+

WO2016013366A1 - Module de conversion thermoélectrique et son procédé de fabrication - Google Patents

Module de conversion thermoélectrique et son procédé de fabrication Download PDF

Info

Publication number
WO2016013366A1
WO2016013366A1 PCT/JP2015/069070 JP2015069070W WO2016013366A1 WO 2016013366 A1 WO2016013366 A1 WO 2016013366A1 JP 2015069070 W JP2015069070 W JP 2015069070W WO 2016013366 A1 WO2016013366 A1 WO 2016013366A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoelectric conversion
temperature side
conversion module
metal film
ceramic substrate
Prior art date
Application number
PCT/JP2015/069070
Other languages
English (en)
Japanese (ja)
Inventor
悦子 高根
藤原　伸一
知丈 東平
石島　善三
孝広 地主
征央 根岸
Original Assignee
日立化成株式会社
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 日立化成株式会社 filed Critical 日立化成株式会社
Publication of WO2016013366A1 publication Critical patent/WO2016013366A1/fr

Links

Images

Classifications

    • 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
    • H10N10/13—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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions

Definitions

  • the present invention relates to the structure of a thermoelectric conversion module that converts thermal energy into electrical energy, and more particularly to a thermoelectric conversion module in which a thermoelectric element is installed on a ceramic substrate having metal films on both sides.
  • thermoelectric conversion module which converts thermal energy into electrical energy using the Seebeck effect, has features such as no drive, simple structure, and maintenance-free, but it has been characterized by low energy conversion efficiency. It has been used only in limited products such as power supplies. However, in order to realize an environment-friendly society, attention is focused on a method of recovering waste heat as thermal energy, and the development of industrial furnaces such as blast furnaces and incinerators, automobile-related products, etc. is being studied. From such a background, the thermoelectric conversion module is desired to improve the durability, improve the conversion efficiency, and reduce the cost.
  • thermoelectric conversion module used by being attached to piping of an industrial furnace such as a blast furnace or an incinerator or an exhaust pipe of a car is used in a high temperature environment of 300 to 600.degree.
  • an industrial furnace such as a blast furnace or an incinerator or an exhaust pipe of a car
  • stress is generated at the junction due to the thermal expansion difference between the thermoelectric conversion element and the electrode, and the fracture in the junction or the thermoelectric conversion element occurs.
  • the stress generated at the joint portion becomes higher as the use environment temperature is higher or as the difference between the linear expansion coefficients of the thermoelectric conversion element and the joint material and the electrode is larger.
  • the module may be accompanied by vibration or impact, and there is a concern that vibration or impact is added to the thermal stress generated in the module to promote destruction in the joint portion or the thermoelectric conversion element.
  • thermoelectric conversion module using a circuit board in which a metal plate (electrode metal plate and metal plate) is joined with an Ag-Cu brazing material on both sides of a ceramic substrate is a thermoelectric conversion element or electrode junction during operation.
  • the thermoelectric conversion element and the electrode metal plate of the ceramic substrate are joined using a brazing material having a melting point higher than the operating temperature of the thermoelectric conversion module in order to suppress the breakage of the part and the thermal stress, and the electrode metal plate and the metal plate
  • a thermoelectric conversion module having a structure in which the thickness ratio ⁇ (electrode metal plate thickness / metal plate thickness) ⁇ 100 (%) ⁇ is 50% or more and 200% or less is described.
  • thermoelectric conversion module which is expected to be used in a high temperature environment of 300 ° C. or more, the influence of thermal stress becomes remarkable, so a thermoelectric conversion module structure having more excellent stress relaxation properties is essential.
  • thermoelectric conversion element made of a half-Heusler material that can be used below with an active metal brazing material (Ag-Cu-Ti or Ag-Cu-Zr), and joining ceramic substrates for high temperature side and low temperature side
  • a thermoelectric conversion module is described which is characterized in that
  • Patent Document 3 describes a thermoelectric conversion module in which a notch is formed in an electrode layer in order to relieve stress generated in the thermoelectric conversion element when the module is in operation.
  • the cutaway portion in the electrode layer, the cutaway portion must be formed in advance on the electrode, and processing on the electrode layer is required, resulting in an increase in cost and breakage of the electrode layer portion. There is a problem that there is a risk of
  • thermoelectric conversion element If the linear expansion coefficients of the thermoelectric conversion element, the bonding material, and the electrode are different, the stress is concentrated on the thermoelectric conversion element and the electrode portion due to the thermal load at the time of joining and the temperature change at the time of operation. There was a problem that it occurred and was damaged.
  • the present invention has been made in view of the problems of the prior art as described above, and an object thereof is a stress relaxation type capable of relieving stress generated in the thermoelectric conversion element and the electrode portion during operation of the thermoelectric conversion module. It is providing a thermoelectric conversion module.
  • the present invention adopts the configuration described in the claims.
  • the present invention includes a plurality of means for solving the above problems, but if one example of the thermoelectric conversion module of the present invention is mentioned, a ceramic substrate having metal films on both sides is used on the high temperature side and the low temperature side.
  • Type and N-type thermoelectric conversion elements are joined in a state of being sandwiched between the ceramic substrates, and some or all of a plurality of P-type thermoelectric conversion elements and a plurality of N-type thermoelectric conversion elements are electrically connected in series
  • the P-type thermoelectric conversion element and the N-type thermoelectric conversion element are paired, and slits are formed in the ceramic substrate only on the low temperature side or only on the high temperature side or both the low temperature side and the high temperature side It is characterized by being.
  • thermoelectric conversion module of this invention the step of installing the high temperature side ceramic substrate which has a metal film containing an electrode metal film on both sides on a support jig, The electrode metal of the said ceramic substrate Installing a bonding material and P-type and N-type thermoelectric conversion elements on the film; and installing a low temperature ceramic substrate having a metal film including the bonding material and an electrode metal film on both surfaces on the thermoelectric conversion element Heating, and collectively bonding the electrode metal film and the thermoelectric conversion element, the high temperature side ceramic substrate only, or the low temperature side ceramic substrate Forming a slit in the ceramic substrate on only the high temperature side and the high temperature side and the low temperature side.
  • thermoelectric conversion module of the present invention a high temperature side ceramic substrate having a metal film including an electrode metal film on both sides on a support jig, a bonding material, and a P type Installing an N-type thermoelectric conversion element, pressing with a pressurizing jig and heating, and collectively bonding the electrode metal film and the thermoelectric conversion element with a bonding material;
  • a step of installing a low temperature side ceramic substrate having a metal film including a bonding material and an electrode metal film on the conversion element, pressing with a pressure jig and heating are carried out, The step of collectively bonding the thermoelectric conversion elements with a bonding material, the ceramic substrate on the high temperature side only, the ceramic substrate on the low temperature side only, or the ceramic substrate on both the high temperature side and the low temperature side In which and a step of forming the door.
  • thermoelectric conversion module it is possible to relieve the stress generated in the thermoelectric conversion element and the electrode portion when the thermoelectric conversion module is in operation.
  • the module operation is achieved by forming a slit in the ceramic substrate of only the low temperature side or only the high temperature side, or both the low temperature side and the high temperature side, with the P type thermoelectric conversion element and the N type thermoelectric conversion element as one pair.
  • the structure is capable of relieving stress generated in the thermoelectric conversion element and the electrode portion at the time of
  • FIG. 1 is a side view of the vicinity of elements of a stress relaxation type thermoelectric conversion module according to a first embodiment of the present invention.
  • 1 is a thermoelectric conversion module element assembly
  • 51 is a P-type thermoelectric conversion element
  • 52 is an N-type thermoelectric conversion element
  • 21 is a metal film
  • 22 is a ceramic substrate
  • 23 is an electrode metal film
  • 31 is a bonding material.
  • the P-type thermoelectric conversion element 51 and the N-type thermoelectric conversion element 52 have metallizations 35 on their bonding surfaces, and are bonded to the electrode metal film 23 through the bonding material 31.
  • the P-type thermoelectric conversion element 51 and the N-type thermoelectric conversion element 52 are silicon-germanium type, iron-silicon type, bismuth-tellurium type, magnesium-silicon type, manganese-silicon type, lead-tellurium type, cobalt-antimony type, It is desirable to use a thermoelectric conversion element made of any combination of bismuth-antimony, Heusler alloy, half-Heusler alloy, and the like.
  • the P-type thermoelectric conversion element 51 will be described as a manganese-silicon element
  • the N-type thermoelectric conversion element 52 as a magnesium-silicon element.
  • metal films of nickel, aluminum, titanium, molybdenum, tungsten, palladium, chromium, gold, silver, tin, etc. are formed on the surfaces (bonding surfaces) of the P-type thermoelectric conversion element 51 and the N-type thermoelectric conversion element 52 as metallization. May be formed.
  • the metallization 35 may be any method as long as it is a plating method, an aerosol deposition method, a thermal spraying method, a sputtering method, an evaporation method, an ion plating method, a simultaneous integral sintering method, or the like.
  • the metallization 35 is described below as nickel.
  • the ceramic substrate having a metal film on both sides is preferably composed of a ceramic substrate containing as a main component at least one selected from aluminum nitride, silicon nitride and alumina excellent in thermal conductivity.
  • the ceramic substrate is made of alumina.
  • the metal film 21 and the electrode metal film 23 bonded to the ceramic substrate 22 are desirably made of 90% by mass or more of Cu, which has high electric conductivity and high thermal conductivity and is suitable as an electrode member.
  • the electrode metal film 23 bonded to the ceramic substrate is a patterned metal film
  • the metal film 21 is a solid metal film, or a metal film patterned in the same shape as the electrode metal film 23.
  • the solid metal film 21 and the electrode metal film 23 will be described.
  • the bonding material 31 contains aluminum, nickel, tin, copper, germanium, magnesium, gold, silver, silicon, indium, lead, bismuth, tellurium, or any of these metals as a main component, titanium, zirconium and hafnium. It is desirable to use an active metal brazing material containing 0.1 to 10% by mass of at least one active metal selected from Hereinafter, the bonding material 31 will be described as an Ag-Cu-Ti brazing material.
  • the P-type thermoelectric conversion element 51, the N-type thermoelectric conversion element 52, and the electrode metal film 23 are joined at the upper end and the lower end via the metallization 35 and the bonding material 31.
  • the manganese-silicon element which is the P-type thermoelectric conversion element 51
  • the magnesium-silicon element which is the N-type thermoelectric conversion element 52
  • thermoelectric conversion module suppresses the softening of the brazing material during module operation by using a brazing material (melting point 780 ° C.) having a melting point higher than the operating temperature of the thermoelectric conversion module. And the peeling of the N-type thermoelectric element 52 are suppressed.
  • the linear expansion coefficient of the manganese-silicon element which is the P-type thermoelectric conversion element 51 is 8.0 ppm / ° C.
  • the linear expansion coefficient of the magnesium-silicon element which is the N-type thermoelectric conversion element 52 is 15.5 ppm / ° C. It can be seen that the amount of expansion and contraction when the temperature change of the environment is applied is different between the P-type thermoelectric conversion element 51 and the N-type thermoelectric conversion element 52.
  • each thermoelectric conversion element is joined to the Cu electrode metal film 23 having a linear expansion coefficient of 16.5 ppm / ° C.
  • the electrode material and each thermoelectric conversion Stress and strain are generated in the vicinity of the joint due to the difference in expansion coefficient of the element, and there is a concern that the joint ruptures and cracks in the P-type thermoelectric conversion element 51 and the N-type thermoelectric conversion element 52.
  • the difference in linear expansion coefficient is caused by the fact that the Cu metal plate having the same linear expansion coefficient is joined to both surfaces of the ceramic substrate and the slits are formed in the ceramic substrate. It is possible to suppress the breakage of the joint portion and the generation of the crack of the thermoelectric conversion element.
  • the metal film 21, the ceramic substrate 22, and the electrode metal film 23 are illustrated in the same size, but the metal film 21 and the electrode metal film 23 may be smaller than the ceramic substrate 22. Further, the end portions of the metal film 21 and the electrode metal film 23 bonded to the ceramic substrate 22 may be tapered. By providing the taper, the thermal stress can be reduced. Further, the shapes of the P-type thermoelectric conversion element 51 and the N-type thermoelectric conversion element 52 may be in the shape of a square pole, a triangular pole, a polygonal pole, a cylinder, an elliptic cylinder, or the like.
  • FIGS. 2A to 2D are flow side views showing a flow of a method of manufacturing the stress relaxation type thermoelectric conversion element assembly in the first embodiment of the present invention.
  • a support jig 41 and a pressure jig 42 are added.
  • the P-type thermoelectric conversion element 51, the N-type thermoelectric conversion element 52, the metal film 21, the ceramic substrate 22, the electrode metal film 23, and the bonding material 31 have the same configuration as in FIG.
  • the support jig 41 and the pressure jig 42 may be any material that does not melt in the bonding process, such as ceramics, carbon, or metal, and is a material that does not react with the metal film 21 and the electrode metal film 23 or does not react with the surface It is desirable to form a layer and suppress the reaction.
  • the flow of the method of assembling the thermoelectric conversion element assembly 1 of FIG. 2 will be described with reference to the method of assembling the thermoelectric conversion module with reference to FIGS. 2A to 2D.
  • a ceramic substrate 25 (for high temperature side) having a metal film on both sides is installed on a support jig 41. Thereafter, alignment and installation are performed in order of the bonding material 31 and the P-type thermoelectric conversion element 51 and the N-type thermoelectric conversion element 52 in which the metallization 35 is formed on the electrode metal film 23.
  • the bonding material 31 is placed again on each of the thermoelectric conversion elements, and finally, the electrode metal film 23 of the ceramic substrate 26 (for low temperature side) having metal films on both sides is placed together.
  • the bonding atmosphere may be any non-oxidizing atmosphere, and specifically, a vacuum atmosphere, a nitrogen atmosphere, a nitrogen-hydrogen mixed atmosphere, or the like can be used.
  • the bonding material 31 in FIGS. 1 and 2 has been described as an Ag—Cu—Ti brazing material, the bonding material 31 may be at least one metal foil selected from aluminum, indium, zinc and the like.
  • the bonding material 31 becomes an intermediate layer 32 by causing a diffusion reaction with the electrode metal film 23, the metallization 35, or each thermoelectric conversion element component during bonding.
  • FIG. 2C the support jig 41 and the pressure jig 42 are removed, and as shown in FIG.
  • thermoelectric conversion element assembly 1 can be formed by forming the slits 53 on the surface 26 using a diamond blade or a diamond wire saw or the like.
  • the bonding materials 31 on the upper and lower surfaces of the high temperature side ceramic substrate and the low temperature side ceramic substrate having the patterned electrode metal film 23 and the solid metal film 21 on both surfaces are collectively joined. Showed the process. By performing such collective bonding, the number of types of bonding materials can be reduced, and the number of heat treatments can be reduced.
  • FIG. 2 shows an example in which the electrode metal film 23 bonded to the low temperature side ceramic substrate is patterned and divided in advance.
  • the electrode metal film 23 is formed into a plate shape and divided at the time of slit formation in FIG. It is good.
  • Table 1 shows the results of stress simulation analysis of the effects of Example 1 of the present invention.
  • the stress evaluation temperature conditions assumed that the high temperature side was 550 ° C. and the low temperature side was 25 ° C., assuming that the thermoelectric conversion module was in operation.
  • the influence of the presence or absence of slits on the low temperature side ceramic substrate was compared at the maximum stress.
  • the thermal stress applied to the device during operation is reduced by forming the slits.
  • thermoelectric conversion module in which a slit was formed on the low temperature side ceramic substrate was made on a trial basis, and it was confirmed that no crack was generated in the thermoelectric conversion element and the electrode portion.
  • thermoelectric conversion module Accordingly, an effect of reducing stress can be obtained by the structure in which the slits are formed in the substrate of the thermoelectric conversion module according to the present invention.
  • Example 1 the bonding materials 31 on the upper and lower surfaces of the high-temperature side and low-temperature side ceramic substrates were made of Ag-Cu-Ti brazing material, and were collectively bonded to form the thermoelectric conversion element assembly 1.
  • the high temperature side ceramic substrate 25 and the thermoelectric conversion element are joined using the Ag-Cu-Ti brazing material as in the first embodiment, but the low temperature side ceramic substrate 26 and the thermoelectric conversion element are joined.
  • the point which uses an aluminum foil as material 33 differs from example 1.
  • FIGS. 3A to 3D A second embodiment of the present invention will be described with reference to FIGS. 3A to 3D.
  • the ceramic substrate 25 for high temperature side having the electrode metal film 23 and the metal film 21 on both sides and one end of the thermoelectric conversion element are activated metal brazing material Ag-Cu of the bonding material 31. -Bond with Ti (melting point 780 ° C).
  • the surface of the electrode metal film 23 of the ceramic substrate 26 for low temperature side having the electrode metal film 23 and the metal film 21 on both sides and the other end of the thermoelectric conversion element are joined.
  • An aluminum foil (melting point 660 ° C.) having an Al content of 90% by mass or more is installed.
  • FIG. 3C pressure is applied from above with a pressure jig 42 and heating is performed at 700 to 800 ° C., and the electrode metal film 23, P-type thermoelectric conversion element 51 and N-type thermoelectric conversion element 52 Are bonded via the bonding material 33.
  • the bonding material 33 forms an intermediate layer 34 by causing a diffusion reaction with the components of the electrode metal film 23 and the metallization 35 during bonding.
  • thermoelectric conversion element assembly 2 can be formed by forming the slits 53 on the ceramic substrate 26 using a diamond blade or a diamond wire saw.
  • the bonding material on the high temperature side and the low temperature side can also be selected in accordance with the operating environment temperature.
  • the bonding material 33 on the low temperature side in FIG. 3 has been described as an aluminum foil, the bonding material 33 may be a brazing material containing copper, aluminum, and molybdenum.
  • FIG. 3 shows an example in which the electrode metal film 23 bonded to the low temperature side ceramic substrate is patterned and divided in advance, the electrode metal film 23 is formed into a plate shape and divided in forming slits in FIG. 3D. Also good.
  • the slits for relieving stress are formed on the low temperature side ceramic substrate 26.
  • the slits 54 are formed on the high temperature side ceramic substrate 25 to cause temperature change due to the high temperature side.
  • a thermoelectric conversion element assembly 3 capable of reducing stress can be formed.
  • the manufacturing method of the stress relaxation type thermoelectric conversion element assembly in a present Example is also the same as that of the manufacturing method of Example 1 fundamentally demonstrated by FIG.
  • a fourth embodiment of the present invention will now be described with reference to FIG.
  • the configuration of the present embodiment is basically the same as that of the second embodiment unless otherwise stated.
  • the slits for relieving stress are formed on the low temperature side ceramic substrate 26.
  • the slits 54 are formed on the high temperature side ceramic substrate 26, thereby causing temperature change on the high temperature side.
  • a thermoelectric conversion element assembly 4 capable of reducing stress can be formed.
  • the manufacturing method of the stress relaxation type thermoelectric conversion element assembly in a present Example is also the same as that of the manufacturing method of Example 2 fundamentally demonstrated by FIG.
  • a fifth embodiment of the present invention will now be described with reference to FIG.
  • the configuration of this embodiment is basically the same as that of Embodiments 1 and 3 unless otherwise noted.
  • the slits for stress relaxation are formed on the low temperature side or the high temperature side ceramic substrate, but in the present embodiment, slits are formed on both the low temperature side ceramic substrate and the high temperature side ceramic substrate.
  • the thermoelectric conversion element assembly 5 can be formed which can reduce stress caused by temperature change from both the low temperature side and the high temperature side.
  • the manufacturing method of the stress relaxation type thermoelectric conversion element assembly in a present Example is also the same as that of the manufacturing method of Example 1 fundamentally demonstrated by FIG.
  • Example 2 and Example 4 the slits for stress relaxation are formed in the low temperature side or high temperature side ceramic substrate, but in this example, slits are formed in both the low temperature side and high temperature side ceramic substrates.
  • thermoelectric conversion element assembly 6 capable of reducing stress due to temperature change from both the low temperature side and the high temperature side.
  • the manufacturing method of the stress relaxation type thermoelectric conversion element assembly in a present Example is also the same as that of the manufacturing method of Example 2 fundamentally demonstrated by FIG.
  • FIGS. 8A to 8D A seventh embodiment of the present invention will now be described with reference to FIGS. 8A to 8D.
  • the configuration of the present embodiment is basically the same as that of the first embodiment unless otherwise stated.
  • the electrode metal film 23 bonded to the ceramic substrate is a patterned metal film, and the metal film 21 is a solid metal film.
  • a metal film corresponding to the metal film 21 of Example 1 24 is a metal film patterned in the same shape as the electrode metal film 23 and manufactured in the same manner as in the manufacturing method of Example 1, thereby forming a thermoelectric conversion element set in which slits are formed on the low temperature side ceramic substrate shown in FIG. A solid 7 can be formed.
  • FIG. 8 shows a process of collectively bonding the bonding materials 31 on the upper and lower surfaces of the high temperature side ceramic substrate and the low temperature side ceramic substrate having the patterned electrode metal film 23 and metal film 24 on both sides.
  • the number of types of bonding materials can be reduced, and the number of heat treatments can be reduced.
  • the thermoelectric conversion element is sandwiched between the ceramic substrates having the electrode films 23 and 24 patterned in the same shape on both sides, and the ceramic substrate for the high temperature side and the low temperature side and the thermoelectric conversion element are collectively joined in a symmetrical state. The thermal distortion can be balanced, and the warpage of the ceramic substrate can be reduced.
  • the slits are formed only on the low temperature side ceramic substrate in the present embodiment, the slits may be formed on both the low temperature side ceramic substrate and the low temperature side ceramic substrate.
  • Example 8 applies the thermoelectric conversion module of the present invention to a car. Attach the high temperature exhaust pipe around 300 ° C to 650 ° C around the automobile engine and muffler with the electrode on the high temperature side of the thermoelectric conversion module in close proximity or contact or brazing.
  • the electrode on the low temperature side may be in contact with a low temperature member such as a chassis via an insulating layer, or may be in contact with a structure through which cooling water flows.
  • fins may be attached to the air for exposure.
  • Example 9 applies the thermoelectric conversion module of this invention to industrial furnaces, such as a blast furnace and an incinerator. Attach the electrode on the high temperature side of the thermoelectric conversion module in close proximity to the high temperature piping of 300 ° C to 650 ° C around the air preheater in the industrial furnace or the white smoke prevention (white prevention) heat exchanger, and attach or contact by brazing.
  • the electrode on the low temperature side may, for example, be in contact with a structure through which cooling water flows, or may be exposed to air, for example, with a fin or the like.
  • power can be generated using the heat of piping of an industrial furnace that has conventionally been waste heat in air.
  • FIG. 9 is a perspective view of an example of the structure of a stress reduction thermoelectric conversion module according to the tenth embodiment of the present invention, in which 44 thermoelectric conversion elements are aligned in a grid and joined.
  • the process shown in FIGS. 2A to 2D or 3A to 3D is applied to produce the thermoelectric conversion module assembly 8 shown in FIG.
  • This thermoelectric conversion module may be enclosed in a case, or may be used as it is.
  • thermoelectric conversion module in the thermoelectric conversion module, it is possible to sufficiently relieve the thermal stress generated at the time of operation of the thermoelectric conversion module at the junction between the thermoelectric conversion element and the electrode. Therefore, the thermoelectric conversion module of the present invention can be attached to piping of an industrial furnace such as a blast furnace or an incinerator or an exhaust pipe of a car under high temperature environment and used for power generation.
  • an industrial furnace such as a blast furnace or an incinerator or an exhaust pipe of a car under high temperature environment and used for power generation.
  • thermoelectric conversion element assembly 8 thermoelectric conversion module assembly 21 metal film 22 ceramic substrate 23 electrode metal film 24 metal film 25 having the same pattern as the electrode metal film 25 ceramic substrate 26 for high temperature side ceramic substrate 31 for low temperature side 31 bonding material 32 Intermediate layer 33 Bonding material 34 Intermediate layer 35 Metallization 41 Support jig 42 Pressure jig 51 P type thermoelectric conversion element 52 N type thermoelectric conversion element 53 Slit (low temperature side) 54 Slit (high temperature side)

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

La présente invention concerne un module de conversion thermoélectrique permettant d'atténuer des contraintes qui se produisent dans des éléments de conversion thermoélectrique et dans des parties électrodes lors du fonctionnement du module de conversion thermoélectrique. Dans le module de conversion thermoélectrique : des substrats céramiques comportant chacun des films métalliques sur leurs deux surfaces sont utilisés sur un côté haute température et sur un côté basse température; de multiples éléments de conversion thermoélectrique de type P et de type N sont reliés entre les substrats céramiques; et une partie ou la totalité des multiples éléments de conversion thermoélectrique de type P et des multiples éléments de conversion thermoélectrique de type N sont électriquement connectés en série. Le module de conversion thermoélectrique est caractérisé en ce que les éléments de conversion thermoélectrique de type P et les éléments de conversion thermoélectriques de type N respectifs sont appariés et des fentes sont formées dans le substrat céramique uniquement sur le côté basse température, ou dans le substrat céramique uniquement sur le côté haute température, ou dans les substrats céramiques sur les deux côtés basse et haute températures.
PCT/JP2015/069070 2014-07-25 2015-07-01 Module de conversion thermoélectrique et son procédé de fabrication WO2016013366A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-151892 2014-07-25
JP2014151892A JP2016029695A (ja) 2014-07-25 2014-07-25 熱電変換モジュールおよびその製造方法

Publications (1)

Publication Number Publication Date
WO2016013366A1 true WO2016013366A1 (fr) 2016-01-28

Family

ID=55162898

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/069070 WO2016013366A1 (fr) 2014-07-25 2015-07-01 Module de conversion thermoélectrique et son procédé de fabrication

Country Status (2)

Country Link
JP (1) JP2016029695A (fr)
WO (1) WO2016013366A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016207995A (ja) * 2015-04-27 2016-12-08 株式会社Ｅサーモジェンテック 熱電変換モジュールとその製造方法、ならびに熱電発電システムとその製造方法
JP2017098284A (ja) * 2015-11-18 2017-06-01 日東電工株式会社 半導体装置の製造方法
JP2018148196A (ja) * 2017-03-08 2018-09-20 三菱マテリアル株式会社 熱電変換モジュール及びその製造方法
CN112331759A (zh) * 2020-11-19 2021-02-05 郑州大学 一种高可靠性热电器件及制备方法
CN112382717A (zh) * 2020-11-19 2021-02-19 郑州大学 一种热电器件封装界面及其连接方法
CN113488578A (zh) * 2021-06-29 2021-10-08 同济大学 一种具有高转换效率的低品位废热回收锑化物热电模块及其制备方法
CN114556600A (zh) * 2019-10-24 2022-05-27 三菱电机株式会社 热电转换元件模块以及热电转换元件模块的制造方法
WO2025081604A1 (fr) * 2023-10-20 2025-04-24 深圳先进技术研究院 Module de production d'énergie thermoélectrique auto-encapsulé et son procédé de préparation

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7151068B2 (ja) * 2016-12-26 2022-10-12 三菱マテリアル株式会社 ケース付熱電変換モジュール
JP6681356B2 (ja) * 2017-03-06 2020-04-15 昭和電線ケーブルシステム株式会社 熱電変換モジュール
WO2018163958A1 (fr) * 2017-03-08 2018-09-13 三菱マテリアル株式会社 Module de conversion thermoélectrique et son procédé de fabrication
KR102340798B1 (ko) * 2017-11-01 2021-12-16 주식회사 엘지화학 열전 소자 및 이를 포함하는 열전 모듈
KR102020155B1 (ko) * 2018-10-24 2019-09-10 엘티메탈 주식회사 열전 소자 및 그 제조방법
JP7252603B2 (ja) * 2019-03-04 2023-04-05 国立大学法人大阪大学 熱電変換モジュール、および、熱電変換モジュールの製造方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000068564A (ja) * 1998-08-18 2000-03-03 Dainippon Screen Mfg Co Ltd ペルチェ素子
JP2006237146A (ja) * 2005-02-23 2006-09-07 Ishikawajima Harima Heavy Ind Co Ltd 熱電変換用カスケードモジュール
JP2006332443A (ja) * 2005-05-27 2006-12-07 Kyocera Corp 熱電変換モジュール及び、これを用いた発電装置及び冷却装置
WO2007105361A1 (fr) * 2006-03-08 2007-09-20 Kabushiki Kaisha Toshiba Module de composant electronique
JP2008112806A (ja) * 2006-10-30 2008-05-15 Komatsu Electronics Inc 熱電モジュールおよびメタライズ基板
JP2009123964A (ja) * 2007-11-15 2009-06-04 Toshiba Corp 熱電子デバイス及び熱電モジュール
JP2010245265A (ja) * 2009-04-06 2010-10-28 Honda Motor Co Ltd 熱電モジュール
JP2013012630A (ja) * 2011-06-30 2013-01-17 Toyota Industries Corp 熱電変換モジュール
JP2013149739A (ja) * 2012-01-18 2013-08-01 Toyota Industries Corp 電子機器モジュール
JP2014078663A (ja) * 2012-10-12 2014-05-01 Hitachi Chemical Co Ltd 熱電変換素子組立体及び熱電変換モジュール及びその製造方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000068564A (ja) * 1998-08-18 2000-03-03 Dainippon Screen Mfg Co Ltd ペルチェ素子
JP2006237146A (ja) * 2005-02-23 2006-09-07 Ishikawajima Harima Heavy Ind Co Ltd 熱電変換用カスケードモジュール
JP2006332443A (ja) * 2005-05-27 2006-12-07 Kyocera Corp 熱電変換モジュール及び、これを用いた発電装置及び冷却装置
WO2007105361A1 (fr) * 2006-03-08 2007-09-20 Kabushiki Kaisha Toshiba Module de composant electronique
JP2008112806A (ja) * 2006-10-30 2008-05-15 Komatsu Electronics Inc 熱電モジュールおよびメタライズ基板
JP2009123964A (ja) * 2007-11-15 2009-06-04 Toshiba Corp 熱電子デバイス及び熱電モジュール
JP2010245265A (ja) * 2009-04-06 2010-10-28 Honda Motor Co Ltd 熱電モジュール
JP2013012630A (ja) * 2011-06-30 2013-01-17 Toyota Industries Corp 熱電変換モジュール
JP2013149739A (ja) * 2012-01-18 2013-08-01 Toyota Industries Corp 電子機器モジュール
JP2014078663A (ja) * 2012-10-12 2014-05-01 Hitachi Chemical Co Ltd 熱電変換素子組立体及び熱電変換モジュール及びその製造方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016207995A (ja) * 2015-04-27 2016-12-08 株式会社Ｅサーモジェンテック 熱電変換モジュールとその製造方法、ならびに熱電発電システムとその製造方法
JP2017098284A (ja) * 2015-11-18 2017-06-01 日東電工株式会社 半導体装置の製造方法
JP2018148196A (ja) * 2017-03-08 2018-09-20 三菱マテリアル株式会社 熱電変換モジュール及びその製造方法
CN114556600A (zh) * 2019-10-24 2022-05-27 三菱电机株式会社 热电转换元件模块以及热电转换元件模块的制造方法
CN112331759A (zh) * 2020-11-19 2021-02-05 郑州大学 一种高可靠性热电器件及制备方法
CN112382717A (zh) * 2020-11-19 2021-02-19 郑州大学 一种热电器件封装界面及其连接方法
CN113488578A (zh) * 2021-06-29 2021-10-08 同济大学 一种具有高转换效率的低品位废热回收锑化物热电模块及其制备方法
CN113488578B (zh) * 2021-06-29 2023-02-07 同济大学 一种具有高转换效率的低品位废热回收锑化物热电模块及其制备方法
WO2025081604A1 (fr) * 2023-10-20 2025-04-24 深圳先进技术研究院 Module de production d'énergie thermoélectrique auto-encapsulé et son procédé de préparation

Also Published As

Publication number Publication date
JP2016029695A (ja) 2016-03-03

Similar Documents

Publication Publication Date Title
WO2016013366A1 (fr) Module de conversion thermoélectrique et son procédé de fabrication
EP2377175B1 (fr) Procédé pour la fabrication de dispositif thermoélectrique
JP6171513B2 (ja) 熱電変換モジュールおよびその製造方法
WO2010101049A1 (fr) Élément de conversion thermoélectrique et module de conversion thermoélectrique
CN104040742B (zh) 热电元件及具备该热电元件的热电模块
WO2017098863A1 (fr) Module de conversion thermoélectrique et son procédé de fabrication
WO2010111462A2 (fr) Dispositif thermoélectrique, matériaux d'électrode et procédé de fabrication associé
JP2015511397A (ja) 熱電発電機モジュ−ル、金属−セラミック基板ならびにそのような種類の金属−セラミック基板の製造方法
JP2017130596A (ja) 熱電変換モジュールおよびその製造方法
JP2011029295A (ja) 熱電変換モジュール及びその製造方法
US20110005810A1 (en) Insulating substrate and method for producing the same
EP2660888A1 (fr) Élément de conversion thermoélectrique
CN109065697B (zh) 一种环形热电发电器件
WO2015133430A1 (fr) Module de conversion thermoélectrique
JP2007109942A (ja) 熱電モジュール及び熱電モジュールの製造方法
US20130139866A1 (en) Ceramic Plate
JP2016174114A (ja) 熱電変換モジュール
WO2017020833A1 (fr) Dispositif de production d'énergie thermoélectrique à transfert de chaleur à changement de phase inhibé et son procédé de fabrication
WO2017047627A1 (fr) Module de conversion thermoélectrique et dispositif de conversion thermoélectrique
JP4917375B2 (ja) パワー半導体モジュールの製造方法
JP2007273661A (ja) 半導体装置
JP2017050477A (ja) 熱電変換モジュール及びその製造方法
JP5733466B2 (ja) 半導体装置の製造方法
JP5666372B2 (ja) 絶縁基板用積層材
JP2012248697A (ja) 絶縁基板用積層材の製造方法

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: 15824915

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15824915

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载