WO2021065670A1 - Module de conversion thermoélectrique - Google Patents

Module de conversion thermoélectrique Download PDF

Info

Publication number
WO2021065670A1
WO2021065670A1 PCT/JP2020/036027 JP2020036027W WO2021065670A1 WO 2021065670 A1 WO2021065670 A1 WO 2021065670A1 JP 2020036027 W JP2020036027 W JP 2020036027W WO 2021065670 A1 WO2021065670 A1 WO 2021065670A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoelectric conversion
thermoelectric
conversion module
heat
conversion element
Prior art date
Application number
PCT/JP2020/036027
Other languages
English (en)
Japanese (ja)
Inventor
邦久 加藤
亘 森田
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2021551155A priority Critical patent/JPWO2021065670A1/ja
Publication of WO2021065670A1 publication Critical patent/WO2021065670A1/fr

Links

Images

Classifications

    • 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
    • H10N10/13—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 heat-exchanging means at the junction

Definitions

  • the present invention relates to a thermoelectric conversion module.
  • thermoelectric conversion having a thermoelectric effect such as the Seebeck effect and the Peltier effect.
  • thermoelectric conversion module that uses a material to directly convert thermal energy into electrical energy.
  • thermoelectric conversion module the use of a so-called ⁇ -type thermoelectric conversion element is known.
  • ⁇ -type a pair of electrodes separated from each other are provided on the substrate, for example, a P-type thermoelectric element is provided on the-one electrode and an N-type thermoelectric element is provided on the other electrode, also separated from each other.
  • thermoelectric conversion element It is configured by connecting the top surfaces of both thermoelectric materials to the electrodes of the opposing substrates. Further, the use of a so-called in-plane type thermoelectric conversion element is known. In the in-plane type, P-type thermoelectric elements and N-type thermoelectric elements are alternately provided in the in-plane direction of the substrate. For example, the lower part of the joint between the two thermoelectric elements is connected in series via an electrode. Has been done. Under these circumstances, from the viewpoint of improving the thermoelectric performance, usually, in order to efficiently impart a temperature difference to the thermoelectric conversion element, a heat radiating member may be provided on the surface of the thermoelectric conversion element on the low temperature side.
  • thermoelectric conversion element when using a thermoelectric conversion element, a heat sink (hereinafter, may be referred to as a "heat dissipation member") is provided on the thermoelectric conversion element, and a part of the heat sink is connected to a heat storage material or the like. , It is disclosed that power generation is efficiently performed based on the temperature difference generated between the heat storage material and the heat sink.
  • thermoelectric conversion module of Patent Document 1 a rigid and three-dimensionally bulky fin or the like is used as a heat radiating member. It may be difficult to install the thermoelectric conversion module, and it may be difficult to use the heat source effectively and efficiently.
  • the present invention has a high degree of freedom in handling the heat radiating member even in a place where the heat source is narrow and the installation space is limited, and thermoelectric conversion capable of efficiently imparting a temperature difference.
  • the challenge is to provide modules.
  • thermoelectric conversion module comprising a thermoelectric conversion element and a first heat radiating member thermally connected to one surface of the thermoelectric conversion element, wherein the first heat radiating member is a wire or a metal leaf.
  • thermoelectric conversion module (2) The above (1), wherein the first heat dissipation member is provided with a thermally connected connecting member at an end opposite to the end connected to one surface of the thermoelectric conversion element. Thermoelectric conversion module. (3) The above (1), wherein the first heat radiating member is provided with a thermally connected housing at an end opposite to the end connected to one surface of the thermoelectric conversion element. Thermoelectric conversion module. (4) The thermoelectric conversion module according to (3) above, wherein the temperature difference between the temperature of one surface of the thermoelectric conversion element and the housing is 10 ° C. or more. (5) The thermoelectric conversion module according to any one of (1) to (4) above, wherein the first heat radiating member is made of a highly thermally conductive material.
  • thermoelectric conversion module according to (5) above, wherein the highly thermally conductive material is selected from gold, copper, silver, iron, nickel, aluminum and brass (brass). (7) The thermoelectric conversion module according to (3) or (4) above, wherein the material of the housing is selected from rubber, resin and metal. (8) The thermoelectric conversion module according to any one of (1) to (7) above, wherein the heat capacity Mh of the housing is larger than the heat capacity Mw of the first heat radiating member. (9) The thermoelectricity according to any one of (1) to (8) above, wherein the ratio (Mh / Mw) of the heat capacity Mh of the housing to the heat capacity Mw of the first heat radiating member is 2 to 5000. Conversion module.
  • thermoelectric conversion according to any one of (1) to (9) above, comprising a second heat radiating member thermally connected between one surface of the thermoelectric conversion element and the first heat radiating member. module.
  • thermoelectric conversion module according to any one of (1) to (10) above, comprising a heat transfer member thermally connected to the other surface of the thermoelectric conversion element.
  • thermoelectric conversion module according to any one of (1) to (11) above, wherein the thermoelectric conversion element is composed of a ⁇ -type thermoelectric conversion element or an in-plane type thermoelectric conversion element.
  • thermoelectric conversion module capable of efficiently applying a temperature difference with a high degree of freedom in handling the heat radiating member can be installed. Can be provided.
  • thermoelectric conversion module of this invention It is sectional drawing for demonstrating an example of the structure of the thermoelectric conversion module of this invention. It is sectional drawing for demonstrating another example of the structure of the thermoelectric conversion module of this invention.
  • thermoelectric conversion module of the present invention includes a thermoelectric conversion element and a first heat radiating member thermally connected to one surface of the thermoelectric conversion element, and the first heat radiating member is a wire or a metal leaf. It is a feature.
  • the first heat radiating member constituting the thermoelectric conversion module is made of a flexible wire or metal foil, so that heat radiated from one surface of the thermoelectric conversion element derived from the heat source is efficiently conducted.
  • rigid and three-dimensionally bulky heat radiating fins, etc. it is possible to efficiently apply a temperature difference to the thermoelectric conversion element, and the heat source is in a narrow place, so that the thermoelectric conversion is performed. Even in a place where the installation space of the module is limited, it is possible to increase the degree of freedom of handling related to the installation of the heat radiating member and the like.
  • FIG. 1 is a cross-sectional configuration diagram for explaining an example of the configuration of the thermoelectric conversion module of the present invention.
  • the thermoelectric conversion module 1A is configured as a so-called ⁇ -type thermoelectric conversion element, and is between the first substrate 2a and the facing second substrate 2b and the first substrate 2a and the facing second substrate 2b.
  • the P-type thermoelectric element layer 4 and the N-type thermoelectric element layer 5 formed in the above, the first electrode 3a formed on the first substrate 2a, and the second substrate 2b facing the first electrode 3a.
  • a bonding material portion 6a is interposed as a first heat radiating member, and a wire 7 is thermally used.
  • the wire 7 extends to the end 8.
  • a wire or a metal foil is used as the first heat radiating member used in the present invention.
  • the wire is not particularly limited as long as it has flexibility, and the cross-sectional shape may be circular, elliptical, rectangular, or the like. Further, the wire may be a single wire, a stranded wire, or a combination thereof, or a plurality of wires may be used independently of each other.
  • the metal foil is not particularly limited as long as it has flexibility. Further, it may be used alone or in combination of a plurality of sheets.
  • the wire used in the present invention it is preferable to use a highly thermally conductive material.
  • the highly thermally conductive material is preferably a single metal such as gold, copper, silver, iron, nickel, or aluminum from the viewpoint of being flexible and efficiently conducting heat dissipation from one surface of the thermoelectric conversion element derived from the heat source. , Brass (brass) and the like, more preferably copper (including oxygen-free copper) and aluminum.
  • each wire used in the present invention is appropriately selected depending on the material used, but is not particularly limited as long as it has flexibility and mechanical strength can be maintained. Usually from 0.008 ⁇ 30.0 mm 2, preferably 0.5 ⁇ 20.0 mm 2, more preferably 1.0 ⁇ 10.0 mm 2, more preferably 2.0 ⁇ 5.0 mm 2. If the cross-sectional area of the wire is within the above range, the degree of freedom of handling as a heat radiating member can be increased even in a place where the heat source is narrow and the installation space of the thermoelectric conversion module is limited.
  • the length per wire used in the present invention is not particularly limited, but is appropriately selected according to the housing to be connected, which will be described later, and is usually about 1 cm to 100 cm.
  • the metal foil used in the present invention is not particularly limited as long as it is a metal, and is preferably gold or copper from the viewpoint of having flexibility and efficiently conducting heat dissipation from one surface of the thermoelectric conversion element derived from the heat source. It is a single metal such as silver, iron, nickel and aluminum, and an alloy such as brass (brass), and more preferably copper (including oxygen-free copper) and aluminum.
  • the thickness of the metal foil used in the present invention is usually 0.1 ⁇ m to 500 ⁇ m, preferably 1 ⁇ m to 300 ⁇ m, more preferably 2 ⁇ m to 200 ⁇ m, and further preferably 3 ⁇ m to 100 ⁇ m. If the thickness of the metal foil is within the above range, the flexibility is further improved, and even in a place where the heat source is narrow and the installation space of the thermoelectric conversion module is limited, the degree of freedom of handling as a heat radiating member is increased. be able to.
  • the length per metal foil used in the present invention is not particularly limited, but is appropriately selected according to the housing to be connected, which will be described later, and is usually about 1 cm to 100 cm.
  • the first heat radiating member is thermally connected to an end portion of the first heat radiating member opposite to the end connected to one surface of the thermoelectric conversion element. It is preferable to provide a housing.
  • the housing efficiently receives the heat conducted from the first heat radiating member, and as a result, lowers the temperature of one surface of the thermoelectric conversion element and increases the temperature difference from the other surface of the thermoelectric conversion element on the heat source side. It is used to make it.
  • FIG. 2 is a cross-sectional configuration diagram for explaining another example of the configuration of the thermoelectric conversion module of the present invention.
  • the thermoelectric conversion module 1B has the same configuration as the thermoelectric conversion module 1A except that the end portion 8 of the wire 7 is thermally connected to the housing 9 via the bonding material portion 6b in the thermoelectric conversion module 1A. ing.
  • the housing used in the present invention preferably has a heat capacity Mh (J / K) larger than the heat capacity Mw (J / K) of the first heat radiation member from the viewpoint of efficiently dissipating heat.
  • the material of the housing may be the same as or different from the high thermal conductive material used as the first heat radiating member. From the viewpoint of installation in a narrow space (miniaturization of the housing), it is more preferable to use a material having a specific heat higher than that of the high thermal conductive material used. Examples of the material of such a housing include rubber, resin, metal, and the like, which can be appropriately selected depending on the highly thermally conductive material used.
  • the ratio (Mh / Mw) of the heat capacity Mh of the housing to the heat capacity Mw of the first heat radiating member depends on the heat capacity of the first heat radiating member to be used, but is preferably more than 1, more preferably 2. It is ⁇ 5000, more preferably 4 ⁇ 5000, and particularly preferably 8 ⁇ 5000. When this ratio is set to this value, heat radiated from one surface of the thermoelectric conversion element is conducted through the first heat radiating member and efficiently stored in the housing, and as a result, the temperature of one surface of the thermoelectric conversion element is lowered, and the heat source The temperature difference between the side thermoelectric conversion element and the other surface can be increased.
  • thermoelectric conversion element From the viewpoint of efficiently dissipating heat from one surface of the thermoelectric conversion element derived from the heat source, one surface of the thermoelectric conversion element (for example, the surface of the second substrate 2b in FIG. 1 opposite to the electrode side). ) And the end of the wire (for example, the end of the wire opposite to the end 8 in FIG. 1), a second heat radiating member (not shown) thermally connected to both. It is preferable to provide.
  • the second heat radiating member is not particularly limited, but it is preferable to use a highly thermally conductive material.
  • Highly thermally conductive materials include single metals such as copper, silver, iron, nickel, chromium and aluminum, and alloys such as stainless steel and brass (brass) from the viewpoint of efficiently conducting heat dissipation from one surface of the thermoelectric conversion element.
  • single metals such as copper, silver, iron, nickel, chromium and aluminum
  • alloys such as stainless steel and brass (brass) from the viewpoint of efficiently conducting heat dissipation from one surface of the thermoelectric conversion element.
  • copper including oxygen-free copper
  • aluminum, and stainless steel are preferable, and copper is more preferable because it has high thermal conductivity and is easy to process.
  • a plurality of the single metals, alloys and the like may be laminated and used.
  • the thickness is preferably 3 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and even more preferably 10 to 50 ⁇ m.
  • a method for forming the second heat radiating member from the viewpoint of simplicity of the process, it is preferable to provide an electroplating method, an electroless plating method, a combination thereof, and a metal foil on the substrate by a welding method. Further, a predetermined pattern can be formed by performing a known chemical treatment mainly on a photolithography method on a highly thermally conductive material, for example, a wet etching treatment of a patterning portion of a photoresist and removing the photoresist. preferable.
  • a heat transfer member for example, the surface of the second substrate 2a on the second substrate 2a opposite to the electrode side in FIG. 1) of the thermoelectric conversion element (FIG. 1). (Not shown) is preferably provided.
  • the heat transfer member is not particularly limited, but it is preferable to use a highly heat conductive material.
  • the highly thermally conductive material is preferably a single metal such as gold, copper, silver, iron, nickel, or aluminum, stainless steel, or brass (brass) from the viewpoint of efficiently conducting heat radiation from the heat source to the other surface of the thermoelectric conversion element.
  • more preferably copper (including anoxic copper) and aluminum may be used.
  • the thickness of the heat transfer member is preferably 3 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and even more preferably 10 to 50 ⁇ m.
  • the method for forming the heat transfer member can be the same as the method for forming the second heat radiation member described above.
  • thermoelectric conversion module of the present invention a connection thermally connected to the end of the first heat radiating member opposite to the end connected to one surface of the thermoelectric conversion element. It is preferable to include a member.
  • the end 8 of the wire 7 as the first heat radiating member is provided with a connecting member (not shown).
  • the connecting member is not particularly limited as long as it can be thermally connected, and general-purpose members such as clips, solders, conductive pastes, conductive adhesives, and bonding agents can be used, depending on the mode of the object to be connected. It can be selected as appropriate.
  • the temperature difference between the temperature of one surface of the thermoelectric conversion element and the temperature of the housing is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, still more preferably 30 ° C. or higher, and particularly preferably 30 ° C. or higher. It is 40 ° C. or higher.
  • the upper limit of the temperature difference is usually 100 ° C. or lower.
  • the thermoelectric conversion module of the present invention preferably includes a first substrate having a first electrode.
  • a first substrate having a first electrode when configured as a ⁇ -type thermoelectric conversion element, it is preferable to include a second substrate having a second electrode facing the first substrate having the first electrode.
  • a second substrate facing the first substrate having the first electrode when configured as an in-plane type thermoelectric conversion element, it is preferable to include a second substrate facing the first substrate having the first electrode.
  • the first substrate and the second substrate facing the first substrate may be the same or different.
  • the first and second substrates are not particularly limited, and glass, ceramics, plastic film, or the like can be used independently of each. Among these, a plastic film is preferable from the viewpoint of having flexibility and having a degree of freedom for installation of a heat source on the surface.
  • a polyimide film, a polyamide film, a polyetherimide film, a polyaramid film, a polyamideimide film, and a polysulfone film are preferable from the viewpoint of high heat resistance and less generation of outgas, and further, from the viewpoint of high versatility.
  • Polyimide film is particularly preferable.
  • the thickness of the first and second substrates is preferably 1 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, still more preferably 20 to 100 ⁇ m, independently from the viewpoint of heat resistance and flexibility. Further, the first and second substrates preferably have a 5% weight loss temperature of 300 ° C. or higher, more preferably 400 ° C. or higher, as measured by thermogravimetric analysis.
  • the heating dimension change rate measured at 200 ° C. according to JIS K7133 (1999) is preferably 0.5% or less, and more preferably 0.3% or less.
  • the coefficient of linear expansion in the plane direction measured in accordance with JIS K7197 (2012) is 0.1 ppm ⁇ °C -1 to 50 ppm ⁇ °C -1 , and 0.1 ppm ⁇ °C -1 to 30 ppm ⁇ °C -1. Is more preferable.
  • the thermoelectric conversion module of the present invention preferably includes a first electrode.
  • the second electrode is included in the second substrate facing the first substrate having the first electrode.
  • the first electrode and the second electrode of the second substrate facing the first substrate may be the same or different.
  • a second electrode may or may not be present.
  • the metal material used for the first electrode and the second electrode is not particularly limited, but independently, copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, or any of these. An alloy containing the metal of is preferred.
  • the thickness of the layers of the first electrode and the second electrode are independently, preferably 10 nm to 200 ⁇ m, more preferably 30 nm to 150 ⁇ m, and further preferably 50 nm to 120 ⁇ m. When the thickness of the layers of the first electrode and the second electrode is within the above range, the electrical conductivity is high and the resistance is low, and sufficient strength as an electrode can be obtained.
  • the formation of the first electrode and the second electrode is performed using the metal material described above.
  • a method for forming the first electrode and the second electrode after providing an electrode having no pattern formed on the substrate, a known physical treatment or chemical treatment mainly composed of a photolithography method, or a method thereof.
  • a method of processing into a predetermined pattern shape by using the above in combination, or a method of directly forming an electrode pattern by a screen printing method, an inkjet method, or the like can be mentioned.
  • Examples of the method for forming the electrode in which the pattern is not formed include PVD (Physical Vapor Deposition) such as vacuum deposition, sputtering, and ion plating, or CVD (Chemical Vapor Deposition) such as thermal CVD and atomic layer deposition (ALD). Dry process such as vapor deposition method), various coating methods such as dip coating method, spin coating method, spray coating method, gravure coating method, die coating method, doctor blade method, wet process such as electrodeposition method, silver salt method , Electrolytic plating method, electroless plating method, lamination of metal foil and the like, and are appropriately selected according to the material of the electrode.
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • ALD atomic layer deposition
  • thermoelectric performance high conductivity and high thermal conductivity are required, so it is preferable to use electrodes formed by a plating method or a vacuum film forming method. Since high conductivity and high thermal conductivity can be easily realized, a vacuum film forming method such as a vacuum vapor deposition method and a sputtering method, and an electrolytic plating method and an electroless plating method are preferable. Although it depends on the dimensions of the forming pattern and the requirements for dimensional accuracy, the pattern can be easily formed by interposing a hard mask such as a metal mask.
  • thermoelectric element layer used in the present invention is preferably a thermoelectric semiconductor composition containing thermoelectric semiconductor particles, a heat-resistant resin, and one or both of an ionic liquid and an inorganic ionic compound on a substrate.
  • thermoelectric semiconductor particles For the thermoelectric semiconductor particles used in the thermoelectric element layer, it is preferable that the thermoelectric semiconductor material is pulverized to a predetermined size by a fine pulverizer or the like.
  • the material constituting the P-type thermoelectric element layer and the N-type thermoelectric element layer used in the present invention is not particularly limited as long as it is a material capable of generating thermoelectromotive force by imparting a temperature difference, and is not particularly limited.
  • P-type bismuth telluride, N-type bismuth telluride, etc. bismuth - telluride thermoelectric semiconductor material; GeTe, telluride based thermoelectric semiconductor materials such as PbTe; antimony - tellurium based thermoelectric semiconductor material; ZnSb, Zn 3 Sb 2, Zn 4 Sb 3 , etc.
  • Zinc-antimon thermoelectric semiconductor materials silicon-germanium thermoelectric semiconductor materials such as SiGe; bismus selenide thermoelectric semiconductor materials such as Bi 2 Se 3 ; ⁇ -FeSi 2 , CrSi 2 , MnSi 1.73 , Mg 2 Si Hydroelectric semiconductor materials such as silicide-based thermoelectric semiconductor materials; oxide-based thermoelectric semiconductor materials; Whistler materials such as FeVAL, FeVALSi, and FeVTiAl, sulfide-based thermoelectric semiconductor materials such as TiS 2, and the like are used.
  • thermoelectric semiconductor material used in the present invention is preferably a bismuth-tellurium-based thermoelectric semiconductor material such as P-type bismuthellide or N-type bismuthellide.
  • P-type bismuth telluride one having a hole as a carrier and a positive Seebeck coefficient, for example, represented by Bi X Te 3 Sb 2-X is preferably used.
  • X is preferably 0 ⁇ X ⁇ 0.8, more preferably 0.4 ⁇ X ⁇ 0.6.
  • X is larger than 0 and 0.8 or less, the Seebeck coefficient and the electric conductivity become large, and the characteristics as a P-type thermoelectric conversion material are maintained, which is preferable.
  • N-type bismuth telluride those having an electron carrier and a negative Seebeck coefficient, for example, represented by Bi 2 Te 3-Y Se Y , are preferably used.
  • the Seebeck coefficient and the electric conductivity become large, and the characteristics as an N-type thermoelectric conversion material are maintained, which is preferable.
  • the blending amount of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass. It is more preferably 50 to 96% by mass, and even more preferably 70 to 95% by mass.
  • the Seebeck coefficient absolute value of the Peltier coefficient
  • the decrease in the electric conductivity is suppressed, and only the thermal conductivity is decreased, so that high thermoelectric performance is exhibited.
  • a film having sufficient film strength and flexibility can be obtained, which is preferable.
  • the average particle size of the thermoelectric semiconductor particles is preferably 10 nm to 200 ⁇ m, more preferably 10 nm to 30 ⁇ m, still more preferably 50 nm to 10 ⁇ m, and particularly preferably 1 to 6 ⁇ m. Within the above range, uniform dispersion can be facilitated and the electrical conductivity can be increased.
  • the method of pulverizing the thermoelectric semiconductor material to obtain thermoelectric semiconductor particles is not particularly limited, and is a jet mill, a ball mill, a bead mill, a colloid mill, a conical mill, a disc mill, an edge mill, a milling mill, a hammer mill, a pellet mill, a willy mill, and a roller.
  • thermoelectric semiconductor particles It may be pulverized to a predetermined size by a known fine pulverizer such as a mill.
  • the average particle size of the thermoelectric semiconductor particles was obtained by measuring with a laser diffraction type particle size analyzer (Mastersizer 3000 manufactured by Malvern), and was used as the median value of the particle size distribution.
  • thermoelectric semiconductor particles are annealed (hereinafter, may be referred to as "annealing treatment A").
  • annealing treatment A By performing the annealing treatment A, the crystallinity of the thermoelectric semiconductor particles is improved, and the surface oxide film of the thermoelectric semiconductor particles is removed, so that the Seebeck coefficient (absolute value of the Peltier coefficient) of the thermoelectric conversion material is increased. , The thermoelectric performance index can be further improved.
  • the annealing treatment A is not particularly limited, but before preparing the thermoelectric semiconductor composition, under an inert gas atmosphere such as nitrogen or argon in which the gas flow rate is controlled so as not to adversely affect the thermoelectric semiconductor particles.
  • thermoelectric semiconductor particles such as hydrogen or under vacuum conditions
  • a mixed gas atmosphere of an inert gas and a reducing gas preferably in a mixed gas atmosphere of an inert gas and a reducing gas.
  • the specific temperature condition depends on the thermoelectric semiconductor particles used, but it is usually preferable to carry out the temperature at a temperature equal to or lower than the melting point of the particles and at 100 to 1500 ° C. for several minutes to several tens of hours.
  • the heat-resistant resin used in the present invention acts as a binder between thermoelectric semiconductor particles and enhances the flexibility of the thermoelectric element layer.
  • the heat-resistant resin is not particularly limited, but when a thin film made of a thermoelectric semiconductor composition is subjected to crystal growth of thermoelectric semiconductor particles by annealing or the like, various factors such as mechanical strength and thermal conductivity as the resin are obtained. Use a heat-resistant resin that maintains its physical properties without being impaired.
  • the heat-resistant resin include polyamide resins, polyamideimide resins, polyimide resins, polyetherimide resins, polybenzoxazole resins, polybenzoimidazole resins, epoxy resins, and copolymers having a chemical structure of these resins. Can be mentioned.
  • the heat-resistant resin may be used alone or in combination of two or more.
  • polyamide resins, polyamideimide resins, polyimide resins, and epoxy resins are preferable and have excellent flexibility because they have higher heat resistance and do not adversely affect the crystal growth of thermoelectric semiconductor particles in the thin film.
  • polyamide resin, polyamideimide resin, and polyimide resin are more preferable.
  • the polyimide resin is more preferable as the heat-resistant resin from the viewpoint of adhesion to the polyimide film and the like.
  • the polyimide resin is a general term for polyimide and its precursor.
  • the heat-resistant resin preferably has a decomposition temperature of 300 ° C. or higher.
  • the decomposition temperature is within the above range, the flexibility of the thermoelectric element layer can be maintained without losing the function as a binder even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the heat-resistant resin preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and further preferably 1% or less at 300 ° C. by thermogravimetric analysis (TG). .. As long as the mass reduction rate is within the above range, the flexibility of the thermoelectric element layer can be maintained without losing the function as a binder even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later. ..
  • the blending amount of the heat-resistant resin in the thermoelectric semiconductor composition is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, and further preferably 1 to 20% by mass.
  • a film having both high thermoelectric performance and film strength can be obtained.
  • the ionic liquid used in the present invention is a molten salt formed by combining a cation and an anion, and refers to a salt that can exist as a liquid in any temperature range of ⁇ 50 to 400 ° C.
  • the ionic liquid is an ionic compound having a melting point in the range of ⁇ 50 ° C. or higher and lower than 400 ° C.
  • the melting point of the ionic liquid is preferably ⁇ 25 ° C. or higher and 200 ° C. or lower, and more preferably 0 ° C. or higher and 150 ° C. or lower.
  • Ionic liquids have features such as extremely low vapor pressure, non-volatility, excellent thermostability and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, as a conductive auxiliary agent, it is possible to effectively suppress the reduction of the electric conductivity between the thermoelectric semiconductor particles. Further, since the ionic liquid exhibits high polarity based on the aprotic ionic structure and has excellent compatibility with the heat-resistant resin, the electric conductivity of the thermoelectric element layer can be made uniform.
  • ionic liquid known or commercially available ones can be used.
  • nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium and their derivatives; tetraalkylammonium-based amine-based cations and their derivatives; phosphonium, trialkylsulfonium, tetraalkylphosphonium and the like.
  • phosphine cations and their derivatives include those composed of an anion component such as.
  • the cation component of the ionic liquid is a pyridinium cation and its derivatives from the viewpoints of high temperature stability, compatibility with thermoelectric semiconductor particles and resins, and suppression of decrease in electrical conductivity between thermoelectric semiconductor particle gaps.
  • At least one selected from imidazolium cations and derivatives thereof is preferably contained.
  • an ionic liquid in which the cation component contains a pyridinium cation and a derivative thereof include 4-methyl-butylpyridinium chloride, 3-methyl-butylpyridinium chloride, 4-methyl-hexylpyridinium chloride, and 3-methyl-hexylpyridinium.
  • Chloride 4-methyl-octylpyridinium chloride, 3-methyl-octylpyridinium chloride, 3,4-dimethyl-butylpyridinium chloride, 3,5-dimethyl-butylpyridinium chloride, 4-methyl-butylpyridinium tetrafluoroborate, 4- Examples thereof include methyl-butylpyridinium hexafluorophosphate, 1 (or N) -butylpyridinium bromide, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate and the like. Of these, 1 (or N) -butylpyridinium bromide, 1-butyl-4-methylpyridinium bromide, and 1-butyl-4-methylpyridinium hexafluorophosphate are preferable.
  • the ionic liquid in which the cation component contains an imidazolium cation and a derivative thereof [1-butyl-3- (2-hydroxyethyl) imidazolium bromide] and [1-butyl-3- (2).
  • the above-mentioned ionic liquid preferably has an electric conductivity of 10-7 S / cm or more.
  • the electric conductivity is within the above range, the reduction of the electric conductivity between the thermoelectric semiconductor particles can be effectively suppressed as a conductivity auxiliary agent.
  • the above-mentioned ionic liquid preferably has a decomposition temperature of 300 ° C. or higher. As long as the decomposition temperature is within the above range, the effect as a conductive auxiliary agent can be maintained even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the above-mentioned ionic liquid preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and further preferably 1% or less at 300 ° C. by thermogravimetric analysis (TG). ..
  • TG thermogravimetric analysis
  • the blending amount of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 20% by mass.
  • the blending amount of the ionic liquid is within the above range, the decrease in electrical conductivity is effectively suppressed, and a film having high thermoelectric performance can be obtained.
  • the inorganic ionic compound used in the present invention is a compound composed of at least cations and anions.
  • the inorganic ionic compound is solid at room temperature, has a melting point in any temperature in the temperature range of 400 to 900 ° C., and has characteristics such as high ionic conductivity. Therefore, it can be used as a conductive auxiliary agent. It is possible to suppress a decrease in electrical conductivity between thermoelectric semiconductor particles.
  • a metal cation is used as the cation.
  • the metal cation include alkali metal cations, alkaline earth metal cations, typical metal cations and transition metal cations, and alkali metal cations or alkaline earth metal cations are more preferable.
  • the alkali metal cation include Li + , Na + , K + , Rb + , Cs +, Fr + and the like.
  • Examples of the alkaline earth metal cation include Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ .
  • the anion such as, F -, Cl -, Br -, I -, OH -, CN -, NO 3 -, NO 2 -, ClO -, ClO 2 -, ClO 3 -, ClO 4 -, CrO 4 2 -, HSO 4 -, SCN - , BF 4 -, PF 6 - , and the like.
  • a cation component such as potassium cation, sodium cation, or lithium cations, Cl -, AlCl 4 -, Al 2 Cl 7 -, ClO 4 - chloride or ion, Br -, etc. of bromide ion, I -, etc. iodide ion, BF 4 -, PF 6 - fluoride ions, F (HF) n, such as - such as halide anions of, NO 3 -, OH -, CN - and the ones mentioned consists the anion component of such Be done.
  • a cation component such as potassium cation, sodium cation, or lithium cations
  • the cationic component of the inorganic ionic compound is potassium from the viewpoints of high temperature stability, compatibility with thermoelectric semiconductor particles and resins, suppression of decrease in electrical conductivity between thermoelectric semiconductor particle gaps, and the like.
  • Sodium, and lithium are preferably included.
  • the anion component of the inorganic ionic compound preferably contains a halide anion, and more preferably contains at least one selected from Cl ⁇ , Br ⁇ , and I ⁇ .
  • Cationic component is, as a specific example of the inorganic ionic compound containing a potassium cation, KBr, KI, KCl, KF , KOH, K 2 CO 3 and the like. Of these, KBr and KI are preferable.
  • Specific examples of the inorganic ionic compound whose cation component contains a sodium cation include NaBr, NaI, NaOH, NaF, Na 2 CO 3 and the like. Of these, NaBr and NaI are preferable.
  • Specific examples of the inorganic ionic compound whose cation component contains a lithium cation include LiF, LiOH, and LiNO 3 . Of these, LiF and LiOH are preferable.
  • the above-mentioned inorganic ionic compound preferably has an electric conductivity of 10-7 S / cm or more, and more preferably 10-6 S / cm or more.
  • the electric conductivity is within the above range, the reduction of the electric conductivity between the thermoelectric semiconductor particles can be effectively suppressed as a conductivity auxiliary agent.
  • the decomposition temperature of the above-mentioned inorganic ionic compound is preferably 400 ° C. or higher. As long as the decomposition temperature is within the above range, the effect as a conductive auxiliary agent can be maintained even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the above-mentioned inorganic ionic compound preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and preferably 1% or less at 400 ° C. by thermogravimetric analysis (TG). More preferred. As long as the mass reduction rate is within the above range, the effect as a conductive auxiliary agent can be maintained even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • TG thermogravimetric analysis
  • the blending amount of the inorganic ionic compound in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 10% by mass. ..
  • the blending amount of the inorganic ionic compound is within the above range, the decrease in electrical conductivity can be effectively suppressed, and as a result, a film having improved thermoelectric performance can be obtained.
  • the total content of the inorganic ionic compound and the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass. It is preferably 0.5 to 30% by mass, more preferably 1.0 to 10% by mass.
  • the thickness of the thermoelectric element layer is not particularly limited, and is preferably 100 nm to 1000 ⁇ m, more preferably 300 nm to 600 ⁇ m, and further preferably 5 to 400 ⁇ m from the viewpoint of thermoelectric performance and film strength.
  • the P-type thermoelectric element layer and the N-type thermoelectric element layer as the thin film made of the thermoelectric semiconductor composition are further subjected to an annealing treatment (hereinafter, may be referred to as "annealing treatment B").
  • annealing treatment B By performing the annealing treatment B, the thermoelectric performance can be stabilized, and the thermoelectric semiconductor particles in the thin film can be crystal-grown, so that the thermoelectric performance can be further improved.
  • the annealing treatment B is not particularly limited, but is usually carried out under an inert gas atmosphere such as nitrogen or argon, a reducing gas atmosphere, or a vacuum condition in which the gas flow rate is controlled, and the resin and the ionic compound to be used are used. Although it depends on the heat-resistant temperature and the like, it is carried out at 100 to 500 ° C. for several minutes to several tens of hours.
  • thermoelectric conversion module of the present invention is not particularly limited, but is preferably composed of a ⁇ -type thermoelectric conversion element or an in-plane type thermoelectric conversion element. Further, it is preferable to use it for power generation in the configuration of a ⁇ -type thermoelectric conversion element or an in-plane type thermoelectric conversion element.
  • thermoelectric conversion module a step of forming an electrode on a substrate (hereinafter, may be referred to as an “electrode forming step”), the thermoelectric semiconductor composition is applied and dried to form a thermoelectric element layer.
  • a step hereinafter, may be referred to as “thermoelectric element layer forming step”
  • annealing treatment step a step of annealing the thermoelectric element layer (hereinafter, may be referred to as “annealing treatment step”), and further annealing-treated substrate.
  • thermoelectric conversion module of the present invention By a method including a step of bonding to another substrate (hereinafter, may be referred to as “bonding process”) and a step of connecting a heat radiating member to the substrate (hereinafter, may be referred to as “radiating member connecting process”). Can be manufactured.
  • bonding process a step of bonding to another substrate
  • radiating member connecting process a step of connecting a heat radiating member to the substrate
  • the electrode forming step is, for example, a step of forming a pattern made of the above-mentioned metal material on the first substrate, and the method of forming on the substrate and the method of forming the pattern are as described above. Further, in particular, when the above-mentioned ⁇ -type thermoelectric conversion module or the like is manufactured, the step of forming a pattern made of the above-mentioned metal material on the second substrate facing the first substrate is included.
  • the thermoelectric element layer forming step is a step of applying the thermoelectric semiconductor composition on, for example, an electrode.
  • a method of applying the thermoelectric semiconductor composition on the electrode on the first substrate a screen printing method, a flexographic printing method, a gravure printing method, a spin coating method, a dip coating method, a die coating method, a spray coating method, and a bar coating method are used.
  • Known methods such as a method and a doctor blade method can be mentioned and are not particularly limited.
  • the coating film is formed into a pattern, a screen printing method, a slot die coating method, or the like, which enables easy pattern formation using a screen plate having a desired pattern, is preferably used.
  • thermoelectric element layer is dried to form a thermoelectric element layer.
  • drying method conventionally known drying methods such as a hot air drying method, a hot roll drying method, and an infrared irradiation method can be adopted.
  • the heating temperature is usually 80 to 150 ° C., and the heating time varies depending on the heating method, but is usually several seconds to several tens of minutes.
  • the heating temperature is not particularly limited as long as the used solvent can be dried. The same applies when the thermoelectric semiconductor composition is applied onto the electrodes on the second substrate.
  • thermoelectric element layer forming step there is a method in which a thermoelectric element layer is prepared in advance as chips of a thermoelectric conversion material, and a plurality of the obtained chips are placed on predetermined electrodes on a substrate and joined.
  • a method for producing a chip of a thermoelectric conversion material for example, a chip of a thermoelectric conversion material made of a thermoelectric semiconductor composition can be produced by the following method. First, a sacrificial layer is formed on a substrate such as glass, and a thermoelectric element layer (hereinafter, may be referred to as a “chip of a thermoelectric conversion material”) is formed on the obtained sacrificial layer by the method described above.
  • thermoelectric conversion material are annealed, and the chips of the thermoelectric conversion material are peeled off from the sacrificial layer on the substrate to manufacture the chips of the thermoelectric conversion material as individual pieces.
  • a resin such as polymethyl methacrylate or polystyrene, a fluorine-based mold release agent, or a mold release agent such as a silicone-based mold release agent is used.
  • the annealing treatment step is, for example, a step of annealing the thermoelectric element layer in the form of having the first substrate, the electrode, and the thermoelectric element layer obtained above in this order.
  • the annealing treatment is performed by the above-mentioned annealing treatment B.
  • the bonding step for example, the first substrate having the electrodes and the thermoelectric element layer obtained in the annealing process is bonded to the second substrate facing the second substrate or the second substrate having the second electrode.
  • the bonding agent used for the bonding include a conductive paste and the like in the case of a second substrate having a second electrode.
  • the conductive paste include copper paste, silver paste, nickel paste and the like, and when a binder is used, epoxy resin, acrylic resin, urethane resin and the like can be mentioned. Further, in the case of the second substrate having no second electrode, a resin material can be used.
  • the resin material preferably contains a polyolefin-based resin, an epoxy-based resin, or an acrylic-based resin. Further, it is preferable that the resin material has adhesiveness, low water vapor transmittance, and insulating property.
  • having adhesiveness means that the resin material has adhesiveness, adhesiveness, and pressure-sensitive adhesiveness that can be adhered by pressure at the initial stage of sticking. Examples of the method of applying the bonding agent on the substrate include known methods such as a screen printing method and a dispensing method.
  • solder receiving layer When a solder material layer is used for bonding with an electrode in the bonding step, a solder receiving layer can be used in order to improve the bonding strength.
  • the method of forming the solder receiving layer on the chip of the thermoelectric conversion material obtained by the above-mentioned manufacturing method is as follows. After forming the solder receiving layer on all the surfaces of the chip of the thermoelectric conversion material having the upper surface, the lower surface and the side surface, among the obtained solder receiving layers, the solder receiving layer formed on the side surface of the chip of the thermoelectric conversion material is formed. A solder receiving layer is formed by removing all or part of the solder.
  • the solder receiving layer preferably contains a metal material.
  • the metal material is preferably at least one selected from alloys containing gold, silver, rhodium, platinum, chromium, palladium, tin, nickel and any of these metal materials. Among these, more preferably, it has a two-layer structure of gold, silver, nickel or tin and gold, nickel and gold, and silver is further preferable from the viewpoint of material cost, high thermal conductivity and bonding stability.
  • the solder receiving layer is required to have high conductivity and high thermal conductivity from the viewpoint of maintaining thermoelectric performance, and from the viewpoint of reducing the contact resistance at the interface of the thermoelectric conversion material with the chip, a plating method or vacuum is used. It is preferable to use a solder receiving layer formed by a film forming method.
  • the solder material constituting the solder material layer may be appropriately selected in consideration of the heat-resistant temperature of the heat-resistant resin contained in the resin film and the chip of the thermoelectric conversion material, as well as conductivity and heat conductivity.
  • Lead-free and / or cadmium-free from the viewpoint of melting point, conductivity, thermal conductivity, 43Sn / 57Bi alloy, 42Sn / 58Bi alloy, 40Sn / 56Bi / 4Zn alloy, 48Sn / 52In alloy, 39.8Sn / 52In / 7Bi / Alloys such as 1.2 Zn alloys are preferred.
  • Examples of the method of applying the solder material on the electrodes of the substrate include known methods such as a screen printing method and a dispensing method.
  • the heat radiating member connecting step one end of the first heat radiating member is seconded by a solder material layer or the like so that the first heat radiating member is thermally connected to the second substrate obtained in the bonding step.
  • This is a step of fixing to a substrate (however, when a second heat radiating member described later is provided on the second substrate, the two heat radiating members) and extending another end of the first heat radiating member.
  • it is preferable to include a step of fixing the other end portion of the first heat radiating member to the housing with a solder material layer or the like. Fixing in the solder material layer can be performed by a known method.
  • the method for manufacturing the thermoelectric conversion module includes a step of forming the second heat radiating member.
  • the second heat radiating member forming step is a step of forming on, for example, a second substrate (in the case of having an electrode, a surface opposite to the electrode side) using the above-mentioned high thermal conductive material.
  • the method for forming the second heat radiating member is as described above.
  • the method for manufacturing the thermoelectric conversion module includes a step of forming a conductive member.
  • the heat transfer member forming step is a step of forming a conductive member on, for example, a first substrate (in the case of having an electrode, a surface opposite to the electrode side) using the above-mentioned high thermal conductive material.
  • the method for forming the heat transfer member is as described above.
  • thermoelectric conversion module of the present invention even in a place where the heat source is narrow and the installation space is limited, the degree of freedom of handling related to the installation of the heat radiating member is high, and an efficient temperature difference is imparted. It is possible to obtain a thermoelectric conversion module capable of
  • thermoelectric performance of the thermoelectric conversion module produced in the examples and comparative examples was evaluated by the following method.
  • thermoelectric conversion module (A) Evaluation of Electrical Resistance of Thermoelectric Conversion Module The electrical resistance R between the take-out electrodes of the obtained thermoelectric conversion module at a set temperature, which will be described later, is measured using a low resistance measuring device (manufactured by Hioki Electric Co., Ltd., model name: RM3545). The measurement was carried out in an environment of 25 ° C. ⁇ 50% RH.
  • thermoelectric conversion module Output voltage and maximum output evaluation of the thermoelectric conversion module
  • C Evaluation of temperature difference With respect to the obtained thermoelectric conversion module, the temperature difference ⁇ T between the copper foil in contact with the heat radiation surface side and the copper foil in contact with the endothermic surface side was measured using a thermocouple (K type).
  • the heat source is a hot plate
  • the other surface of the thermoelectric conversion module (heating surface: the surface on the side that does not have a wire as the first heat radiation member) is 40 ° C, 50 ° C, 60 ° C, 70 ° C, 80 ° C and 90.
  • Electrical resistance between the take-out electrodes of the thermoelectric conversion module, output voltage, maximum output, and temperature between the heating surface and the cooling surface at each temperature when heating is set to ° C (excluding 90 ° C in Comparative Example 1). The difference was evaluated.
  • thermoelectric semiconductor composition production of thermoelectric semiconductor particles
  • P-type bismuth tellurium Bi 0.4 Te 3 Sb 1.6 manufactured by High Purity Chemical Laboratory, particle size: 90 ⁇ m
  • Thermoelectric semiconductor particles T1 having an average particle size of 2.0 ⁇ m were produced by pulverizing in an air atmosphere using -7).
  • N-type bismuth tellurium Bi 2 Te 3 (manufactured by High Purity Chemical Laboratory, particle size: 90 ⁇ m), which is a bismuth-tellurium thermoelectric semiconductor material, is pulverized in the same manner as described above, and thermoelectric semiconductor particles having an average particle size of 2.0 ⁇ m are pulverized.
  • T2 was prepared.
  • the thermoelectric semiconductor particles T1 and T2 obtained by pulverization were subjected to particle size distribution measurement with a laser diffraction type particle size analyzer (Mastersizer 3000 manufactured by Malvern).
  • Coating liquid (P) 83.3 parts by mass of particles T1 of P-type bismasterlide Bi 0.4 Te 3.0 Sb 1.6 obtained above, and polyamide-imide as a heat-resistant resin (manufactured by Arakawa Chemical Industry Co., Ltd., product name: Composelan AI301, Solvent: N-methylpyrrolidone, solid content concentration: 18% by mass) 2.7 parts by mass, and 14 parts by mass of N-butylpyridinium bromide as an ionic liquid are mixed and dispersed in a coating liquid (P) consisting of a thermoelectric semiconductor composition. Prepared.
  • Coating liquid (N) 92.1 parts by mass of the obtained N-type bismasterlide Bi 2.0 Te 3.0 particles T2, polyamide-imide as a heat-resistant resin (manufactured by Arakawa Chemical Industry Co., Ltd., product name: composelan AI301, solvent: N-methylpyrrolidone) , Solid content concentration: 18% by mass) 3.0 parts by mass, and 4.9 parts by mass of N-butylpyridinium bromide as an ionic liquid were mixed and dispersed to prepare a coating liquid (N) consisting of a thermoelectric semiconductor composition.
  • thermoelectric conversion material Polymethylmethyl methacrylate resin (PMMA) (Sigma Aldrich Co., Ltd.) as a sacrificial layer on a glass substrate (manufactured by Kawamura Kuzo Shoten Co., Ltd., trade name: blue plate glass) with a thickness of 0.7 mm.
  • PMMA Polymethylmethyl methacrylate resin
  • a glass substrate manufactured by Kawamura Kuzo Shoten Co., Ltd., trade name: blue plate glass
  • a thickness of 0.7 mm Made by spin-coating a polymethylmethyl methacrylate resin solution having a solid content concentration of 10% by mass, which is obtained by dissolving (trade name: polymethyl methacrylate) in toluene, so that the thickness after drying becomes 10.0 ⁇ m. Filmed.
  • the coating liquid (P) prepared in (1) above was applied onto the sacrificial layer via a metal mask by a screen printing method, dried at a temperature of 120 ° C. for 7 minutes in the air, and thickened. Formed a thin film of 200 ⁇ m.
  • thermoelectric conversion material chip The thin film is annealed, particles of thermoelectric semiconductor material are grown into crystals, and the upper and lower surfaces are 1.65 mm ⁇ 1.65 mm, respectively, and the thickness is 1.65 mm ⁇ 1.65 mm, which contains P-type bismuth sterlide Bi 0.4 Te 3 Sb 1.6.
  • a 200 ⁇ m rectangular parallelepiped thermoelectric conversion material chip was obtained. Further, the upper and lower surfaces each containing the N-type bismuth telluride Bi 2 Te 3 are similarly 1 except that the coating liquid (N) prepared in the above (1) is changed and held at 360 ° C. for 1 hour for annealing treatment.
  • a rectangular parallelepiped thermoelectric conversion material chip having a thickness of .65 mm ⁇ 1.65 mm and a thickness of 200 ⁇ m was obtained.
  • solder receiving layer The chips of each thermoelectric conversion material after annealing are peeled off from the glass substrate, and the solder receiving layer [Ni] is applied to all surfaces of the chips of each thermoelectric conversion material by electroless plating. (Thickness: 3 ⁇ m) was laminated with Au (thickness: 40 nm)]. Next, the solder receiving layer on the side surface of the chip of P-type and N-type thermoelectric conversion material is machine-polished, that is, sandpaper (count 2000) is used so that the chip has a size of 1.5 mm ⁇ 1.5 mm. The chips were removed to obtain chips of P-type and N-type thermoelectric conversion materials having solder receiving layers only on the upper and lower surfaces. In addition, in order to completely remove the solder receiving layer, a part of the side wall was also polished.
  • thermoelectric conversion module Manufacturing of thermoelectric conversion module
  • a ⁇ -type thermoelectric conversion element consisting of 18 pairs of P-type and N-type thermoelectric conversion material chips each is as follows. Made in. First, a substrate (manufactured by Ube Eximo Co., Ltd., product name: Iupicel N, polyimide substrate, thickness: 12.5 ⁇ m, copper foil, thickness: 12 ⁇ m) with copper foil attached on both sides was prepared, and the copper foil of the film substrate was prepared.
  • a nickel layer (thickness: 3 ⁇ m) and a gold layer (thickness: 40 nm) are laminated in this order by electroless plating, and then electrode patterns (10 ⁇ 10 mm square, 18 pieces, adjacent electrodes) are formed on only one side.
  • a substrate having electrodes was formed by forming a distance between the centers (17 mm, 6 columns ⁇ 3 rows) (lower electrode film).
  • a solder material layer was stencil-printed (thickness: 30 ⁇ m) on the electrode using a solder paste 42Sn / 57Bi / Ag alloy (manufactured by Nippon Solder Co., Ltd., product name: PF141-LT7H0) as a solder material.
  • solder material layer one surface of each of the solder receiving layers of the P-type and N-type thermoelectric conversion material chips obtained above is placed on the solder material layer, heated at 180 ° C. for 1 minute, and then cooled. Chips of P-type and N-type thermoelectric conversion materials were placed on the electrodes, respectively. Further, the solder paste is printed as a solder material layer on the other surface of each solder receiving layer of the P-type and N-type thermoelectric conversion material chips (thickness before heating: 50 ⁇ m), and the upper electrode film (lower electrode film) is printed. An electrode film in which electrodes are arranged in a pattern so that a ⁇ -type thermoelectric conversion element can be obtained when bonded together; the substrate, electrode material, thickness, etc.
  • thermoelectric conversion element consisting of 18 pairs of chips of P-type and N-type thermoelectric conversion materials was obtained.
  • a wire as a first heat dissipation member with solder interposed on the cooling surface of the obtained thermoelectric conversion element [Silicon coated wire manufactured by SWITCH SCIENCE] Copper wire, thermal conductivity: 400 W / m ⁇ K, length 10 cm, Connect one end of the thickness: 1.4 mm (cross-sectional area: 1.54 mm 2 ), heat capacity Mw: 0.53 J / K], and bring the other end of the wire to room temperature (25 ° C).
  • thermoelectric conversion module It was connected to the installed housing (material: copper, heat capacity Mh: 685J / K) via solder to form a thermoelectric conversion module.
  • the obtained thermoelectric conversion module was evaluated for electrical resistance, output voltage, maximum output, and temperature difference between the heating surface and the cooling surface at each of the above-mentioned temperatures. The evaluation results are shown in Table 1.
  • Example 2 In Example 1, the thermoelectric conversion module of Example 2 was produced in the same manner as in Example 1 except that the cross-sectional area of the wire was doubled (3.08 mm 2; heat capacity Mw: 1.06 J / K). With respect to the obtained thermoelectric conversion module, the electric resistance, the output voltage and the maximum output, and the temperature difference between the heating surface and the cooling surface were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • thermoelectric conversion module of Comparative Example 1 (a mode of only the thermoelectric conversion element) was produced in the same manner as in Example 1 except that the wire was not connected to the cooling surface and the housing (natural cooling).
  • the obtained thermoelectric conversion module was set to 40 ° C, 50 ° C, 60 ° C, 70 ° C and 80 ° C on a hot plate with respect to the heating surface and heated, and the electrical resistance and output voltage at each temperature. , Maximum output, and temperature difference between the heating surface and the cooling surface were evaluated. The results are shown in Table 1.
  • thermoelectric conversion modules of Examples 1 and 2 having a configuration in which a wire and a housing are thermally connected to one surface of the thermoelectric conversion element are naturally air-cooled and have no specific heat dissipation means. It can be seen that a large temperature difference is applied and a high output can be obtained as compared with the conversion module. Further, it can be seen that the thermoelectric conversion module of Example 2 in which the cross-sectional area of the wire of the thermoelectric conversion module of Example 1 is doubled (the heat capacity is doubled) can obtain a higher output. Furthermore, it can be seen that the output increases more significantly with increasing set temperature.
  • thermoelectric conversion module of the present invention is applied to power generation applications that convert exhaust heat from various combustion furnaces such as factories, waste combustion furnaces, cement combustion furnaces, automobile combustion gas exhaust heat, and electronic equipment exhaust heat into electricity. Can be considered.
  • the heat source when the heat source is applied in a narrow space and the installation space of the thermoelectric conversion module is limited, the heat source can be used effectively and efficiently because the degree of freedom of handling for installing the heat radiating member is high. ..
  • Thermoelectric conversion module 2a First substrate 2b: Second substrate 3a: First electrode 3b: Second electrode 4: P-type thermoelectric element layer 5: N-type thermoelectric element layer 6a, 6b: Bonding material portion 7: Wire 8: End (wire) 9: Housing

Landscapes

  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)

Abstract

L'invention concerne un module de conversion thermoélectrique qui a un degré élevé de liberté par rapport à l'installation d'un élément de dissipation de chaleur et peut être efficacement fourni avec une différence de température même lorsqu'une source de chaleur est dans un espace confiné et l'espace d'installation est limité, ledit module comprenant un élément de conversion thermoélectrique et un premier élément de dissipation de chaleur qui est relié thermiquement à une surface de l'élément de conversion thermoélectrique, le premier élément de dissipation de chaleur étant soit un fil soit une feuille métallique.
PCT/JP2020/036027 2019-09-30 2020-09-24 Module de conversion thermoélectrique WO2021065670A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021551155A JPWO2021065670A1 (fr) 2019-09-30 2020-09-24

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019180230 2019-09-30
JP2019-180230 2019-09-30

Publications (1)

Publication Number Publication Date
WO2021065670A1 true WO2021065670A1 (fr) 2021-04-08

Family

ID=75336455

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/036027 WO2021065670A1 (fr) 2019-09-30 2020-09-24 Module de conversion thermoélectrique

Country Status (2)

Country Link
JP (1) JPWO2021065670A1 (fr)
WO (1) WO2021065670A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113161474A (zh) * 2021-05-06 2021-07-23 先导薄膜材料（广东）有限公司 一种p型碲化铋基合金材料及其制备方法
US20230044413A1 (en) * 2019-12-16 2023-02-09 Lintec Corporation Thermoelectric conversion body, thermoelectric conversion module, and method for manufacturing thermoelectric conversion body

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006204646A (ja) * 2005-01-31 2006-08-10 Yamaha Corp 体温利用発電装置およびそれを用いた人工内耳システム
JP2008205783A (ja) * 2007-02-20 2008-09-04 Matsushita Electric Ind Co Ltd 固体撮像素子の放熱構造
WO2016132533A1 (fr) * 2015-02-20 2016-08-25 富士通株式会社 Module de conversion thermoélectrique, module de capteur, et système de traitement d'informations
WO2018168837A1 (fr) * 2017-03-16 2018-09-20 リンテック株式会社 Matériau d'électrode pour modules de conversion thermoélectrique et module de conversion thermoélectrique l'utilisant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006204646A (ja) * 2005-01-31 2006-08-10 Yamaha Corp 体温利用発電装置およびそれを用いた人工内耳システム
JP2008205783A (ja) * 2007-02-20 2008-09-04 Matsushita Electric Ind Co Ltd 固体撮像素子の放熱構造
WO2016132533A1 (fr) * 2015-02-20 2016-08-25 富士通株式会社 Module de conversion thermoélectrique, module de capteur, et système de traitement d'informations
WO2018168837A1 (fr) * 2017-03-16 2018-09-20 リンテック株式会社 Matériau d'électrode pour modules de conversion thermoélectrique et module de conversion thermoélectrique l'utilisant

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230044413A1 (en) * 2019-12-16 2023-02-09 Lintec Corporation Thermoelectric conversion body, thermoelectric conversion module, and method for manufacturing thermoelectric conversion body
US11974504B2 (en) * 2019-12-16 2024-04-30 Lintec Corporation Thermoelectric conversion body, thermoelectric conversion module, and method for manufacturing thermoelectric conversion body
CN113161474A (zh) * 2021-05-06 2021-07-23 先导薄膜材料（广东）有限公司 一种p型碲化铋基合金材料及其制备方法
CN113161474B (zh) * 2021-05-06 2022-08-05 先导薄膜材料（广东）有限公司 一种p型碲化铋基合金材料及其制备方法

Also Published As

Publication number Publication date
JPWO2021065670A1 (fr) 2021-04-08

Similar Documents

Publication Publication Date Title
JP7245652B2 (ja) フレキシブル熱電変換素子及びその製造方法
JP7406756B2 (ja) 熱電変換モジュール及びその製造方法
WO2021065670A1 (fr) Module de conversion thermoélectrique
JP2019179911A (ja) 熱電変換モジュール
JP7346427B2 (ja) 熱電変換材料のチップの製造方法及びその製造方法により得られたチップを用いた熱電変換モジュールの製造方法
JPWO2019188862A1 (ja) 熱電変換モジュール
JP7207858B2 (ja) 熱電変換モジュール
JP6937452B1 (ja) 熱電変換体、熱電変換モジュール、及び、熱電変換体の製造方法
JP7348192B2 (ja) 半導体素子
WO2021200264A1 (fr) Module de conversion thermoélectrique
WO2021193358A1 (fr) Module de conversion thermoélectrique
WO2020022228A1 (fr) Unité de conversion thermoélectrique
WO2020071424A1 (fr) Puce constituée de matériau de conversion thermoélectrique
WO2021200265A1 (fr) Module de conversion thermoélectrique
WO2020203611A1 (fr) Procédé de formation d'une couche de réception de brasure sur une puce de matériau de conversion thermoélectrique
JP7401361B2 (ja) 熱電変換モジュール
WO2020196709A1 (fr) Procédé pour fabriquer une puce d'un matériau de conversion thermoélectrique
JP7506089B2 (ja) 窓及び窓用スペーサ部材
JP2021158237A (ja) 熱電変換モジュール

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20872562

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021551155

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20872562

Country of ref document: EP

Kind code of ref document: A1