversion sheet is applied.
  • the pad electrode occupation ratio X is high, the space between the pad electrodes becomes small.
  • the gap between the pad electrodes is reduced, the probability that the protruding silver paste short-circuits adjacent pad electrodes increases, and the yield decreases.
  • the adhesive yield Y3 was 70% or more, and the pad electrode occupation ratio X was 90% or less.
  • the adhesive yield Y3 was 90% or more, and the pad electrode occupation ratio X was 85% or less.
  • the pad electrode occupation ratio X is desirably 52% to 90%, and more desirably 65% to 85%.
  • the pad electrode occupation ratio X was set to 66%, and a yield of 90% was obtained.
  • the occupation ratio X was set to 80%, and a yield of 99.5% was obtained for the occupation ratio X.
  • FIG. 28 shows the L1 / L2 ratio dependency of the wiring contact yield Y4 and the power generation amount per unit area in the thermoelectric power generation element of this embodiment.
  • the L1 / L2 ratio is desirably 50% or less. Since the power generation amount per unit area increases in inverse proportion to L1, it is more preferably 37% or less. After all, the L1 / L2 ratio is desirably 7% to 50%, and more desirably 13% to 37%. In the thermoelectric power generation element of this embodiment, the L1 / L2 ratio was set to 20%, and both a 98% wiring contact yield and a high power generation amount per unit area were achieved.
  • FIG. 29 is a diagram showing a cross-sectional structure of the thermoelectric generator of this embodiment.
  • FIG. 30 is a diagram illustrating a planar structure of the thermoelectric generator of the present embodiment.
  • the configuration of this thermoelectric power generation element is the same as that of the thermoelectric power generation elements of FIGS. 17 and 18, but was manufactured by a different method.
  • the basic configuration of the thermoelectric power generation element includes a support base 51, a base 52, a top 53, a first bottom 54, a second bottom 55, a first slope 56, a second slope 57,
  • the first thermoelectric conversion layer 58, the second thermoelectric conversion layer 59, the fine wiring portion 61, the first electrode 62, the second electrode 63, and the pad electrode portion 64 are included.
  • the pad electrode and the fine wiring are formed by screen-printing a conductive paste, which is a mixture of silver particles and a resin, on the substrate 52 using a printing mask, and then sintering. Is formed.
  • the thickness of the pad electrode and the fine wiring is 15 ⁇ m, and the width of the fine wiring is 40 ⁇ m. Since the cross-sectional area of the fine wiring is small, the effect of maintaining the temperature difference between the bottom and the top is high.
  • the thermoelectric conversion layer was formed by forming a PEDOT / PSS in ink form on a base material on which pad electrodes and fine wiring were formed by screen printing, heating at 80 ° C. and drying. The thickness of the thermoelectric conversion layer is 30 ⁇ m. The thermoelectric conversion layer was bonded to the pad electrode and the substrate. Since the electrical resistance of the conductive paste is high, the output power is halved. Since all the thermoelectric generators can be formed by printing, a low-cost thermoelectric generator can be realized.
  • FIG. 31 is a plan structural view of the thermoelectric generator of this embodiment. The bottom is formed by folding at the valley fold line 75, and the top is formed by folding at the mountain fold line 76.
  • FIG. 32 is a structural diagram of pad electrodes and wirings of the thermoelectric generator of this embodiment. FIG. 32 shows an example of dimensions of the extraction electrode 71, the copper electrode 72, the fine copper wiring 74, and the like.
  • FIG. 33 is an external view of the thermoelectric generator of this embodiment.
  • the thermoelectric power generation element includes a corrugated substrate film 82, a thermoelectric conversion layer film 73, a copper electrode 72, a fine copper wiring 74, a folded wiring 77, a lead electrode 71, a lead electrode 78, a lead wire 79, and a lower support.
  • a base film 81 and an upper support base film 83 are included.
  • the basic configuration is the same as that in the case of using rolled copper, and here has 240 thermoelectric conversion layers.
  • thermoelectric power generation element The dimensions at the time of assembly were 60 mm ⁇ 60 mm ⁇ 14 mm. Since the height is relatively high at 14 mm, the temperature difference in the direction perpendicular to the installation surface is large. A temperature difference of 10 ° C. was given to this thermoelectric power generation element, an external resistance of about 240 ⁇ was connected, and the voltage was measured, and an output of 60 ⁇ W was obtained.
  • thermoelectric generator When PEDOT / PSS was used, the Seebeck coefficient was 100 ( ⁇ V / K). The output of 60 ⁇ W is an output capable of wireless communication. When this thermoelectric generator is combined with a sensor, it can be used in a sensor network that collects information obtained by the sensor by wireless communication.
  • a structure in which the base material 2 is reinforced with the reinforcing material 12 shown in FIG. 7 of the first embodiment is also possible.
  • the structure which protects the thermoelectric power generation element shown in FIG. 8 with the protective layer 13 is possible.
  • stacked the thermoelectric power generation element shown in FIG. 9 is possible.
  • the structure which forms a thermoelectric conversion layer and wiring in both surfaces of the surface of the base material 2 and a back surface shown in FIG. 10 is possible.
  • thermoelectric power generation element that connects a plurality of thermoelectric conversion layers in series
  • the thermoelectric generator has a corrugated base material composed of a bottom and a top
  • the thermoelectric conversion layer has a first thermoelectric conversion layer along a first slope between the top and a first bottom connected to the top;
  • the thermoelectric conversion layer has a second thermoelectric conversion layer along a second slope between the top and a second bottom connected to the top;
  • the first thermoelectric conversion layer and the second thermoelectric conversion layer have the same type,
  • the first thermoelectric conversion layer is on the top side and the first bottom side
  • the second thermoelectric conversion layer has connection points with wirings on the top side and the second bottom side, respectively.
  • connection between the first thermoelectric conversion layer and the second thermoelectric conversion layer is The wiring connected at the connection point on the top side of the first thermoelectric conversion layer is connected along the second slope, and connected at the connection point on the bottom side of the second thermoelectric conversion layer, Alternatively, the wiring connected at the connection point on the top side of the second thermoelectric conversion layer is a connection connected at the connection point on the bottom side of the first thermoelectric conversion layer along the first slope.
  • a thermoelectric power generation element, wherein both ends of the series connection are open electrodes.
  • thermoelectric power generation element that connects a plurality of thermoelectric conversion layers in series
  • the thermoelectric power generation element has a substrate having a wave shape structure in which a bottom portion and a top portion are alternately repeated,
  • the thermoelectric conversion layer has a first thermoelectric conversion layer along a first slope between the top and a first bottom connected to the top;
  • the thermoelectric conversion layer has a second thermoelectric conversion layer along a second slope between the top and a second bottom connected to the top;
  • the first thermoelectric conversion layer and the second thermoelectric conversion layer have the same type,
  • the first thermoelectric conversion layer is on the top side and the first bottom side
  • the second thermoelectric conversion layer has connection points with wirings on the top side and the second bottom side, respectively.
  • thermoelectric conversion layer Connection between the first thermoelectric conversion layers, The first thermoelectric conversion line adjacent to the first thermoelectric conversion layer is connected to the connection point on the top side of the first thermoelectric conversion layer along the second slope and at the second bottom part.
  • a connection that connects at the connection point on the bottom side of the layer, Connection between the second thermoelectric conversion layers, The wiring connected at the connection point on the top side of the second thermoelectric conversion layer is along the first slope, the second thermoelectric conversion next to the second thermoelectric conversion layer at the first bottom portion.
  • thermoelectric power generation element wherein both ends of the series connection are open electrodes. (Appendix 3) The thermoelectric power generation element according to any one of appendices 1 to 2, wherein the thermoelectric conversion layer is a P-type semiconductor.
  • thermoelectric power generation element The thermoelectric power generation element according to any one of appendices 1 to 3, wherein the thermoelectric conversion layer is a conductive polymer layer.
  • Appendix 5 The thermoelectric power generation element according to appendix 4, wherein the conductive polymer has at least one selected from polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, and derivatives thereof.
  • Appendix 6) The thermoelectric power generation element according to any one of appendices 4 to 5, wherein the conductive polymer has a thickness of 0.01 mm or more and 2 mm or less.
  • Appendix 7) The thermoelectric power generation element according to any one of appendices 1 to 6, wherein the base material has flexibility.
  • thermoelectric power generation element according to any one of appendices 1 to 7, wherein the base material is formed of a material that reversibly expands and contracts by 10% or more.
  • Appendix 9 Appendix 1 characterized in that the substrate has at least one selected from polyimide, polyethylene naphthalate, polyethylene terephthalate, polycarbonate, epoxy resin, aramid resin, silicone resin, ABS resin, silicone rubber, polybutadiene rubber.
  • the thermoelectric power generation element according to any one of 1 to 8. (Appendix 10) The thermoelectric power generation element according to any one of appendices 1 to 9, wherein the base material has at least one selected from a silicon filler and a glass fiber.
  • thermoelectric power generation element according to any one of appendices 1 to 10, wherein the base material has a thickness of 0.01 mm or more and 2 mm or less.
  • Appendix 12 The length of the wiring connecting the first thermoelectric conversion layer and the first thermoelectric conversion layer adjacent to the first thermoelectric conversion layer is adjacent to the first thermoelectric conversion layer and the first thermoelectric conversion layer.
  • the length of the wiring connecting the second thermoelectric conversion layer and the second thermoelectric conversion layer adjacent to the second thermoelectric conversion layer is adjacent to the second thermoelectric conversion layer and the second thermoelectric conversion layer.
  • thermoelectric power generation element according to any one of appendices 1 to 12, wherein the thermoelectric power generation element is longer by 10% or more than a length between matching second thermoelectric conversion layers.
  • Appendix 14 14. The thermoelectric power generation element according to any one of appendices 1 to 13, wherein a length of the thermoelectric conversion layer along the inclined direction of the slope is not less than 0.5 mm and not more than 10 mm.
  • Appendix 15 The thermoelectric power generation element according to any one of appendices 1 to 14, wherein the wiring has a loop shape, a bellows shape, or a lattice shape.
  • thermoelectric power generation element The thermoelectric power generation element according to any one of appendices 1 to 15, wherein a heat conduction amount of the wiring is smaller than a heat conduction amount of the thermoelectric conversion layer.
  • thermoelectric generator according to any one of appendices 1 to 16, wherein the wiring includes at least one selected from gold, silver, aluminum, copper, gallium, indium, and conductive nanofibers.
  • the wiring is copper, and the cross-sectional area perpendicular to the direction along the slope of the wiring with respect to the cross-sectional area perpendicular to the direction along the slope of the thermoelectric conversion layer is 1/10 or less.
  • the thermoelectric power generation element according to any one of appendices 1 to 17.
  • the wiring is copper, and the cross-sectional area perpendicular to the direction along the slope of the wiring with respect to the cross-sectional area perpendicular to the direction along the slope of the thermoelectric conversion layer is 1/30 or less.
  • the thermoelectric power generation element according to any one of claims 1 to 17. (Appendix 20) The wiring is gold, and the cross-sectional area perpendicular to the direction along the slope of the wiring with respect to the cross-sectional area perpendicular to the direction along the slope of the thermoelectric conversion layer is 1/30 or less.
  • thermoelectric power generation element according to any one of appendices 1 to 17.
  • Appendix 22 The thermoelectric power generation element according to any one of appendices 1 to 21, wherein an electrode is provided in the connection portion.
  • Appendix 23 The thermoelectric power generation element according to any one of appendices 1 to 22, wherein the thermoelectric conversion layer and the wiring are formed on both surfaces of the base material.
  • thermoelectric power generation element The thermoelectric power generation element according to any one of appendices 1 to 23, wherein the thermoelectric power generation element is covered with a protective layer.
  • a thermoelectric power generation element comprising a plurality of layers of the thermoelectric power generation elements according to any one of appendices 1 to 24.
  • thermoelectric power generation element according to appendix 26, wherein the substrate has a thickness of 0.01 mm or more and 2 mm or less.
  • Appendix 28 28.
  • the step of forming the thermoelectric conversion layer is a method of printing and drying a paste in which a thermoelectric conversion material is dissolved in a solvent, or a method of cutting and pasting a bulk material of a conductive polymer that is a thermoelectric conversion material, or 29.
  • thermoelectric power generation element The method for manufacturing a thermoelectric power generation element according to any one of appendices 26 to 28, comprising a method of printing while dispersing and orienting a conductive polymer monomer in ink.
  • Appendix 30 30.
  • Appendix 31 The method for producing a thermoelectric power generation element according to appendix 30, wherein the step of forming the electrode includes a method of printing a conductive paste, or a gas phase growth method such as vapor deposition or sputtering.
  • Appendix 32 32.
  • thermoelectric power generation element The method of manufacturing a thermoelectric power generation element according to any one of appendices 30 to 31, wherein the step of forming the electrode includes a step of processing the surface of the electrode into irregularities.
  • step of processing the surface of the electrode into irregularities is a nanoimprint method.
  • step of connecting the wiring includes a method of printing a paste-like wiring material, or a method of adhering or welding a bulk-like wiring material.
  • a method for manufacturing a thermoelectric generator. Appendix 35.
  • thermoelectric power generation element according to any one of appendices 26 to 34, wherein the step of forming the corrugated structure includes a hot embossing method.
  • Appendix 36 It has a pad electrode which connects the said thermoelectric conversion layer and the said wiring, The said pad electrode is provided in contact with the surface of the said base material, The appendix 1 thru
  • thermoelectric generator according to any one of appendices 36 to 37, wherein the pad electrode and the wiring are rolled copper or rolled copper having a surface plated with gold or silver.
  • Appendix 39 38.
  • Appendix 40 40.
  • the thermoelectric generator according to any one of appendices 36 to 39, wherein the thickness of the substrate is 40 ⁇ m to 80 ⁇ m.
  • Appendix 41 41.
  • the thermoelectric power generation element according to any one of appendices 36 to 40 wherein the thickness of the pad electrode is 10 ⁇ m or more and 40 ⁇ m or less.
  • thermoelectric generator according to any one of appendices 36 to 40, wherein the pad electrode has a thickness of 15 ⁇ m or more and 35 ⁇ m or less.
  • Appendix 43 43.
  • Power generation element 43.
  • thermoelectric power generation elements of Claim 1 The ratio L1 / L2 between the distance L1 between the adjacent bottoms and the length L2 from the bottom to the top of the base material is 7% or more and 50% or less, Additional Notes 36 to 44 Any one of the thermoelectric power generation elements of Claim 1.
  • Appendix 46 The ratio L1 / L2 of the distance L1 between the adjacent bottoms and the length L2 from the bottom to the top of the base material is 13% or more and 37% or less, Additional Notes 36 to 44 Any one of the thermoelectric power generation elements of Claim 1.
  • thermoelectric power generation element A step of pretreating the base material, a step of forming a pad electrode and wiring on the base material, a step of forming a thermoelectric conversion layer in contact with the pad electrode, and a step of molding the base material into a corrugated structure
  • a method for manufacturing a thermoelectric power generation element comprising: (Appendix 48) 48.
  • the thermoelectric power generation element according to appendix 47, wherein the step of forming the pad electrode and the wiring is performed by photolithography and etching.
  • (Appendix 49) The thermoelectric power generation element according to appendix 47, wherein the step of forming the pad electrode and the wiring is performed by screen printing.
  • the present invention relates to an organic thermoelectric power generation element using an organic conductive polymer material and a method for manufacturing the same.
  • Thermoelectric power generation element 2 Base material 3 Top part 4 1st bottom part 5 2nd bottom part 6 1st slope 7 2nd slope 8 1st thermoelectric conversion layer 9 2nd thermoelectric conversion layer 10 Connection part 11 Wiring 12 Reinforcement Material 13 Protective layer 14 Bellows structure wiring 15 Grid structure wiring 16 P-type semiconductor material 17 N-type semiconductor material 18 Electrode 19 Wiring 20 Ceramic substrate 21 Heat absorption 22 Heat dissipation 23 Temperature difference 30, 50, 70, 80, 90, 100, 110, 120, 140 Thermoelectric power generation element 32, 52 Base material 33, 53 Top 34, 54 First bottom 35, 55 Second bottom 36, 56 First slope 37, 57 Second slope 38, 58 First thermoelectric Conversion layer 39, 59 Second thermoelectric conversion layer 40, 64 Pad electrode part 41, 61 Fine wiring part 42, 62 First electrode 43, 63 Second electrode 71 78 extraction electrode 72 copper electrodes 73 thermoelectric conversion layer film 74 fine copper wiring 75 inward fold lines 76 mountain fold lines 77 folded lines

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Abstract

L'invention concerne un élément générateur de puissance thermoélectrique ayant une pluralité de couches de conversion thermoélectrique connectées en série, ledit élément générateur de puissance thermoélectrique ayant un matériau de base ayant une structure en forme d'onde dans laquelle des sections de creux et des sections de pic sont répétées alternativement. Les couches de conversion thermoélectrique ont : une première couche de conversion thermoélectrique le long d'une première surface en pente entre une section de pic et une première section de creux connectée à la section supérieure ; et une seconde couche de conversion thermoélectrique le long d'une seconde surface en pente entre une section de pic et une seconde section de creux connectée à la section de pic. La première couche de conversion thermoélectrique et la seconde couche de conversion thermoélectrique ont la même forme. La première couche de conversion thermoélectrique et la seconde couche de conversion thermoélectrique ont des points de connexion à un câblage, respectivement, sur le côté pic et le côté première section de creux et sur le côté pic et le côté seconde section de creux.
PCT/JP2013/000450 2012-02-03 2013-01-29 Élément générateur de puissance thermoélectrique organique et son procédé de production WO2013114854A1 (fr)

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WO2014176084A1 (fr) * 2013-04-26 2014-10-30 Eastman Chemical Company Stratifiés auto-ondulés utiles dans la fabrication de dispositifs thermoélectriques et structures ondulées associées
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JP2016207933A (ja) * 2015-04-27 2016-12-08 日本精工株式会社 熱電変換素子およびその製造方法
JPWO2015046254A1 (ja) * 2013-09-25 2017-03-09 リンテック株式会社 熱伝導性接着シート、その製造方法及びそれを用いた電子デバイス
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JPWO2015046253A1 (ja) * 2013-09-25 2017-03-09 リンテック株式会社 熱伝導性接着シート、その製造方法及びそれを用いた電子デバイス
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JP2017073490A (ja) * 2015-10-08 2017-04-13 大日本印刷株式会社 熱電変換モジュールの製造方法、および熱電変換モジュール
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JPWO2017208929A1 (ja) * 2016-05-31 2019-04-04 富士フイルム株式会社 熱電変換モジュール
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US10439124B2 (en) 2015-12-25 2019-10-08 Fujifilm Corporation Thermoelectric conversion module, heat conductive laminate, and method of producing thermoelectric conversion module
JP2019220546A (ja) * 2018-06-19 2019-12-26 三菱マテリアル株式会社 熱電変換モジュール、及び、熱電変換モジュールの製造方法
CN110970548A (zh) * 2018-10-01 2020-04-07 现代自动车株式会社 热电模块、用于其的框架以及包括热电模块的车辆
CN112542541A (zh) * 2020-11-27 2021-03-23 上海应用技术大学 一种热发电装置及其制备方法
US20210313503A1 (en) * 2020-04-01 2021-10-07 The University Of Chicago Functionally graded organic thermoelectric materials and uses thereof

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JP2014146640A (ja) * 2013-01-28 2014-08-14 Kri Inc 熱電変換部材
WO2014176084A1 (fr) * 2013-04-26 2014-10-30 Eastman Chemical Company Stratifiés auto-ondulés utiles dans la fabrication de dispositifs thermoélectriques et structures ondulées associées
US9064994B2 (en) 2013-04-26 2015-06-23 Eastman Chemical Company Self-corrugating laminates useful in the manufacture of thermoelectric devices and corrugated structures therefrom
JPWO2015046253A1 (ja) * 2013-09-25 2017-03-09 リンテック株式会社 熱伝導性接着シート、その製造方法及びそれを用いた電子デバイス
JPWO2015046254A1 (ja) * 2013-09-25 2017-03-09 リンテック株式会社 熱伝導性接着シート、その製造方法及びそれを用いた電子デバイス
JP2015195643A (ja) * 2014-03-31 2015-11-05 Ｊｆｅスチール株式会社 熱電発電装置および熱電発電方法
JP2016207933A (ja) * 2015-04-27 2016-12-08 日本精工株式会社 熱電変換素子およびその製造方法
JPWO2017038525A1 (ja) * 2015-08-31 2018-08-02 富士フイルム株式会社 熱電変換デバイス
WO2017038717A1 (fr) * 2015-08-31 2017-03-09 富士フイルム株式会社 Module de conversion thermoélectrique
WO2017038553A1 (fr) * 2015-08-31 2017-03-09 富士フイルム株式会社 Module de conversion thermoélectrique
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WO2017110589A1 (fr) * 2015-12-25 2017-06-29 富士フイルム株式会社 Dispositif de conversion thermoélectrique
US10439124B2 (en) 2015-12-25 2019-10-08 Fujifilm Corporation Thermoelectric conversion module, heat conductive laminate, and method of producing thermoelectric conversion module
JPWO2017110589A1 (ja) * 2015-12-25 2018-11-22 富士フイルム株式会社 熱電変換デバイス
WO2017130751A1 (fr) * 2016-01-25 2017-08-03 ポリマテック・ジャパン株式会社 Élément de conversion thermoélectrique et structure de montage d'élément de conversion thermoélectrique
JP2017188574A (ja) * 2016-04-06 2017-10-12 積水化学工業株式会社 熱電変換デバイス
JPWO2017208929A1 (ja) * 2016-05-31 2019-04-04 富士フイルム株式会社 熱電変換モジュール
JP2019525454A (ja) * 2016-06-23 2019-09-05 スリーエム イノベイティブ プロパティズ カンパニー 熱電テープ
JP2018088445A (ja) * 2016-11-28 2018-06-07 積水化学工業株式会社 熱電変換デバイス、積層熱電変換デバイス及び放熱構造体
EP3373335A3 (fr) * 2017-03-10 2018-10-24 Center For Advanced Soft Electronics Dispositif thermoélectrique et son procédé de fabrication
CN108574036A (zh) * 2017-03-10 2018-09-25 纳米基盘柔软电子素子研究团 热电器件及其制造方法
JP2019220546A (ja) * 2018-06-19 2019-12-26 三菱マテリアル株式会社 熱電変換モジュール、及び、熱電変換モジュールの製造方法
CN112368851A (zh) * 2018-06-19 2021-02-12 三菱综合材料株式会社 热电转换模块及热电转换模块的制造方法
US20210265552A1 (en) * 2018-06-19 2021-08-26 Mitsubishi Materials Corporation Thermoelectric conversion module and method for producing thermoelectric conversion module
CN110970548A (zh) * 2018-10-01 2020-04-07 现代自动车株式会社 热电模块、用于其的框架以及包括热电模块的车辆
US20210313503A1 (en) * 2020-04-01 2021-10-07 The University Of Chicago Functionally graded organic thermoelectric materials and uses thereof
CN112542541A (zh) * 2020-11-27 2021-03-23 上海应用技术大学 一种热发电装置及其制备方法

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