WO2017057259A1 - Module de conversion thermoélectrique et dispositif de conversion thermoélectrique - Google Patents

Module de conversion thermoélectrique et dispositif de conversion thermoélectrique Download PDF

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Publication number
WO2017057259A1
WO2017057259A1 PCT/JP2016/078237 JP2016078237W WO2017057259A1 WO 2017057259 A1 WO2017057259 A1 WO 2017057259A1 JP 2016078237 W JP2016078237 W JP 2016078237W WO 2017057259 A1 WO2017057259 A1 WO 2017057259A1
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WIPO (PCT)
Prior art keywords
thermoelectric conversion
conversion element
wiring board
conversion module
wiring
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PCT/JP2016/078237
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English (en)
Japanese (ja)
Inventor
中田　嘉信
長瀬　敏之
雅人 駒崎
長友　義幸
Original Assignee
三菱マテリアル株式会社
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Priority claimed from JP2016179109A external-priority patent/JP6794732B2/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to EP16851430.5A priority Critical patent/EP3358635B1/fr
Priority to US15/759,658 priority patent/US10573798B2/en
Priority to CN201680056456.7A priority patent/CN108140713B/zh
Priority to KR1020187010595A priority patent/KR20180059830A/ko
Publication of WO2017057259A1 publication Critical patent/WO2017057259A1/fr

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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/81—Structural details of the junction
    • H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered

Definitions

  • the present invention relates to a thermoelectric conversion module in which a plurality of P-type thermoelectric conversion elements and N-type thermoelectric conversion elements are arranged in combination, and a thermoelectric conversion apparatus using the thermoelectric conversion module.
  • thermoelectric conversion module a pair of P-type thermoelectric conversion elements and N-type thermoelectric conversion elements are combined in a connected state with electrodes between a pair of wiring boards, in the order of P, N, P, and N. It is set as the structure electrically connected in series so that it may be arrange
  • thermoelectric conversion module when both ends are connected to a DC power supply and a DC current is passed, the Peltier effect moves heat in each thermoelectric conversion element (in the same direction as the current in the P type and in the opposite direction to the current in the N type). Heat).
  • thermoelectric conversion module for cooling, heating, or power generation.
  • thermoelectric conversion performance of each of the P-type and N-type thermoelectric conversion elements is expressed by a dimensionless figure of merit called ZT, which is a guideline for element selection, but even if the same base material is used, the same use Even in a temperature environment, the same thermoelectric conversion performance is not always obtained in the P-type and the N-type, and adjustment is necessary.
  • ZT dimensionless figure of merit
  • Patent Document 1 an element that is normally formed in a prismatic shape having a square cross section is formed in a rectangular shape in cross section, and in different shapes depending on the carrier concentration of each of P type and N type. It is described to form.
  • Patent Document 2 describes that when a thermoelectric conversion element is soldered to a warped substrate, the thickness of the solder layer is varied according to the distance between the substrate and the element.
  • thermoelectric conversion performance ZT
  • P-type and N-type thermoelectric conversion elements with different base materials. Since the expansion coefficient and the like are different, the damage of the low-strength element is increased (the element breaks preferentially).
  • Patent Document 3 proposes a thermoelectric conversion module in which a stress relaxation layer made of a Cr—Cu alloy is formed between a thermoelectric conversion element and an electrode.
  • the present invention has been made in view of such circumstances, prevents the occurrence of cracks and the like of thermoelectric conversion elements, enables the use of thermoelectric conversion elements made of different materials, and has stable thermoelectric conversion performance.
  • the object is to obtain a thermoelectric conversion module.
  • the thermoelectric conversion module of the present invention is a thermoelectric conversion module comprising a pair of opposing wiring boards and a plurality of thermoelectric conversion elements connected between the wiring boards via the wiring boards,
  • the wiring board includes a ceramic substrate and an electrode portion formed on a surface of the ceramic substrate and connected to the thermoelectric conversion element.
  • the thermoelectric conversion element includes a first thermoelectric conversion element having a large coefficient of thermal expansion;
  • the second thermoelectric conversion element having a small coefficient of thermal expansion, and the length along the facing direction of the wiring board in the first thermoelectric conversion element is the facing direction of the wiring board in the second thermoelectric conversion element
  • the conductive spacer is interposed between at least one of both ends of the first thermoelectric conversion element and the ceramic substrate of the wiring board.
  • thermoelectric conversion element with a small thermal expansion coefficient may be peeled off from the wiring board due to the difference in thermal expansion amount, or the thermoelectric conversion element may crack. May occur. If the thermoelectric conversion element is peeled off or a crack occurs in the thermoelectric conversion element, electricity will not flow or the electrical conductivity will be greatly reduced, making the module inoperable or inoperable. However, there is a problem that the amount of power generation is greatly reduced.
  • thermoelectric conversion element having a large thermal expansion coefficient is made shorter than a thermoelectric conversion element having a small thermal expansion coefficient, thereby suppressing the generation of stress generated in the module due to the difference in thermal expansion between both thermoelectric conversion elements.
  • the conductive spacer interposed between the thermoelectric conversion element having a large thermal expansion coefficient and the wiring board can maintain the electrical conductivity while absorbing the dimensional change of the gap caused by the thermal expansion.
  • thermoelectric conversion module with stable performance can be obtained by aligning the performance of both thermoelectric conversion elements.
  • thermoelectric conversion module of the present invention the difference in length between the first thermoelectric conversion element and the second thermoelectric conversion element is set to a difference equal to or greater than the difference in thermal expansion between the two thermoelectric conversion elements at the highest temperature in the usage environment. Good.
  • the difference in length between the thermoelectric conversion element having a large coefficient of thermal expansion and the thermoelectric conversion element having a small coefficient of thermal expansion may be set according to the difference in thermal expansion of both thermoelectric conversion elements at the maximum temperature in the use environment. Since the difference in thermal expansion is very small, the design is facilitated by setting the difference to be greater than the difference in thermal expansion.
  • the difference in length is preferably 30 ⁇ m or more and 500 ⁇ m or less. If the thickness is less than 30 ⁇ m, when attempting to produce at low cost, the irregularities and undulations on the end face of the thermoelectric element become larger than the difference in thermal expansion coefficient, and there is a risk that power generation performance will be reduced. If it exceeds 500 ⁇ m, a thick conductive spacer is required, and more expensive conductive spacers need to be used in order to ensure thermal conductivity and electrical conductivity between the wiring board and the thermoelectric conversion element. Yes, cost is high.
  • the conductive spacer is composed of a resin powder-coated body coated with metal, an inorganic powder-coated body coated with metal, a conductive resin, graphite, a porous metal, and a carbon nanofiber structure. , Graphene, and a foil or a plate made of aluminum (4N—Al) having a purity of 99.99% by mass or more.
  • the conductive spacer is interposed in each of two locations between both ends of the first thermoelectric conversion element and the wiring board, and the wiring board that is on the low temperature side when used,
  • the conductive spacer between the first thermoelectric conversion element is formed of either a resin powder-coated body coated with metal or a conductive resin, and the wiring substrate that is on a high temperature side when used and the first
  • the conductive spacer between the thermoelectric conversion element is a combination of inorganic powder coated with metal, graphite, porous metal, carbon nanofiber structure, graphene, aluminum having a purity of 99.99% by mass or more (4N ⁇ You may make it form with either the foil or board which consists of Al).
  • conductive spacers made of resin As a base material on the low temperature side and conductive spacers made of metal, carbon, etc. on the high temperature side, heat resistance according to the thermal environment during use can be exhibited. it can.
  • the ceramic substrate of the wiring board is provided with a heat transfer layer made of aluminum having a purity of 99.99 mass% or more on the surface opposite to the side where the electrode portion is provided. Also good.
  • thermoelectric conversion module a heat sink for heat absorption bonded to the heat transfer layer in one wiring board, and a heat sink with a heat sink bonded to the heat transfer layer in the other wiring board. It may be a conversion module. And it can also be set as the thermoelectric conversion apparatus provided with the thermoelectric conversion module with the heat sink, and the liquid cooling type cooler fixed to the said heat sink for thermal radiation.
  • thermoelectric conversion element since it is possible to prevent the occurrence of cracks in the thermoelectric conversion element, separation from the wiring board, etc., there are choices of materials such as combining P-type and N-type thermoelectric conversion elements made of different materials. And a stable thermoelectric conversion module can be obtained by aligning the performance of both thermoelectric conversion elements.
  • FIG. 2 is a cross-sectional plan view taken along the line AA in FIG.
  • FIG. 3 is a cross-sectional plan view taken in the direction of the arrows along line BB in FIG.
  • thermoelectric conversion apparatus which arrange
  • FIG. 2 which shows the thermoelectric conversion module of 4th Embodiment of this invention.
  • FIG. 3 of the fourth embodiment.
  • FIG. 3 of the fourth embodiment.
  • FIG. 3 of the fourth embodiment.
  • FIG. 3 of the fourth embodiment.
  • FIG. 3 of the fourth embodiment It is a longitudinal cross-sectional view which shows the example of the thermoelectric conversion apparatus formed by attaching a heat sink to a thermoelectric conversion module, and installing in a heat source.
  • the thermoelectric conversion module 1 of the first embodiment includes a P-type thermoelectric conversion element 3 and an N-type thermoelectric conversion element 4 between a pair of opposingly arranged wiring boards 2A and 2B. It is the structure arranged in a line (one-dimensional).
  • FIGS. 1 to 3 show an example in which two pairs of P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4 are arranged. It is provided in a line.
  • the P-type thermoelectric conversion element 3 is expressed as “P”
  • the N-type thermoelectric conversion element 4 is expressed as “N”.
  • the thermoelectric conversion module 1 is entirely housed in a case 5 and is attached so as to be interposed between a high temperature side channel 6 through which high temperature gas flows and a low temperature side channel 7 through which cooling water flows.
  • a conversion device 81 is configured.
  • the wiring substrates 2A and 2B are aluminum nitride (AlN), alumina (Al 2 O 3 ), silicon nitride (Si 3 N 4 ), silicon carbide (SiC), carbon plate, diamond thin film substrate formed on a graphite plate, etc.
  • the insulating ceramic substrate 30 having a high thermal conductivity is formed with an electrode portion and the like described later.
  • a silicide-based material As a material of the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4, a silicide-based material, an oxide-based material, a skutterudite (intermetallic compound of transition metal and pnictogen), a half-Whistler, and the like can be used. For example, the combinations shown in Table 1 are used.
  • silicide-based materials that have little impact on the environment and have abundant resource reserves have attracted attention. This embodiment will be described using silicide-based materials.
  • Manganese silicide (MnSi 1.73 ) and magnesium silicide (Mg 2 Si), which are silicide-based materials, are respectively prepared as mother alloys and pulverized to, for example, a particle size of 75 ⁇ m or less by a ball mill, followed by plasma discharge sintering, hot pressing, For example, a disk-shaped or square-plate-shaped bulk material is manufactured by a hot isostatic pressing method, and the thermoelectric conversion elements 3 and 4 are obtained by cutting the bulk material into, for example, a prismatic shape.
  • a metallized layer including any one of nickel, copper, silver, gold, cobalt, molybdenum, and titanium is formed on both end faces of the thermoelectric conversion elements 3 and 4 by plating or sputtering.
  • the metallized layer may be formed through a barrier layer (not shown) made of a single layer made of either nickel or titanium or a laminated structure thereof.
  • the P-type thermoelectric conversion element 3 made of manganese silicide and the N-type thermoelectric conversion element 4 made of magnesium silicide are connected side by side between a pair of wiring boards 2A and 2B made of a ceramic substrate.
  • manganese silicide (P-type thermoelectric conversion element 3) and magnesium silicide (N-type thermoelectric conversion element 4) have different compressive strength, and manganese silicide is, for example, 2300 MPa at room temperature (1200 MPa at 500 ° C.).
  • magnesium silicide is, for example, 1000 MPa at room temperature (260 MPa at 500 ° C.).
  • thermoelectric conversion elements 3 and 4 are linearly arranged, the P-type thermoelectric conversion elements 3 having high strength among the thermoelectric conversion elements 3 and 4 are arranged at both ends of the row. Between the wiring boards 2A and 2B, the P-type thermoelectric conversion element 3, the N-type thermoelectric conversion element 4, the N-type thermoelectric conversion element 4, and the P-type thermoelectric conversion element 3 are arranged in this order from one end (left end in FIG. 1).
  • thermoelectric conversion elements 3 and 4 are formed in a square column shape having a square cross section (for example, 1 mm to 8 mm on one side), for example, and the length (the length along the facing direction of the wiring boards 2A and 2B) is 2 mm. It can be set to 10 mm or less.
  • the manganese silicide constituting the P-type thermoelectric conversion element 3 and the magnesium silicide constituting the N-type thermoelectric conversion element 4 have different coefficients of thermal expansion, so that the lengths of both the thermoelectric conversion elements 3 and 4 (facing the wiring substrates 2A and 2B)
  • the length along the direction) is an N-type thermoelectric conversion element (first thermoelectric conversion element of the present invention) 4 having a large thermal expansion coefficient.
  • the length of the N-type thermoelectric conversion element (second thermoelectric conversion element of the present invention) is 4 The length is set to be shorter than 3.
  • the lengths of the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are set to about 6 mm, depending on the difference in thermal expansion coefficient between the thermoelectric conversion elements 3 and 4 and the use environment temperature. There is a slight difference in length.
  • the thermal expansion coefficient of manganese silicide (P-type thermoelectric conversion element 3) is 10.8 ⁇ 10 ⁇ 6 / K
  • the thermal expansion coefficient of magnesium silicide (N-type thermoelectric conversion element 4) is 12.5 ⁇ 10 ⁇ 6.
  • thermoelectric conversion elements 3 and 4 when the maximum temperature in the use environment of 500 ° C., the thermal expansion difference between the thermoelectric conversion elements 3 and 4 becomes 4.9 [mu] m ⁇ 18.0. Since this difference is extremely small, when determining the specific lengths of the two thermoelectric conversion elements 3 and 4, in order to facilitate the design, a difference in length larger than this thermal expansion difference, for example, 30 ⁇ m to 500 ⁇ m. Difference in length within the range.
  • the length of the N-type thermoelectric conversion element 4 having a large thermal expansion coefficient can be set within a range of 0.917 to 0.995 times the length of the P-type thermoelectric conversion element 3. .
  • thermoelectric conversion elements 3 and 4 are almost the same length at the maximum temperature of the usage environment (in the case of the above-described manganese silicide and magnesium silicide). (4.9 ⁇ m to 18.0 ⁇ m).
  • Two electrode portions 11 having a rectangular shape as viewed are formed.
  • the thermoelectric conversion elements 3 and 4 connected by the electrode section 12 and the electrode section 11 of the first wiring board 2A, one pair of N-type thermoelectric conversion elements 4 and the other pair of P-type thermoelectric elements.
  • the thermoelectric conversion elements 3 and 4 are connected in series between the wiring boards 2A and 2B. Yes.
  • Electrodes 11 and 12 are formed by bonding copper, aluminum, molybdenum, or a laminate of these to the surface of the ceramic substrate 30.
  • the sizes of the electrode portions 11 and 12 are appropriately set according to the size of the thermoelectric conversion elements 3 and 4.
  • the electrode portion 11 is formed in a 5 mm ⁇ 10 mm rectangle, and the electrode portion 12 is formed in a 4.5 mm square shape.
  • the thickness of the electrode portions 11 and 12 can be in the range of 0.05 mm to 2.0 mm, and a thickness of 0.3 mm is preferable.
  • the ceramic substrate 30 of the wiring boards 2A and 2B is formed in a planar shape that can secure a space of 2 mm or more in width between and around the electrode portions 11 and 12, and the thickness is, for example, aluminum nitride, When it is made of alumina, it can be in the range of 0.1 mm to 1.5 mm, and when it is made of silicon nitride, it can be in the range of 0.05 mm to 1.5 mm. As a preferred example, a ceramic plate made of aluminum nitride is used as the ceramic substrate 30 and the size is 30 mm ⁇ 12.5 mm and the thickness is 0.6 mm.
  • the wiring portions 13, 14 ⁇ / b> A, 14 ⁇ / b> B are formed of a wire material made of, for example, copper, aluminum, gold, and silver, and are joined to the surface of the ceramic substrate 30 like the electrode portions 11, 12.
  • the width is in the range of 0.3 mm to 2.0 mm, and the thickness is in the range of 0.05 mm to 4.0 mm.
  • the conductive spacer 15 includes a resin powder bonded body coated with metal or an inorganic powder bonded body coated with metal, conductive resin, graphite, porous metal, carbon nanofiber structure, graphene, purity 99. It is formed of either a foil or a plate made of 99% by mass or more of aluminum (4N—Al), and one of these or two or more of them having a laminated structure is formed into a sheet shape.
  • the resin powder coated with metal is a powder (coated resin powder) obtained by coating a resin powder such as an acrylic resin with a metal such as silver, gold, aluminum, or copper by electroless plating or sputtering.
  • the resin powder may have a particle size of 2 ⁇ m to 10 ⁇ m, and a coating amount of the metal may be 40% by mass to 90% by mass.
  • the conductive resin 15 can be formed by dispersing the coating resin powder in a solvent such as water, forming a paste, applying the paste, and drying.
  • the conductive spacer 15 can be formed by applying the coating thickness to 25 to 500 nm and heating at 100 to 180 ° C. for 10 to 60 minutes.
  • SiO 2 powder SiO 2 powder, ceramic powder, hollow silica powder, hollow ceramic powder, hollow glass powder and the like can be used.
  • the hollow silica powder is mainly composed of silica (SiO 2 ), has an average particle diameter of 5 to 120 nm, a shell thickness of 1 to 35 nm, and the number of silanol groups ( ⁇ Si—OH groups) per unit surface area.
  • the core is made of an organic polymer
  • the shell is made of silica / core powder, and then the core is removed.
  • the core organic polymer particles have an average particle size of 5 produced by soap-free polymerization in which a polymerizable monomer is a main component and an ionic comonomer is copolymerized at a molar ratio of 150: 1 to 2: 1. Particles of ⁇ 90 nm.
  • a cationic water-soluble polymer and a nonionic water-soluble polymer are added to the liquid containing the core particles, and the liquid containing the core particles is replaced with alcohol from water, and then alkoxysilane, water, and a basic substance are added. Then, the core particles are coated with silica, and a powder comprising core-shell particles having an average particle diameter of 5 to 120 nm and a silica shell thickness of 1 to 35 nm is manufactured, and then the core is removed.
  • Silax registered trademark
  • This Sirinax has a particle size of 80 to 130 nm and a bulk density of 0.03 to 0.07 g / ml.
  • the hollow silica powder is used in a state in which a metal such as silver, gold, aluminum, or copper is coated on the surface by electroless plating or sputtering.
  • the coating amount of the metal is 40% by mass to 90% by mass with respect to the total particle mass.
  • the conductive spacer 15 can be formed by drying the paste containing the hollow silica powder (coated hollow silica powder) coated with this metal.
  • a paste can be obtained by dispersing the hollow silica powder coated with metal (metal-coated hollow silica powder) in water so that the content is 10% by mass to 25% by mass.
  • an aqueous dispersant may be added.
  • the aqueous dispersant amine-based, phosphoric acid-based, sulphonic acid-based and citric acid can be used, and the addition amount is preferably 1% by mass to 10% by mass with respect to the whole paste.
  • the conductive spacer 15 made of a composite of coated hollow silica powder can be formed by applying this paste in a thickness of 30 ⁇ m to 500 ⁇ m and drying at 100 ° C. to 180 ° C. for 10 minutes to 60 minutes.
  • silver nanocolloid particles can be added to the paste.
  • the silver nanocolloid particles have a particle size of 5 nm to 40 nm and the addition amount is 0.2 mass% to 1.4 mass% with respect to the whole paste.
  • Porous metal is a porous metal including a large number of pores, and the diameter of the pores is generally from several ⁇ m to several cm.
  • the porous metal include foam metal and metal sponge.
  • the foam metal is a metal having a three-dimensional network shape having a large number of bubbles produced by utilizing the gas foaming phenomenon, and is also referred to as a metal foam.
  • the metal foam coated on the skeleton surface of the porous resin, and then the resin is burned out to form a three-dimensional network metal skeleton is included in the foam metal.
  • the metal sponge is composed of a metal wire that is continuous in a three-dimensional network shape, and has a relatively high porosity among porous metals.
  • the carbon nanofiber structure is a nonwoven fabric in which carbon nanofibers are formed in a random network.
  • Graphene is a foil-like structure in which a six-membered network of carbon spreads in a plane, and graphite is a single-layer graphene layered by several tens of layers. This is also called graphene for convenience. There is. A dispersion liquid in which this graphene is dispersed in isopropyl alcohol so as to be 5% by mass is applied and dried to form a conductive spacer.
  • Carbon nanotubes are rolled up graphene.
  • This carbon nanotube has a single-layer structure (one layer constituting the tube) and a multi-layer structure.
  • Carbon nanofibers are a kind of multi-wall carbon nanotubes, and have a relatively large size with a diameter of 100 nm and a length of 100 ⁇ m. Is the feature.
  • a conductive spacer serving as a carbon nanofiber structure is formed by applying and drying a liquid in which carbon nanofibers are dispersed in water to 2% by mass.
  • thermoelectric conversion elements 3 and 4 are thermally expanded and contracted in these conductive spacers 15 in a use environment, so that the thermal expansion and contraction of the thermoelectric conversion elements 3 and 4 does not occur due to the thermal expansion and contraction.
  • Deformability elastic deformability or plastic deformability to the extent that can be absorbed.
  • These conductive spacers 15 include a resin powder bonded body coated with metal or an inorganic powder bonded body coated with metal, porous metal such as foam metal and metal sponge, aluminum having a purity of 99.99% by mass or more (4N).
  • the foil or plate made of -Al) is bonded to the thermoelectric conversion element and the wiring board by brazing using silver brazing or silver paste.
  • the conductive resin is bonded to the thermoelectric conversion element and the wiring board by an adhesive.
  • carbon nanofiber structures, graphene, and graphite are sandwiched between the thermoelectric conversion element and the wiring board, and are bonded to the thermoelectric conversion element and the wiring board by applying physical pressure and physically bonding. Is done.
  • thermoelectric conversion element with a nickel metallization layer
  • carbon nanofibers, graphene, and carbon sheets are pressure-bonded before drying, and dried at 100 ° C. to join the thermoelectric conversion element and the wiring board. Is done.
  • the conductive spacer 15 provided on the low temperature side (the second wiring board 2B side) is coated with the above-described paste of silver coat powder and silver paste. It is formed by drying.
  • the conductive spacer 15 provided on the high temperature side (the first wiring board 2A side) uses an aluminum foil having a thickness of 150 ⁇ m and a purity of 99.99% by mass or more, and the electrode part 11 and the N-type thermoelectric conversion element 4 are silver brazing. Join with etc.
  • the area of the conductive spacer 15 is the same as the area of the cross section of the N-type thermoelectric conversion element 4.
  • the area of the conductive spacer 15 can be set to 1 to 1.27 times the area of the cross section of the thermoelectric conversion elements 3 and 4.
  • thermoelectric conversion element 3 is directly connected between the electrode portions 11 and 12 of the both wiring boards 2A and 2B, and the N-type thermoelectric conversion element 4 is connected via the conductive spacer 15, respectively.
  • the thermoelectric conversion elements 3 and 4 are connected in series between the external wiring portions 14 ⁇ / b> A and 14 ⁇ / b> B by using a bonding material such as a silver solder or a bonding material using silver paste.
  • a silver paste containing silver powder having a particle size of 0.05 ⁇ m to 100 ⁇ m, a resin, and a solvent is used as the bonding material using the silver paste.
  • thermoelectric conversion elements 3 and 4 are joined and integrated between the wiring boards 2A and 2B while forming a sintered body of silver.
  • thermoelectric conversion elements 3 and 4 joined and integrated between the wiring boards 2A and 2B are hermetically accommodated in a case 5 formed of stainless steel or the like, and the inside is kept in a vacuum or reduced pressure state. Then, the thermoelectric conversion module 1 is produced and packaged. Note that the case 5 is not necessarily required, and the case 5 may not be provided.
  • thermoelectric conversion elements 3 and 4 At the time of packaging, a compressive load acts on each of the thermoelectric conversion elements 3 and 4, but in this embodiment, the strength is high because the P-type thermoelectric conversion elements 3 having high strength are arranged at both ends of the row.
  • the thermoelectric conversion element 3 can support the load at both end positions of the array, reduce the load of the load on the thermoelectric conversion element 4 having low strength, and prevent the occurrence of cracks and the like.
  • the external wiring portions 14 ⁇ / b> A and 14 ⁇ / b> B are drawn out to the outside in an insulated state with respect to the case 5.
  • thermoelectric conversion module 1 configured in this way is an exhaust gas of an internal combustion engine.
  • the high-temperature side flow path 6 through which a high-temperature fluid such as circulates is contacted, and the low-temperature side flow path 7 through which cooling water circulates as a heat medium is in contact with the other wiring board (second wiring board) 2B side.
  • an electromotive force corresponding to the temperature difference between the wiring boards 2A and 2B is generated in each thermoelectric conversion element 3 and 4, and the thermoelectric conversion elements 3 and 4 are connected between the external wiring portions 14A and 14B at both ends of the array.
  • a heat sink (heat sink for heat absorption) 8 having rod-like heat absorption fins 8a is provided in the high temperature side flow path 6, and an elastic member 9 such as a spring for pressing the heat absorption fins toward the first wiring board 2A.
  • the thermoelectric conversion device 81 is configured by being provided.
  • thermoelectric conversion elements 3 and 4 there is a difference in thermal expansion between the thermoelectric conversion elements 3 and 4, but the length of the N-type thermoelectric conversion element 4 having a large thermal expansion coefficient is longer than the length of the P-type thermoelectric conversion element 3 in advance. Since the length of the thermoelectric conversion element is set to be shorter than the thermal expansion difference, the difference in length between the two thermoelectric conversion elements is small even at the operating environment temperature, but the length of the N-type thermoelectric conversion element 4 is reduced. Is shorter than the length of the P-type thermoelectric conversion element 3. In addition, since the conductive spacer 15 is interposed between the N-type thermoelectric conversion element 4 and the wiring boards 2A and 2B, the difference in length due to thermal expansion is reduced by the deformation of the conductive spacer 15. Absorbed.
  • thermoelectric conversion element 3 it is possible to suppress the tensile stress due to the thermal expansion of the P-type thermoelectric conversion element 3 from acting on the N-type thermoelectric conversion element 4 having a low strength, and cracks in the thermoelectric conversion elements 3 and 4 and the wiring board 2A, Generation
  • thermoelectric conversion element 4 In the first embodiment shown in FIG. 1, the conductive spacers 15 are interposed at both the two ends between the both ends of the thermoelectric conversion element 4 and the two wiring boards 2A and 2B, respectively, but the second embodiment shown in FIG. Of the thermoelectric conversion element 4 only between one end of the thermoelectric conversion element 4 and the first wiring board 2A as in the thermoelectric conversion module 10 of the embodiment, or like the thermoelectric conversion module 20 of the third embodiment shown in FIG. It is good also as a structure interposed only between the other front-end
  • FIGS. 4 and 5 the same reference numerals are assigned to the same elements as those in the first embodiment to simplify the description.
  • thermoelectric conversion module the structure of the high temperature side flow path 6, the low temperature side flow path 7, the heat sink 8, and the like is common, so that the thermoelectric conversion device is denoted by the same reference numeral 81. did.
  • the conductive spacer 15 only needs to be interposed in at least one of the two locations between both ends of the thermoelectric conversion element 4 and the wiring boards 2A and 2B.
  • a conductive spacer having a base material of metal, carbon, or the like is preferable.
  • the conductive spacers 15 are provided at both ends of the thermoelectric conversion element 4, it is preferable to interpose a high-temperature conductive spacer on the high temperature side and a low-temperature conductive spacer on the low temperature side of the element.
  • conductive spacers of the same material may be interposed at both ends of the thermoelectric conversion element 4.
  • thermoelectric conversion module 21 shows a thermoelectric conversion module 21 according to a fourth embodiment in which P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4 are arranged in a planar shape (two-dimensional).
  • the longitudinal sectional structure is substantially the same as that of FIG. 1, and will be described with reference to FIG. 1 as necessary.
  • thermoelectric conversion module 21 a total of eight pairs of P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4 are provided between a pair of wiring boards 22A and 22B, and a square plane of 4 columns ⁇ 4 rows. It is supposed to be arranged.
  • the P-type thermoelectric conversion elements 3 having high strength are arranged at the four corners of the square.
  • the P-type thermoelectric conversion elements 3 are collectively arranged at the center of the square, but if the P-type thermoelectric conversion elements 3 are arranged at the four corners, the center Is not limited to the arrangement of this figure.
  • the first wiring board 22A of both wiring boards 22A and 22B is connected to each of the pair of adjacent P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4 as shown in FIG.
  • Eight electrode portions 11 having a rectangular shape in plan view are formed.
  • the second wiring substrate 22B as shown in FIG. 7, eight electrode portions 12 having a square shape in plan view for connecting one P-type thermoelectric conversion element 3 or N-type thermoelectric conversion element 4 alone are formed.
  • four electrode parts 23 having a rectangular shape in plan view are formed to connect two P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4 that are different from the first wiring board 22A. .
  • the eight electrode parts 12 having a square shape in plan view six electrode parts 12 are paired and connected obliquely by the internal wiring part 24, and the electrodes of the first wiring board 22A
  • the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are connected in a combination different from the pair of thermoelectric conversion elements that are connected by the unit 11.
  • thermoelectric conversion elements 3 and 4 are connected between the wiring substrates 22A and 22B.
  • thermoelectric conversion elements 3 and 4 are connected in series between the external wiring portions 25A and 25B.
  • both the wiring boards 22A and 22B are formed in, for example, a 30 mm square when the thermoelectric conversion elements 3 and 4 have the same dimensions as in the first embodiment. Further, if the P-type thermoelectric conversion elements 3 are arranged at the four corners, the specific connection form such as the shape of each electrode part, the connection order, etc. is not limited to the illustrated example.
  • the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are formed of the same material as in the first embodiment. For this reason, the length of the N-type thermoelectric conversion element (first thermoelectric conversion element) 4 having a large thermal expansion coefficient is set to be shorter than the length of the P-type thermoelectric conversion element (second thermoelectric conversion element) 3.
  • a conductive spacer 15 (approximately in FIGS. 6 and 7, refer to FIG. 1) is provided between the thermoelectric conversion element 4 and the electrode portion 11 so as to fill the gap. Yes.
  • the conductive spacer 15 may be interposed between the N-type thermoelectric conversion element 4 and the other electrode portion 12, or both ends of the N-type thermoelectric conversion element 4 and both You may interpose between electrode parts 11 and 12.
  • thermoelectric conversion module 21 is configured by being hermetically accommodated in the case 5 formed by the above (see FIG. 1) and holding the inside in a vacuum or a reduced pressure state.
  • the external high-temperature channel 6 is connected to one wiring board (first wiring board) 22A side of both wiring boards 22A and 22B, and the other wiring board (second wiring board).
  • first wiring board first wiring board
  • second wiring board second wiring board
  • the high-strength P-type thermoelectric conversion element 3 supports loads at the four corners, and reduces the load on the low-strength N-type thermoelectric conversion element 4. The occurrence of such cracks can be prevented.
  • the length of the N-type thermoelectric conversion element 4 having a large thermal expansion coefficient is set to be shorter than the length of the P-type thermoelectric conversion element 3, the thermal expansion and contraction of both thermoelectric conversion elements 3 and 4 in the operating temperature environment.
  • thermoelectric conversion module As shown in FIG. 8, a structure in which a heat sink is joined to a thermoelectric conversion module can be used.
  • the thermoelectric conversion module 50 is made of aluminum or an aluminum alloy (preferably aluminum having a purity of 99.99% by mass or more) on the surface opposite to the electrode portions 11 and 12 of the ceramic substrate 30 in the wiring substrates 2A and 2B on both sides thereof.
  • the heat transfer layer 51 is joined.
  • the thickness of the heat transfer layer 51 is preferably about the same as that of the electrode portions 11 and 12.
  • the heat sinks 60 and 61 are made of aluminum or aluminum alloy, copper or copper alloy, aluminum silicon carbide composite (AlSiC) formed by impregnating aluminum or aluminum alloy in a porous body made of silicon carbide, or the like.
  • the heat sink may be provided with pin-shaped fins 62 or may be a flat plate without the fins 62.
  • a flat heat sink (heat absorption heat sink) 60 is provided on the high temperature side
  • a heat sink (heat dissipation heat sink) 61 having pin-like fins 62 is provided on the low temperature side.
  • the thickness of the top plate portion 61a can be set to 0.5 mm to 8 mm, respectively.
  • the high-temperature side is fixed in a state where a flat heat sink 60 is in contact with a heat source 65 such as a furnace wall, and the low-temperature side is a heat sink having fins 62 in a liquid-cooled cooler 70 through which cooling water or the like can flow.
  • 61 is fixed to constitute the thermoelectric converter 82.
  • the liquid cooling cooler 70 has a flow path 71 formed therein, and is fixed in a state where the top plate portion 61 a of the heat sink 61 is in contact with the periphery of the opening 72 on the side wall, and the fins 62 are connected to the flow path 71 from the opening 72. It is arranged in the inserted state.
  • Reference numeral 76 denotes a resin seal member interposed between the liquid cooling type cooler 70 and the top plate portion 61 a of the heat sink 61. In FIG. 8, the case 5 used in the embodiment shown in FIG. 1 is not used.
  • the heat transfer layer 51 and the heat sinks 60 and 61 are vacuum brazed using an Al—Si brazing material, brazing in a nitrogen atmosphere using a flux, or flux using an Al brazing material containing Mg. Bonded by means of brazing or solid phase diffusion bonding.
  • a prismatic P-type thermoelectric conversion element made of manganese silicide and a prismatic N-type thermoelectric conversion element made of magnesium silicide were produced.
  • the bottom surface is 4 mm ⁇ 4 mm, the length is 7 mm, 5 mm, or 3.5 mm for the P-type thermoelectric conversion element, and the difference in length between the two thermoelectric conversion elements is the dimension shown in Table 2, so that the N-type thermoelectric conversion element The length of was shortened.
  • thermoelectric conversion module was prepared by combining eight each of these P-type thermoelectric conversion elements and N-type thermoelectric conversion elements.
  • As the ceramic substrate of the wiring substrate aluminum nitride having a thickness of 0.6 mm was used, and copper was used as the electrode portion.
  • the conductive spacers (high temperature side spacers, low temperature side spacers) and thicknesses were as shown in Table 2.
  • the “graphite sheet” uses the “PGS” graphite sheet S type manufactured by Panasonic Corporation
  • the “carbon nanofiber structure” uses the carbon nanofiber nonwoven fabric manufactured by Nisshinbo Co., Ltd.
  • the “porous aluminum” An aluminum foam metal having a porosity of 85% was used
  • a “graphene sheet” was a graphene flower sheet manufactured by Incubation Alliance.
  • the “silver coated hollow silica” used was a silver coated silica gel (registered trademark) manufactured by Nittetsu Mining Co., Ltd.
  • the silver coating was performed by an electroless plating method, and the silver coating amount was 90% silver: 10% hollow silica (mass ratio).
  • silver nano colloid A-1 As the “nano silver particles”, silver nano colloid A-1 manufactured by Mitsubishi Materials Corporation was used.
  • thermoelectric conversion module For the obtained thermoelectric conversion module, the high temperature side is heated by an electric heater between 450 ° C and 300 ° C in 30-minute cycles, and the temperature is repeatedly lowered and the low temperature side is kept at 60 ° C by a chiller (cooler). Then, a cycle test for 48 hours was conducted, and the power generation performance and the occurrence rate of defects such as cracks and peeling of the thermoelectric conversion elements were investigated.
  • the power generation performance was defined as the amount of power at the maximum temperature difference of 390 ° C. in the last cycle after 48 hours.
  • the amount of electric power was measured by measuring the open circuit voltage and short circuit current of the thermoelectric conversion module, and multiplying by half of the open circuit voltage and half of the short circuit current.
  • the element defect occurrence rate caused peeling (including partial peeling) of the elements on the high temperature side and the low temperature side using an ultrasonic image measuring instrument (INSIGHT-300 manufactured by Insight Co., Ltd.) after the cycle test. The ratio of the element was evaluated. When the peeling rate was 10% or more, it was judged as a defect.
  • thermoelectric conversion module having a high power generation performance and a low element defect occurrence rate can be obtained when the difference between the two is 30 ⁇ m or more.
  • the electrode portion is formed on the surface of the ceramic substrate, and the conductive spacer is interposed between the electrode portion and the thermoelectric conversion element, but the electrode portion is formed on the ceramic substrate via the conductive spacer, You may join a thermoelectric conversion element to the electrode part.
  • thermoelectric conversion elements When arranging both thermoelectric conversion elements in a planar shape, not only an arrangement that is a square in a plan view but also an arrangement that is a rectangle, a circle, or the like in a plan view. In that case, it is only necessary to arrange thermoelectric conversion elements having high strength at a plurality of locations at appropriate intervals in the circumferential direction in the peripheral portion, and it is preferable to arrange them uniformly.
  • each thermoelectric conversion element is also a square, it may be formed in a rectangle, a circle, or the like.
  • both wiring boards are brought into contact with the high temperature side flow path or the low temperature side flow path, they are not necessarily limited to the flow path configuration, and may be anything that contacts the heat source and the cooling medium.
  • the thermal expansion coefficient of the N-type thermoelectric conversion element is larger than that of the P-type thermoelectric conversion element.
  • the thermal expansion coefficient of the P-type thermoelectric conversion element is larger than that of the N-type thermoelectric conversion element.
  • the P-type thermoelectric conversion element is the first thermoelectric conversion element, and the length thereof is shorter than that of the N-type thermoelectric conversion element (second thermoelectric conversion element).
  • a conductive spacer may be interposed between the two.
  • Thermoelectric conversion module can be used for a cooling device, a heating device, or a power generation device.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)

Abstract

La présente invention concerne un module de conversion thermoélectrique (1), pour lequel une pluralité d'éléments de conversion thermoélectriques de type p (3) et d'éléments de conversion thermoélectriques de type N (4), qui sont combinés en paires, sont raccordés en série les uns aux autres entre une paire de substrats de câblage opposés (2A, 2B) par le biais des substrats de câblage (2A, 2B). Des parties d'électrode (11, 12), auxquelles sont raccordés les éléments de conversion thermoélectrique (3, 4), sont formées sur des surfaces de substrats en céramique (30) des substrats de câblage (2A, 2B). Parmi les éléments de conversion thermoélectrique, l'élément de conversion thermoélectrique ayant un coefficient de dilatation thermique plus important possède la longueur, dans une direction dans laquelle les substrats de câblage sont orientés les uns vers les autres, qui est inférieure à la longueur, dans une direction dans laquelle les substrats de câblage sont orientés les uns vers les autres, de l'élément de conversion thermoélectrique ayant un coefficient de dilatation thermique plus petit. Une entretoise conductrice (15) est intercalée entre au moins l'une des deux extrémités de l'élément de conversion thermoélectrique présentant un coefficient de dilatation thermique plus important et le substrat en céramique du substrat de câblage.
PCT/JP2016/078237 2015-09-28 2016-09-26 Module de conversion thermoélectrique et dispositif de conversion thermoélectrique WO2017057259A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP16851430.5A EP3358635B1 (fr) 2015-09-28 2016-09-26 Module de conversion thermoélectrique et dispositif de conversion thermoélectrique
US15/759,658 US10573798B2 (en) 2015-09-28 2016-09-26 Thermoelectric conversion module and thermoelectric conversion device
CN201680056456.7A CN108140713B (zh) 2015-09-28 2016-09-26 热电转换模块及热电转换装置
KR1020187010595A KR20180059830A (ko) 2015-09-28 2016-09-26 열전 변환 모듈 및 열전 변환 장치

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JP2015-190273 2015-09-28
JP2015190273 2015-09-28
JP2016179109A JP6794732B2 (ja) 2015-09-28 2016-09-14 熱電変換モジュール及び熱電変換装置
JP2016-179109 2016-09-14

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CN108172681A (zh) * 2017-12-28 2018-06-15 浙江大学 一种三维集成中基于纳米材料的热电转换系统
WO2019203392A1 (fr) * 2018-04-16 2019-10-24 한국전력공사 Matériau d'électrode pour module de génération de puissance thermoélectrique et son procédé de fabrication
EP3855518A3 (fr) * 2020-01-27 2021-08-18 Hitachi, Ltd. Module de conversion thermoélectrique
US11588089B2 (en) * 2019-07-25 2023-02-21 Ibiden Co., Ltd. Printed wiring board having thermoelectric emlement accommodatred therein

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CN108172681A (zh) * 2017-12-28 2018-06-15 浙江大学 一种三维集成中基于纳米材料的热电转换系统
CN108172681B (zh) * 2017-12-28 2019-10-29 浙江大学 一种三维集成中基于纳米材料的热电转换系统
WO2019203392A1 (fr) * 2018-04-16 2019-10-24 한국전력공사 Matériau d'électrode pour module de génération de puissance thermoélectrique et son procédé de fabrication
US11588089B2 (en) * 2019-07-25 2023-02-21 Ibiden Co., Ltd. Printed wiring board having thermoelectric emlement accommodatred therein
EP3855518A3 (fr) * 2020-01-27 2021-08-18 Hitachi, Ltd. Module de conversion thermoélectrique

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