WO2023277028A1 - 熱電体、熱電体の製造方法、熱電デバイス、及び、熱電デバイスの製造方法 - Google Patents

熱電体、熱電体の製造方法、熱電デバイス、及び、熱電デバイスの製造方法 Download PDF

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Publication number
WO2023277028A1
WO2023277028A1 PCT/JP2022/025808 JP2022025808W WO2023277028A1 WO 2023277028 A1 WO2023277028 A1 WO 2023277028A1 JP 2022025808 W JP2022025808 W JP 2022025808W WO 2023277028 A1 WO2023277028 A1 WO 2023277028A1
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thermoelectric
thermoelectric body
present
cross
manufacturing
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English (en)
French (fr)
Japanese (ja)
Inventor
貴大 田口
亨 ▲高▼橋
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2023531987A priority Critical patent/JPWO2023277028A1/ja
Priority to CN202280045474.0A priority patent/CN117581655A/zh
Publication of WO2023277028A1 publication Critical patent/WO2023277028A1/ja
Priority to US18/503,686 priority patent/US20240077363A1/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K1/00—Details of thermometers not specially adapted for particular types of thermometer
    • G01K1/16—Special arrangements for conducting heat from the object to the sensitive element
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect

Definitions

  • the present invention relates to a thermoelectric body, a method for manufacturing a thermoelectric body, a thermoelectric device, and a method for manufacturing a thermoelectric device.
  • Patent Document 1 discloses a film-like heat flux sensor as an example of a thermoelectric device that converts heat into electricity using a temperature difference within a material.
  • the heat flux sensor described in Patent Document 1 includes a flexible film-like insulating member having a first surface and a second surface opposite to the first surface, and arranged inside the insulating member.
  • thermoelectric members made of a first thermoelectric material
  • second thermoelectric member arranged inside the insulating member and made of a second thermoelectric material different from the first thermoelectric material
  • the plurality of first thermoelectric members are a plurality of second thermoelectric members arranged alternately with each other; arranged on the first surface side with respect to the plurality of first thermoelectric members and the plurality of second thermoelectric members; of the second thermoelectric members, a plurality of first conductor patterns connecting the first thermoelectric members and the second thermoelectric members arranged side by side, and the plurality of first thermoelectric members and the plurality of second thermoelectric members a plurality of second conductor patterns arranged on the second surface side and connecting the first thermoelectric members and the second thermoelectric members arranged side by side among the plurality of first thermoelectric members and the plurality of second thermoelectric members; Prepare.
  • the heat flux sensor described in Patent Document 1 includes an extensible member having higher extensibility than the insulating member under the same dimensional conditions as the insulating member.
  • the heat flux sensor described in Patent Document 1 is installed on the measurement surface of the object to be measured with one of the first surface and the second surface in contact with the measurement surface of the object.
  • a heat flow passes through the heat flux sensor in a direction from one of the first surface and the second surface of the heat flux sensor to the other.
  • a temperature difference occurs between the first surface side and the second surface side of the heat flux sensor. That is, a temperature difference occurs between one side and the other side of each of the first thermoelectric member and the second thermoelectric member that are connected to each other.
  • a thermoelectromotive force is generated in the first thermoelectric member and the second thermoelectric member due to the Seebeck effect.
  • the heat flux sensor described in Patent Document 1 outputs this thermoelectromotive force, specifically voltage, as a sensor signal.
  • the heat flux sensor described in Patent Document 1 is a structure in which a plurality of members such as an insulating member, a first thermoelectric member, a second thermoelectric member, a first conductor pattern, a second conductor pattern, and an extensible member are combined. Therefore, flexibility tends to be lacking. Therefore, if the heat flux sensor described in Patent Document 1 is attached to a heat source (object) with a small curvature radius, such as a thin cylindrical heating element or cooling element, the heat flux sensor cannot be attached to the heat source. Not only is it difficult to attach the heat flux sensor, but the heat flux sensor may break (disconnect). Thus, when using the heat flux sensor described in Patent Document 1, there is a limit to the radius of curvature of the heat source that can be attached.
  • the heat flux when measuring the heat flux using a heat flux sensor, the heat flux can generally be measured with high accuracy by minimizing the thermal resistance at the contact portion between the heat flux sensor and the heat source.
  • the heat flux sensor described in Patent Document 1 cannot completely eliminate the thermal resistance of the extensible member.
  • the present invention was made to solve the above problems, and aims to provide a thermoelectric body that can be attached to an object with a small radius of curvature and has a high thermoelectromotive force.
  • a further object of the present invention is to provide a method for manufacturing the above thermoelectric body.
  • Another object of the present invention is to provide a thermoelectric device having the above thermoelectric body.
  • Another object of the present invention is to provide a method for manufacturing the thermoelectric device.
  • thermoelectric body of the present invention includes a thermoelectric material having an anomalous Nernst effect, has a plate-like shape, an average thickness of 10 ⁇ m or more and 100 ⁇ m or less, and an average cross-sectional area of a cross section perpendicular to the longitudinal direction of 0.008 mm 2 . Above, it is characterized by being 1 mm 2 or less.
  • the method for producing a thermoelectric body of the present invention uses a liquid quenching method to produce the thermoelectric body of the present invention, and the liquid quenching method includes a melt spinning method (single roll method),
  • the Euler number is in the range of 0.001 or more and 0.1 or less when the thermoelectric body is produced by the liquid quenching method including the roll method or the strip casting method.
  • thermoelectric device of the present invention is characterized by comprising the thermoelectric body of the present invention.
  • thermoelectric device of the present invention is characterized by comprising the step of manufacturing a thermoelectric body by the method for manufacturing a thermoelectric body of the present invention.
  • thermoelectric body that can be attached to an object with a small radius of curvature and has a high thermoelectromotive force. Furthermore, according to the present invention, it is possible to provide a method for manufacturing the thermoelectric body. Further, according to the present invention, it is possible to provide a thermoelectric device having the above thermoelectric body. Further, according to the present invention, it is possible to provide a method for manufacturing the above thermoelectric device.
  • FIG. 1 is a photograph showing the appearance of an example of the thermoelectric body of the present invention (main component: Fe 3 Al).
  • FIG. 2 is an image showing crystal grains of a thermoelectric material in an example of the thermoelectric body of the present invention.
  • FIG. 3 is a schematic diagram showing an example of how a thermoelectric body is produced by the melt spinning method.
  • FIG. 4 is a photograph showing an example of how a thermoelectric body (main component: Fe 3 Al) is produced by the melt spinning method.
  • FIG. 5 is an image diagram for explaining the Eu number in the melt spinning method.
  • thermoelectric body The thermoelectric body, the method for manufacturing the thermoelectric body, the thermoelectric device, and the method for manufacturing the thermoelectric device of the present invention will be described below.
  • present invention is not limited to the following configurations, and can be appropriately modified and applied without changing the gist of the present invention. Combinations of two or more of the individual desirable configurations described below are also part of the present invention.
  • thermoelectric body of the present invention includes a thermoelectric material having an anomalous Nernst effect, has a plate-like shape, an average thickness of 10 ⁇ m or more and 100 ⁇ m or less, and an average cross-sectional area of a cross section perpendicular to the longitudinal direction of 0.008 mm 2 . Above, it is characterized by being 1 mm 2 or less.
  • thermoelectric body of the present invention includes a thermoelectric material having an anomalous Nernst effect.
  • thermoelectric body of the present invention includes a thermoelectric material having a magneto-thermoelectric effect based on the anomalous Nernst effect.
  • thermoelectromotive force due to the anomalous Nernst effect can be expressed by the following equation.
  • V is the thermoelectromotive force
  • SN is the anomalous Nernst coefficient
  • ⁇ T is the temperature difference inside the thermoelectric body or thermoelectric device
  • t is the thickness parallel to the heat flux direction caused by the temperature difference inside the thermoelectric body or thermoelectric device
  • L is the length parallel to the current direction caused by the electromotive force of the thermoelectric body or device.
  • Thermoelectric materials contained in the thermoelectric body of the present invention include, for example, Fe3Al , Fe3Ga, Mn3Sn , Mn3Ga , Co2MnGa , Co2MnAl , Co2MnIn , Mn3Ge , Fe2NiGa ,
  • the main component is an intermetallic compound represented by a chemical composition such as CoTiSb, CoVSb, CoCrSb, CoMnSb, TiGa 2 Mn.
  • the main component means the component with the highest weight ratio.
  • thermoelectric material contained in the thermoelectric body of the present invention preferably has an ordered phase.
  • Fe 3 Al and Fe 3 Ga have a DO3 structure
  • Mn 3 Sn has a structure in which two layers of Kagome lattices are laminated in the [0001] direction
  • Mn 3 Ga has a tetragonal D022 structure
  • Co 2 MnGa has an L21 cubic structure. is a full Heusler structure.
  • thermoelectric material contained in the thermoelectric body of the present invention preferably contains an ordered phase of an intermetallic compound.
  • FIG. 1 is a photograph showing the appearance of an example of the thermoelectric body of the present invention (main component: Fe 3 Al).
  • thermoelectric material contained in the thermoelectric body of the present invention may have a Weyl magnetic material as its main component.
  • thermoelectric body of the present invention has a plate shape.
  • the plate shape also includes a ribbon shape.
  • thermoelectric body of the present invention preferably has a substantially rectangular cross section perpendicular to the longitudinal direction.
  • thermoelectric body of the present invention has an average thickness of 10 ⁇ m or more and 100 ⁇ m or less.
  • the average thickness of the thermoelectric body is less than 10 ⁇ m, the mechanical strength of the thermoelectric body decreases, so the thermoelectric body cannot be attached to an object with a small radius of curvature, and the thermoelectric body breaks. Furthermore, if the average thickness of the thermoelectric body is less than 10 ⁇ m, the temperature difference between the two main surfaces facing each other in the thickness direction orthogonal to the longitudinal direction of the thermoelectric body becomes too small. Since the temperature gradient becomes too small, the thermoelectromotive force becomes low.
  • thermoelectric body If the average thickness of the thermoelectric body is larger than 100 ⁇ m, the geometrical moment of inertia becomes large, so the thermoelectric body cannot be attached to an object with a small radius of curvature, and the thermoelectric body breaks.
  • thermoelectric body If the average cross-sectional area of the cross section perpendicular to the longitudinal direction of the thermoelectric body is smaller than 0.008 mm 2 , the electrical resistance of the thermoelectric body becomes too high, resulting in a low thermoelectromotive force.
  • thermoelectric body When the average cross-sectional area of the cross section orthogonal to the longitudinal direction of the thermoelectric body is larger than 1 mm2 , the geometrical moment of inertia becomes large, so the thermoelectric body cannot be attached to an object with a small radius of curvature, and the thermoelectric body It breaks.
  • the average thickness of the thermoelectric body and the average cross-sectional area of the cross section orthogonal to the longitudinal direction of the thermoelectric body are determined by the method described in the examples below.
  • thermoelectric body normally generates a thermoelectromotive force in proportion to the internal temperature difference. Therefore, a thermoelectric body having a shape, thickness, etc. that can be attached to an object with a small radius of curvature tends to have a small temperature difference inside, making it difficult to obtain a desired thermoelectromotive force. On the other hand, it is difficult to attach a conventional thermoelectric body having a shape, thickness, etc. that tends to increase the internal temperature difference to an object with a small radius of curvature.
  • thermoelectric body of the present invention as described above, (1) the shape is plate-like, (2) the average thickness is 10 ⁇ m or more and 100 ⁇ m or less, and (3) the The average cross-sectional area of the cross section is 0.008 mm 2 or more and 1 mm 2 or less. can do.
  • thermoelectric body of the present invention it is possible to reduce the number of locations where electrodes are connected to the thermoelectric body having specific material properties as much as possible, and the thermoelectric body itself is flexible and has no risk of breakage. Affixing to an object with a small radius of curvature is possible.
  • a high thermoelectromotive force can be obtained by controlling the shape of the thermoelectric body, the thickness of the thermoelectric body, and the cross-sectional area of the thermoelectric body.
  • to stick also includes aspects such as “to wrap around”.
  • thermoelectric material of the present invention preferably has an average crystal grain size of 2 ⁇ m or more and 100 ⁇ m or less in a cross section orthogonal to the longitudinal direction.
  • thermoelectric material in the cross section perpendicular to the longitudinal direction of the thermoelectric material is smaller than 2 ⁇ m, the toughness of the thermoelectric material decreases as can be seen from the inverse Hall-Petch law.
  • the thermoelectric element may break because it cannot be attached to an object.
  • thermoelectric material in the cross section orthogonal to the longitudinal direction of the thermoelectric body is larger than 100 ⁇ m, the thermal conductivity of the thermoelectric body becomes too high.
  • the temperature difference between the major surfaces becomes too small, and as a result, the temperature gradient between the major surfaces becomes too small, which can lead to a low thermoelectromotive force.
  • the average crystal grain size of the thermoelectric material in the cross section orthogonal to the longitudinal direction of the thermoelectric body is the same in the region near one main surface and the region near the other main surface of the thermoelectric body. There may be, or they may be different from each other.
  • the average crystal grain size of the thermoelectric material in the cross section orthogonal to the longitudinal direction of the thermoelectric body is determined by the method described in the examples below.
  • thermoelectric material in the cross section perpendicular to the longitudinal direction of the thermoelectric body is measured in the image shown in FIG.
  • FIG. 2 is an image showing crystal grains of a thermoelectric material in an example of the thermoelectric body of the present invention.
  • the limit bending radius of the thermoelectric body of the present invention is preferably 50 mm or less, more preferably 25 mm or less.
  • thermoelectric body The critical bending radius of the thermoelectric body is determined by the method described in the examples below.
  • thermoelectric body of the present invention contains, for example, a thermoelectric material mainly composed of Fe 3 Al
  • the thermoelectric body is bent at a bending angle of 180° so that one end and the other end of the thermoelectric body are in contact with each other.
  • thermoelectric body The bending angle of a thermoelectric body is measured as follows. First, a thermoelectric piece having a length of 40 mm is cut out from the thermoelectric body along the longitudinal direction (the molten metal outlet direction in the liquid quenching method). Next, the thermoelectric piece is bent along a line perpendicular to the longitudinal direction and parallel to the width direction at the center position in the longitudinal direction. At this time, the bending angle before bending the thermoelectric piece is set to 0°, and the bending angle in the bent state of the thermoelectric piece is measured with a protractor, and the obtained measured value is the bending angle of the thermoelectric body. .
  • the surface of the thermoelectric body of the present invention is preferably electrically insulated with an insulating coat (coating).
  • the insulating coat is required to be thin, so the insulating coat preferably contains an oxide film or a resin such as polyimide.
  • the surface roughness of the thermoelectric body of the present invention is preferably small, and the average surface roughness Ra of the thermoelectric body of the present invention is preferably 10 ⁇ m or less, for example.
  • the average surface roughness Ra of the thermoelectric body is measured as follows. First, three regions with a length of 2 cm or more and 3 cm or less are randomly sampled along the longitudinal direction of the thermoelectric body (the hot melt direction in the liquid quenching method). Next, the surface roughness Ra at the central portion of each region is measured using a roughness measuring machine (eg, SJ-210 (manufactured by Mitutoyo)). Then, the average value of the measured values of the surface roughness Ra obtained in the above three regions is taken as the average surface roughness Ra of the thermoelectric body.
  • a roughness measuring machine eg, SJ-210 (manufactured by Mitutoyo)
  • thermoelectric manufacturing method The method for producing a thermoelectric body of the present invention uses a liquid quenching method to produce the thermoelectric body of the present invention, and the liquid quenching method includes a melt spinning method (single roll method), The Euler number is in the range of 0.001 or more and 0.1 or less when the thermoelectric body is produced by the liquid quenching method including the roll method or the strip casting method.
  • thermoelectric body of the present invention having the above characteristics can be manufactured using, for example, a liquid quenching method, a spinning method in a rotating liquid, a solution spinning method, or the like.
  • thermoelectric body of the present invention is produced by a method such as a liquid quenching method, a spinning method in a rotating liquid, or a solution spinning method, the density of the thermoelectric body can be increased, so that the electric resistivity of the thermoelectric body can be lowered. It is preferable from the viewpoint of increasing the mechanical strength of the thermoelectric body.
  • thermoelectric body of the present invention is preferably manufactured using a liquid quenching method.
  • a thermoelectric body manufactured using a liquid quenching method tends to be plate-like (for example, ribbon-like), so that it can be easily attached to an object having a small radius of curvature.
  • thermoelectric bodies manufactured using the liquid quenching method tend to be plate-like (for example, ribbon-like), which makes it easier for the thermoelectric bodies to come into surface contact with each other, which improves the thermal conductivity of the entire thermoelectric body.
  • the temperature gradient between the main surfaces facing each other in the thickness direction tends to increase, and as a result, a high thermoelectromotive force can be obtained.
  • thermoelectric material as a raw material here, a thermoelectric material containing an intermetallic compound as a main component
  • a container is placed in a container and melted at a high temperature to form a molten alloy (molten metal).
  • molten metal molten metal
  • materials for the container include ceramics and glass containing SiO 2 .
  • a nozzle nozzle slit
  • a molten metal outlet is formed at the bottom of the container.
  • the liquid quenching method includes the melt spinning method (single roll method), twin roll method, or strip casting method.
  • FIG. 3 is a schematic diagram showing an example of how a thermoelectric body is produced by the melt spinning method.
  • FIG. 4 is a photograph showing an example of how a thermoelectric body (main component: Fe 3 Al) is produced by the melt spinning method.
  • FIG. 5 is an image diagram for explaining the Eu number in the melt spinning method.
  • the Eu number is in the range of 0.001 or more and 0.1 or less.
  • the tapping pressure ( ⁇ P) of the molten alloy is the pressure applied to the molten alloy (molten metal) present at the tip of the nozzle.
  • a pool of molten alloy formed in the gap between the tip of the nozzle and the quench roll when the molten alloy is injected to the quench roll is called a paddle. If the tapping pressure is too low, the inertial force ( ⁇ U 2 where ⁇ is the density of the molten thermoelectric material) derived from the rotational peripheral speed (U) of the quench roll has the effect of dragging the paddle in the horizontal direction perpendicular to the tapping direction. becomes large and the average thickness of the formed thermoelectric body becomes too small.
  • the tapping pressure is too low, the puddle formation becomes unstable and the molten alloy splatters.
  • the tapping pressure is too high, the force of the tapping pressure pressing down the paddle is too strong, so that the average thickness of the formed thermoelectric body becomes too large. Furthermore, if the tapping pressure is too high, the paddle will have a collapsed shape and the thermoelectric body will not form steadily.
  • the rotation peripheral speed of the quench roll is the peripheral speed of the quench roll. If the rotational peripheral speed of the quench roll is too low, the amount of molten metal supplied to the paddle will be relatively large with respect to the amount of solidified thermoelectric material drawn out in the direction of rotation of the roll, resulting in a large thickness of the formed thermoelectric material. Become. If the rotational peripheral speed of the quench roll becomes too low, the effect of the tapping pressure on the inertial force becomes relatively large, so the paddle is crushed and becomes unstable, causing the molten alloy to scatter.
  • the rotational peripheral speed of the quench roll is too high, the molten alloy in contact with the quench roll solidifies and is immediately pulled out in the direction of rotation of the roll, so that the thickness of the formed thermoelectric body becomes small. If the rotational peripheral speed of the quench roll becomes too high, the effect of inertial force on the tapping pressure becomes relatively large, so that the paddle is dragged by the quench roll and the molten alloy scatters.
  • the distance between the nozzle and the quench roll is the gap between the tip of the nozzle and the quench roll. If the distance between the nozzle and the quenching roll is too narrow, the paddle will be easily crushed and unstable, so that the thermoelectric body will not be formed steadily. In addition, when the molten alloy adheres to the tip of the nozzle, the solidified molten alloy contacts the quench roll and the nozzle is broken. On the other hand, if the distance between the nozzle and the quenching roll is too large, the paddle becomes difficult to press against the surface of the quenching roll, resulting in instability, which increases the possibility of scattering of the molten alloy. In the liquid quench method, there is an appropriate nozzle-quench roll distance depending on the thermoelectric material to be molten alloy.
  • thermoelectric body of the present invention in the liquid quenching method, the thermoelectric body is produced by adjusting the various conditions described above so that the Eu number is in the range of 0.001 or more and 0.1 or less, whereby the abnormal Nernst effect A good thermoelectric body having a high thermoelectromotive force can be produced.
  • thermoelectric bodies In the liquid quenching method, if an attempt is made to produce a thermoelectric body with an Eu number in the range of less than 0.001, the inertial force derived from the rotating peripheral speed of the quenching roll becomes too large with respect to the tapping pressure of the molten alloy. The average thickness of the formed thermoelectric body becomes too small.
  • a paddle which is a pool of molten alloy, is formed in the gap between the tapping part (nozzle tip) and the quench roll. As a result, thermoelectric bodies cannot be manufactured.
  • thermoelectric body with an Eu number in the range of greater than 0.1 if an attempt is made to manufacture a thermoelectric body with an Eu number in the range of greater than 0.1, the tapping pressure of the molten alloy becomes too large against the inertial force derived from the rotating peripheral speed of the quenching roll. The average thickness of the formed thermoelectric body becomes too large.
  • the molten alloy will scatter from the tapping portion (nozzle tip), resulting in the production of a thermoelectric body. Can not.
  • thermoelectric device A thermoelectric device of the present invention is characterized by comprising the thermoelectric body of the present invention.
  • thermoelectric device of the present invention has, for example, the following structure.
  • thermoelectric device of Structural Example 1 of the present invention has a structure in which a plurality of sheets made of thermoelectric bodies are laminated while being joined by welding, soldering, a conductive adhesive, or the like.
  • a plurality of thermoelectric sheets may be connected by metal wires containing copper, aluminum or the like, metal foils or the like.
  • thermoelectric device of Structural Example 2 of the present invention has a structure in which a thermoelectric body is wound around a heat source.
  • the thermoelectric body may be spirally wound, concentrically wound, or spirally and concentrically wound around the heat source.
  • thermoelectric device of the present invention is, for example, a heat flux sensor, an energy harvester, or the like.
  • thermoelectric device of the present invention preferably further comprises terminals for outputting voltage.
  • the thermoelectric device of the present invention further includes a heat dissipation member.
  • a heat dissipation member for example, by adhering a highly thermally conductive sheet as a heat dissipation member between the thermoelectric element of the present invention and a heating element, which is an example of an object to which the thermoelectric element of the present invention is attached, the electromotive force of the thermoelectric device can be increased. can be enhanced. Furthermore, from the viewpoint of promoting heat dissipation and increasing the temperature gradient inside the thermoelectric body, the electromotive force of the thermoelectric device can be further increased by attaching a heat dissipation member to the surface of the thermoelectric device located on the side opposite to the heat generating body.
  • thermoelectric device A method of manufacturing a thermoelectric device of the present invention is characterized by comprising a step of manufacturing a thermoelectric body by the method of manufacturing a thermoelectric body of the present invention.
  • thermoelectric device of the present invention As examples of the method of manufacturing the thermoelectric device of the present invention, the method of manufacturing the thermoelectric device of Structural Example 1 and the method of manufacturing the thermoelectric device of Structural Example 2 will be described.
  • thermoelectric body is manufactured by the method for manufacturing a thermoelectric body of the present invention.
  • the thermoelectric body is cut and processed into sheets to produce a plurality of sheets made of the thermoelectric body.
  • a thermoelectric device having a structure in which a plurality of thermoelectric sheets are laminated is manufactured by laminating a plurality of thermoelectric sheets while joining them by welding, soldering, a conductive adhesive, or the like.
  • the plurality of thermoelectric sheets may be connected by a metal wire containing copper, aluminum, or the like, a metal foil, or the like.
  • thermoelectric body is manufactured by the method for manufacturing a thermoelectric body of the present invention. Then, by winding the thermoelectric body around the heat source, a thermoelectric device having a structure in which the thermoelectric body is wound around the heat source is produced. When the thermoelectric body is wound around the heat source, the thermoelectric body may be spirally wound, concentrically wound, or spirally wound and concentrically wound.
  • thermoelectric body of the present invention examples that more specifically disclose the thermoelectric body of the present invention are shown below. It should be noted that the present invention is not limited only to these examples.
  • Example 1 to 9 and Comparative Examples 1 to 7 Thermoelectric bodies of Examples 1 to 9 and Comparative Examples 1 to 7 were produced by the following method.
  • reagents were weighed so that the at % ratio of Fe and Al or Fe and Ga was 3:1. Then, the weighed reagent was loaded into an alumina crucible and melted in an Ar atmosphere while applying high frequency in a small high frequency induction melting furnace VF-HMF500 (manufactured by Makabe Giken Co., Ltd.). Subsequently, the obtained melt was poured into a Cu mold, cooled, and solidified to produce an ingot as a raw material for a thermoelectric body. The obtained ingot was then crushed with a jaw crusher.
  • VF-HMF500 small high frequency induction melting furnace
  • thermoelectric body was manufactured by the melt spinning method. Specifically, first, a batch of 20 g ingots was loaded into a quartz glass slit nozzle and melted by applying a high-frequency current to a heating coil to obtain a molten alloy (molten metal). At this time, a slit nozzle was used in which the slit size was appropriately changed according to the manufacturing level of each example so that the thickness, cross-sectional area, etc. of the thermoelectric body to be manufactured later were within the target range.
  • VF-HMF150 manufactured by Makabe Giken Co., Ltd.
  • thermoelectric body After that, the temperature of the molten metal is monitored with a radiation thermometer installed in front of the quenching device.
  • a plate-shaped thermoelectric element was manufactured by pouring a molten alloy onto the surface of a quenched copper roll rotating at a rotational peripheral speed of .
  • Table 1 shows the number of Eu in manufacturing the thermoelectric body.
  • thermoelectric bodies of Examples 1 to 9 and Comparative Examples 1 to 7 were evaluated as follows. The results are shown in Table 1.
  • ⁇ Average thickness> First, three regions with a length of 2 cm or more and 3 cm or less were randomly sampled along the longitudinal direction of the thermoelectric body (the direction of molten metal ejection in the melt spinning method). Next, the thickness at the central portion of each region was measured using a micrometer BMS-25MX (manufactured by Mitutoyo). Then, the average value of the thickness measurement values obtained in the above three regions was taken as the average thickness of the thermoelectric body.
  • ⁇ Average cross-sectional area> First, three regions with a length of 2 cm or more and 3 cm or less were randomly sampled along the longitudinal direction of the thermoelectric body (the direction of molten metal ejection in the melt spinning method). Next, in the central portion of each region, the cross-sectional area of the cross section was measured by image analysis of the cross section perpendicular to the longitudinal direction. Then, the average value of the cross-sectional area measurements obtained in the above three regions was taken as the average cross-sectional area of the cross section perpendicular to the longitudinal direction of the thermoelectric body.
  • ⁇ Average grain size> First, a resin structure was produced by embedding a thermoelectric element in resin. A sample for measurement was prepared by polishing the obtained resin structure so that a cross section perpendicular to the longitudinal direction of the thermoelectric body was exposed. Next, a cross section perpendicular to the longitudinal direction of the thermoelectric body exposed in the measurement sample was observed with an optical microscope and a scanning electron microscope (SEM), and multiple images of the cross section were taken. Note that means for observing the cross section of the thermoelectric body are not limited to optical microscopes and scanning electron microscopes. Subsequently, the grain size of each crystal grain within the image field was measured as an equivalent circle diameter by image analysis of a plurality of captured cross-sectional images using software.
  • the average value of the measured values of the obtained crystal grain sizes was taken as the average crystal grain size of the thermoelectric material in the cross section perpendicular to the longitudinal direction of the thermoelectric body.
  • the average crystal grain size of the thermoelectric material in the cross section orthogonal to the longitudinal direction of the thermoelectric body may be a measured value measured in accordance with "Method for measuring grain size of fine ceramics" defined in JIS R1670. It may be an average value of values calculated multiple times in multiple fields of view by the linear intercept method.
  • thermoelectric element sufficiently longer than the outer diameter of the jig around the jig to see if it is possible to wind it around once. confirmed no. At this time, if the thermoelectric body cracked or broke, it was determined that it was impossible to wind the thermoelectric body around the jig by one turn.
  • thermoelectric element If it is determined that it is possible to wind the thermoelectric element around the jig once, is it possible to reduce the outer diameter of the jig by 1 mm and wind the thermoelectric element once around the jig as described above? confirmed no. In this way, the above confirmation work was repeated while reducing the outer diameter of the jig by 1 mm. Then, at the stage when it is judged that it is impossible to wind the thermoelectric body around the jig for one turn, a value 1 mm larger than the jig radius (half the outer diameter) at that stage is taken as the limit bending radius. did.
  • thermoelectromotive force of the thermoelectric element was measured while the thermoelectric element was attached to the heating element.
  • a heater having an outer diameter of 25 mm and a length of 300 mm was used as the heating element.
  • the temperature of the heating element was fixed at 100°C. From the surface of the thermoelectric element located on the opposite side of the heating element, heat was radiated into the atmosphere at 25°C.
  • the external magnetic field was set to 2T.
  • the anomalous Nernst coefficient of the thermoelectric body was 3 ⁇ V/K when a magnetic field of 2 T was applied.
  • the anomalous Nernst coefficient of the thermoelectric body was measured with a device that added the heat transport option (TTO) to the physical property measurement system (PPMS) (manufactured by Quantum Design).
  • TTO heat transport option
  • PPMS physical property measurement system
  • the sample fixed to the holder had a length of about 7 mm and a width of about several mm.
  • As the wiring a gold-plated copper wire with a diameter of 0.1 mm was used.
  • the electromotive force is measured in the presence of a magnetic field in the range of -2T or more and +2T or less (20 Oe/sec) by a superconducting magnet. In the process of +1T ⁇ 1T, it was held for 1200 seconds every 0.1T, and in the process of ⁇ 1T ⁇ 2T, it was held every 0.2T for 1200 seconds.
  • thermoelectric bodies of Examples 1 to 9 thermoelectric bodies that can be attached to an object with a small radius of curvature and have a high thermoelectromotive force were realized.
  • thermoelectric element of Comparative Example 1 which had an average thickness of less than 10 ⁇ m, had a limit bending radius of more than 50 mm and broke when it was attached to the heating element. Therefore, in the thermoelectric body of Comparative Example 1, the thermoelectromotive force could not be measured.
  • thermoelectric element of Comparative Example 2 which had an average thickness of more than 100 ⁇ m, had a limit bending radius of more than 50 mm, and broke when it was attached to the heating element. Therefore, in the thermoelectric body of Comparative Example 2, the thermoelectromotive force could not be measured.
  • thermoelectric element of Comparative Example 3 in which the average cross-sectional area of the cross section perpendicular to the longitudinal direction was smaller than 0.008 mm 2 , had a lower thermoelectromotive force than the thermoelectric elements of Examples 1-9.
  • thermoelectric element of Comparative Example 4 in which the average cross-sectional area of the cross section orthogonal to the longitudinal direction was greater than 1 mm 2 , had a limit bending radius greater than 50 mm and broke when it was attached to the heating element. Therefore, in the thermoelectric body of Comparative Example 4, the thermoelectromotive force could not be measured.
  • thermoelectric element of Comparative Example 5 in which the average cross-sectional area of the cross section perpendicular to the longitudinal direction was greater than 1 mm 2 , had a limit bending radius greater than 50 mm and broke when it was attached to the heating element. Therefore, in the thermoelectric body of Comparative Example 5, the thermoelectromotive force could not be measured.
  • thermoelectric body In Comparative Example 6, an attempt was made to produce a thermoelectric body by setting the Eu number in the liquid quenching method (here, the melt spinning method) to a range much smaller than 0.001, but the thermoelectric body could not be produced.
  • thermoelectric body In Comparative Example 7, an attempt was made to produce a thermoelectric body by setting the Eu number in the liquid quenching method (here, melt spinning method) to a range much larger than 0.1, but the thermoelectric body could not be produced.
  • the melt spinning method (single roll method) was used as the liquid quenching method to produce the thermoelectric body. It was confirmed that similar results were obtained when the body was produced.

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WO2024147216A1 (ja) * 2023-01-05 2024-07-11 株式会社村田製作所 熱電体、熱電体の製造方法、熱電デバイス、及び、熱電デバイスの製造方法
WO2024203138A1 (ja) * 2023-03-31 2024-10-03 日東電工株式会社 熱電変換素子及びセンサ

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JP2004071953A (ja) * 2002-08-08 2004-03-04 Toshiba Corp 熱電半導体部材とその製造方法、およびそれを用いた熱電素子
JP2004076046A (ja) * 2002-08-13 2004-03-11 Showa Denko Kk フィルドスクッテルダイト系合金、その製造方法および熱電変換素子
JP2020047615A (ja) * 2018-09-14 2020-03-26 日本電気株式会社 熱電変換装置
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JP2004071953A (ja) * 2002-08-08 2004-03-04 Toshiba Corp 熱電半導体部材とその製造方法、およびそれを用いた熱電素子
JP2004076046A (ja) * 2002-08-13 2004-03-11 Showa Denko Kk フィルドスクッテルダイト系合金、その製造方法および熱電変換素子
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JPWO2024147216A1 (https=) * 2023-01-05 2024-07-11
WO2024203138A1 (ja) * 2023-03-31 2024-10-03 日東電工株式会社 熱電変換素子及びセンサ

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