WO2019009202A1 - Module de conversion thermoélectrique et procédé de production de module de conversion thermoélectrique - Google Patents

Module de conversion thermoélectrique et procédé de production de module de conversion thermoélectrique Download PDF

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Publication number
WO2019009202A1
WO2019009202A1 PCT/JP2018/024828 JP2018024828W WO2019009202A1 WO 2019009202 A1 WO2019009202 A1 WO 2019009202A1 JP 2018024828 W JP2018024828 W JP 2018024828W WO 2019009202 A1 WO2019009202 A1 WO 2019009202A1
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Prior art keywords
thermoelectric conversion
layer
silver
aluminum
conversion element
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PCT/JP2018/024828
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English (en)
Japanese (ja)
Inventor
皓也 新井
修司 西元
雅人 駒崎
長友　義幸
黒光　祥郎
Original Assignee
三菱マテリアル株式会社
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Priority claimed from JP2018118764A external-priority patent/JP7163631B2/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 CN201880036600.XA priority Critical patent/CN110710008B/zh
Priority to KR1020197034156A priority patent/KR20200026797A/ko
Priority to EP18828546.4A priority patent/EP3651217A4/fr
Priority to US16/608,469 priority patent/US20210111327A1/en
Publication of WO2019009202A1 publication Critical patent/WO2019009202A1/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 thermoelectric conversion elements are electrically connected, and a method of manufacturing the thermoelectric conversion module.
  • thermoelectric conversion element is an electronic element capable of mutually converting thermal energy and electrical energy by the Seebeck effect or Peltier effect.
  • the Seebeck effect is a phenomenon in which an electromotive force is generated when a temperature difference is generated between both ends of a thermoelectric conversion element, and thermal energy is converted into electrical energy.
  • the electromotive force generated by the Seebeck effect is determined by the characteristics of the thermoelectric conversion element. In recent years, development of thermoelectric generation utilizing this effect has been brisk.
  • the Peltier effect is a phenomenon in which when an electrode or the like is formed at both ends of a thermoelectric conversion element to generate a potential difference between the electrodes, a temperature difference occurs at both ends of the thermoelectric conversion element, and electrical energy is converted to thermal energy.
  • An element having such an effect is particularly called a Peltier element, and is used for cooling and temperature control of precision instruments, small refrigerators and the like.
  • thermoelectric conversion module using the above-mentioned thermoelectric conversion element, for example, one having a structure in which an n-type thermoelectric conversion element and a p-type thermoelectric conversion element are alternately connected in series is proposed.
  • heat transfer plates are disposed respectively on one end side and the other end side of a plurality of thermoelectric conversion elements, and the thermoelectric conversion elements are connected in series by the electrode portions disposed on the heat transfer plate.
  • an insulating circuit board provided with an insulating layer and an electrode part may be used.
  • the Seebeck effect generates electrical energy by causing a temperature difference between the heat transfer plate disposed at one end of the thermoelectric conversion element and the heat transfer plate disposed at the other end of the thermoelectric conversion element. It can be done. Alternatively, by supplying a current to the thermoelectric conversion element, between the heat transfer plate disposed at one end of the thermoelectric conversion element and the heat transfer plate disposed at the other end of the thermoelectric conversion element by the Peltier effect. It is possible to generate a temperature difference.
  • thermoelectric conversion module in order to improve the thermoelectric conversion efficiency, it is necessary to suppress the electrical resistance in the electrode portion connected to the thermoelectric conversion element to a low level. For this reason, conventionally, when joining a thermoelectric conversion element and an electrode part, the silver paste etc. which were especially excellent in electroconductivity are used. Moreover, an electrode part itself may be formed with a silver paste, and it may join with a thermoelectric conversion element.
  • thermoelectric conversion element since the sintered body of silver paste has a relatively large number of pores, the electrical resistance can not be suppressed sufficiently low. Moreover, there existed a possibility that the thermoelectric conversion element might deteriorate by the gas which exists in the pore. In order to reduce the number of pores by densifying the sintered body of silver paste, it is conceivable to perform liquid phase sintering by heating to the melting point (960 ° C.) of silver or more. Under such high temperature conditions, thermoelectric conversion is performed during bonding. The element may be degraded by heat.
  • Patent Document 1 proposes a method of joining a thermoelectric conversion element by forming an electrode portion using a silver solder having a melting point lower than that of silver.
  • coating a glass solution to the whole outer peripheral surface of a joining layer and drying in air is performed. Proposed.
  • thermoelectric conversion module 1 silver solder having a melting point lower than that of silver is used, but the melting point of the silver solder used is, for example, 750 to prevent melting of the silver solder even at the operating temperature of the thermoelectric conversion module. 800 ° C. is preferred (see Patent Document 1, paragraph 0023).
  • the thermoelectric conversion elements are joined under such relatively high temperature conditions, there is also a possibility that the characteristics of the thermoelectric conversion elements may be deteriorated by the heat at the time of joining.
  • thermoelectric conversion module since the pores are present inside the bonding layer, the electric resistance in the electrode portion connected to the thermoelectric conversion element can not be suppressed low, and thus the thermoelectric conversion module could not improve the thermoelectric conversion efficiency.
  • thermoelectric conversion module excellent in the thermoelectric conversion efficiency
  • thermoelectric conversion module of the present invention comprises a plurality of thermoelectric conversion elements, a first electrode portion disposed on one end side of the thermoelectric conversion elements, and a second on the other end side. It is an thermoelectric conversion module which has an electrode part and a plurality of thermoelectric conversion elements are electrically connected via the 1st electrode part and the 2nd electrode part.
  • a first insulating circuit board including a first insulating layer and the first electrode portion formed on one surface of the first insulating layer is disposed on one end side of the thermoelectric conversion element. .
  • Said 1st electrode part is 1st silver baking which consists of the 1st aluminum layer which consists of aluminum or aluminum alloys, and the sintered body of silver formed in the surface on the opposite side to said 1st insulating layer of this 1st aluminum layer
  • the first aluminum layer has a thickness in the range of 50 ⁇ m to 2000 ⁇ m
  • the first first silver fired layer has a thickness at least in the region where the thermoelectric conversion element is disposed.
  • the porosity is 5% or more and the porosity is less than 10%.
  • the first insulating layer and the first electrode portion formed on one surface of the first insulating layer are provided on one end side of the thermoelectric conversion element.
  • An insulating circuit substrate is disposed, and the first electrode portion is formed on a first aluminum layer made of aluminum or an aluminum alloy, and a surface of the first aluminum layer opposite to the first insulating layer.
  • the first aluminum layer has a thickness in the range of 50 ⁇ m to 2000 ⁇ m, and the first silver fired layer has at least the thermoelectric conversion. In the region where the element is disposed, the thickness is 5 ⁇ m or more and the porosity is less than 10%, so that the first silver fired layer becomes dense and the thickness of the entire first electrode portion is secured. , Can reduce the electrical resistance.
  • the number of pores in the first silver fired layer is small, it is possible to suppress the deterioration of the thermoelectric conversion element due to the gas of the pores.
  • the first electrode portion is provided with the first aluminum layer made of aluminum or aluminum alloy which is a relatively soft metal, the metal is compared to the case where a substrate in which silver or copper is joined to the insulating layer is used. It is possible to suppress the damage of the insulating layer due to the thermal expansion difference between the first and second insulating layers.
  • the bonding temperature (baking temperature) can be set to a relatively low temperature condition, and the deterioration of the thermoelectric conversion element during bonding can be suppressed.
  • the first silver baked layer itself is made of silver, it can be stably operated even at an operating temperature of about 500.degree.
  • the first silver fired layer may have a thickness of 20 ⁇ m or more.
  • the thickness of the first silver fired layer is formed relatively thick as 20 ⁇ m or more, the conductivity is secured by the first silver fired layer, and electricity between the plurality of thermoelectric conversion elements is obtained. It is possible to keep the resistance low.
  • thermoelectric conversion module the other end side of the thermoelectric conversion element is provided with a second insulating layer and the second electrode portion formed on one surface of the second insulating layer.
  • a second insulating circuit board is disposed, and the second electrode portion is formed on a second aluminum layer made of aluminum or an aluminum alloy, and a surface of the second aluminum layer opposite to the second insulating layer.
  • the second aluminum layer has a thickness in the range of 50 ⁇ m or more and 2000 ⁇ m or less, and the second and third silver fired layers have at least the thermoelectric power layer. In a region in which the conversion element is disposed, the thickness may be 5 ⁇ m or more, and the porosity may be less than 10%.
  • a second insulating circuit board is disposed on the other end side of the thermoelectric conversion element, and the second electrode portion of the second insulating circuit board is also a second aluminum layer made of aluminum or an aluminum alloy, and And a second silver fired layer formed of a fired body of silver formed on the surface opposite to the second insulating layer of the second aluminum layer, and the second aluminum layer has a thickness of 50 ⁇ m to 2000 ⁇ m.
  • the second silver fired layer has a thickness of 5 ⁇ m or more and a porosity of less than 10%, at least in the region where the thermoelectric conversion element is disposed.
  • the fired layer becomes dense, and the thickness of the entire second electrode portion is secured, so that the electric resistance can be reduced.
  • the number of pores in the second silver fired layer is small, the deterioration of the thermoelectric conversion element due to the gas of the pores can be suppressed.
  • the second electrode portion is provided with a second aluminum layer made of aluminum or an aluminum alloy which is a relatively soft metal, the metal is compared to the case where a substrate in which silver or copper is joined to the insulating layer is used. It is possible to suppress the damage of the insulating layer due to the thermal expansion difference between the first and second insulating layers.
  • the bonding temperature (baking temperature) can be set to a relatively low temperature condition, and the deterioration of the thermoelectric conversion element during bonding can be suppressed.
  • the second silver baked layer itself is made of silver, it can be operated stably even at an operating temperature of about 500.degree.
  • the second silver fired layer may have a thickness of 20 ⁇ m or more.
  • the thickness of the second silver fired layer is formed to be relatively large such as 20 ⁇ m or more, the conductivity is ensured by the second silver fired layer, and electricity between the plurality of thermoelectric conversion elements is obtained. It is possible to keep the resistance low.
  • thermoelectric conversion module comprises a plurality of thermoelectric conversion elements, a first electrode portion disposed on one end side of the thermoelectric conversion elements, and a second electrode portion disposed on the other end side. It is a manufacturing method of the thermoelectric conversion module which has a plurality of said thermoelectric conversion elements electrically connected via said 1st electrode part and said 2nd electrode part.
  • the thermoelectric conversion module is a first insulating circuit board including a first insulating layer on one end side of the thermoelectric conversion element, and the first electrode portion formed on one surface of the first insulating layer. It is arranged.
  • Said 1st electrode part is 1st silver baking which consists of the 1st aluminum layer which consists of aluminum or aluminum alloys, and the sintered body of silver formed in the surface on the opposite side to said 1st insulating layer of this 1st aluminum layer And a layer.
  • a silver paste application step of applying a silver paste containing silver to a thickness of more than 5 ⁇ m on one side of the first aluminum layer, and firing the silver paste to form the first aluminum layer A firing step of forming the first electrode portion having the first silver firing layer, a stacking step of stacking the first insulating layer on one end side of the thermoelectric conversion element via the first electrode portion, and And a thermoelectric conversion element bonding step of pressing and heating the conversion element and the first insulating layer in the stacking direction and bonding the thermoelectric conversion elements.
  • thermoelectric conversion element bonding step a glass-containing silver paste is applied at least to the lowermost layer in contact with the first aluminum layer, and in the thermoelectric conversion element bonding step, the pressure load is in the range of 20 MPa to 50 MPa,
  • the heating temperature is set to 300 ° C. or more and 400 ° C. or less.
  • the region where at least the thermoelectric conversion element of the first silver fired layer is disposed has a thickness of 5 ⁇ m or more, and a porosity of less than 10%.
  • the heating load is set to 300 ° C. or more and 400 ° C. or less within the range of 20 MPa to 50 MPa. Therefore, the thickness can be 5 ⁇ m or more and the porosity can be less than 10% in at least the area where the thermoelectric conversion element of the first silver fired layer is disposed. Moreover, since it is set as comparatively low temperature conditions, deterioration of the thermoelectric conversion element at the time of joining (at the time of baking) can be suppressed.
  • the glass-containing silver paste is applied to at least the lowermost layer in contact with the first aluminum layer, it is formed on the surface of the first aluminum layer by the glass component of the glass-containing silver paste.
  • the oxide film can be removed, and the first aluminum layer and the first silver fired layer can be reliably bonded.
  • the method for manufacturing a thermoelectric conversion module according to the present invention may further include a blasting step of blasting the first silver fired layer after the firing step.
  • a blasting step of blasting the first silver fired layer since the blasting step of blasting the first silver fired layer is provided, the electrical resistance between the first silver fired layer and the first aluminum layer is reduced, and the first electrode portion is formed.
  • the conductivity in the above can be improved.
  • the thermoelectric conversion element may be disposed after applying and drying a silver paste on the first electrode portion in the laminating step.
  • the thermoelectric conversion element is disposed, and then the thermoelectric conversion element is joined under the above-described conditions, so The sintered body of the silver paste applied onto the first electrode portion can also be densified to have a porosity of less than 10%.
  • thermoelectric conversion module may further include: a second insulating layer on the other end side of the thermoelectric conversion element; and the second insulating layer on one side of the second insulating layer. And a second insulating circuit substrate having two electrodes, wherein the second electrode is a second aluminum layer made of aluminum or an aluminum alloy, and the second insulating layer of the second aluminum layer. And a second silver fired layer composed of a fired body of silver stacked on the opposite side to the second silver fired layer.
  • a silver paste containing silver is applied with a thickness of 5 ⁇ m or more on one surface of the first aluminum layer and the second aluminum layer, and at least the first aluminum layer and the second Glass-containing silver paste is applied to the lowermost layer in contact with the aluminum layer.
  • the silver paste is fired, and the first electrode portion including the first aluminum layer and the first silver fired layer, and the second electrode layer including the second aluminum layer and the second silver fired layer. 2 Form an electrode part.
  • the first insulating layer is stacked on the one end side of the thermoelectric conversion element via the first electrode portion, and the second insulating portion is stacked on the other end side of the thermoelectric conversion element via the second electrode portion. Stack the insulating layer.
  • thermoelectric conversion element bonding step the first insulating layer, the thermoelectric conversion element, and the second insulating layer are pressurized and heated in the stacking direction, and the first electrode portion, the thermoelectric conversion element, and The thermoelectric conversion element and the second electrode portion are joined.
  • the pressure load is in the range of 20 MPa to 50 MPa
  • the heating temperature is 300 ° C. to 400 ° C.
  • the thickness is at least 5 ⁇ m and at least in the region where the thermoelectric conversion element is disposed.
  • the porosity can be less than 10%.
  • the glass-containing silver paste is applied to at least the lowermost layer in contact with the first aluminum layer and the second aluminum layer, so the first aluminum layer is made of the glass component of the glass-containing silver paste.
  • the oxide film formed on the surface of the second aluminum layer can be removed, and the first aluminum layer and the first silver fired layer, and the second aluminum layer and the second silver fired layer can be assured Can be bonded to
  • the method for manufacturing a thermoelectric conversion module according to the present invention may further include a blasting step of blasting the first silver fired layer and the second silver fired layer after the firing step.
  • a blasting step of blasting the first silver fired layer and the second silver fired layer after the firing step.
  • the thermoelectric conversion element may be disposed after applying and drying a silver paste on the second electrode portion in the laminating step.
  • the thermoelectric conversion element is disposed, and then the thermoelectric conversion element is joined under the above-described conditions, so The sintered body of the silver paste applied on the second electrode portion can also be densified to have a porosity of less than 10%.
  • thermoelectric conversion module having a low electrical resistance in the electrode portion and suppressing deterioration of the thermoelectric conversion element at the time of bonding, and having excellent thermoelectric conversion efficiency, and a method of manufacturing the thermoelectric conversion module.
  • thermoelectric conversion module which is embodiment of this invention. It is a flowchart which shows the manufacturing method of the thermoelectric conversion module which is embodiment of this invention. It is a schematic explanatory drawing of the manufacturing method of the thermoelectric conversion module which is embodiment of this invention. It is a schematic explanatory drawing of the manufacturing method of the thermoelectric conversion module which is embodiment of this invention. It is a schematic explanatory drawing of the thermoelectric conversion module which is other embodiment of this invention.
  • thermoelectric conversion module 10 is arranged on a plurality of columnar thermoelectric conversion elements 11 and one end side (lower side in FIG. 1) of the thermoelectric conversion elements 11 in the length direction.
  • a first heat transfer plate 20 is provided, and a second heat transfer plate 30 disposed on the other end side (upper side in FIG. 1) of the thermoelectric conversion elements 11 in the longitudinal direction.
  • the first electrode portion 25 is formed on the first heat transfer plate 20 disposed on one end side of the thermoelectric conversion element 11, and the first heat transfer plate 20 is disposed on the other end side of the thermoelectric conversion element 11.
  • a second electrode portion 35 is formed on the heat transfer plate 30, and a plurality of columnar thermoelectric conversion elements 11 are electrically connected in series by the first electrode portion 25 and the second electrode portion 35. .
  • the first heat transfer plate 20 includes a first insulating layer 21 and a first electrode portion 25 formed on one surface (upper surface in FIG. 1) of the first insulating layer 21. It consists of In the present embodiment, in the first insulating circuit substrate to be the first heat transfer plate 20, as shown in FIG. 1, the first heat dissipation layer 26 is formed on the other surface (the lower surface in FIG. 1) of the first insulating layer 21. Is formed.
  • the first insulating layer 21 is made of, for example, a highly insulating ceramic material such as aluminum nitride (AlN), silicon nitride (Si 3 N 4 ), alumina (Al 2 O 3 ), or an insulating resin.
  • the first insulating layer 21 is made of aluminum nitride (AlN).
  • the thickness of the first insulating layer 21 made of aluminum nitride is in the range of 100 ⁇ m to 2000 ⁇ m.
  • the first electrode portion 25 is opposite to the first aluminum layer 25a disposed on one surface of the first insulating layer 21 and the first insulating layer 21 of the first aluminum layer 25a. And a first silver fired layer 25b made of a fired body of silver stacked on the side surface.
  • the first electrode portion 25 is formed in a pattern on one surface (upper surface in FIG. 1) of the first insulating layer 21.
  • the thickness of the first aluminum layer 25a is in the range of 50 ⁇ m to 2000 ⁇ m.
  • the first aluminum layer 25 a is formed by bonding a first aluminum plate 45 a to one surface of the first insulating layer 21.
  • the first aluminum plate 45a is made of aluminum having a purity of 99 mass% or more and aluminum having a purity of 99.99 mass% or more.
  • the first silver fired layer 25b is composed of a fired body of silver, and the lowermost layer in contact with one surface of the first aluminum layer 25a is composed of a fired body of a glass-containing silver paste containing a glass component .
  • the entire first silver fired layer 25 b is formed of a fired body of a glass-containing silver paste.
  • the thickness of the first silver fired layer 25 b is 5 ⁇ m or more at least in the region where the thermoelectric conversion element 11 is disposed.
  • the thickness of the first silver fired layer 25 b is preferably 20 ⁇ m or more. By setting the thickness of the first silver fired layer 25 b to 20 ⁇ m or more, the electrical resistance can be reliably reduced. Moreover, it is preferable that the thickness of the 1st silver baking layer 25b is 100 micrometers or less. By setting the thickness of the first silver fired layer 25b to 100 ⁇ m or less, generation of large thermal stress in the thermoelectric conversion element 11 can be suppressed when a cooling thermal cycle is applied, and generation of cracks can be prevented. Become. Therefore, the thickness of the first silver fired layer 25 b is preferably in the range of 20 ⁇ m to 100 ⁇ m. The lower limit of the thickness of the first silver fired layer 25 b is more preferably 30 ⁇ m or more, and the upper limit of the thickness of the first silver fired layer 25 b is more preferably 60 ⁇ m or less.
  • the porosity P is less than 10% at least in the region where the thermoelectric conversion element 11 is disposed.
  • the porosity P of the first silver fired layer 25 b can be calculated as follows. After mechanically polishing the cross section of the first silver fired layer 25b, Ar ion etching (cross section polisher SM-09010 manufactured by Nippon Denshi Co., Ltd.) is performed, and cross section observation is performed using a laser microscope (VKX-200 manufactured by Keyence Inc.) Carried out. The obtained image was binarized, the white portion was Ag, and the black portion was pores. The area of the black part was determined from the binarized image, and the porosity was calculated by the following equation.
  • Porosity P (%) black area (pores) area / observed area of first silver fired layer 21b ⁇ 100
  • the first aluminum layer 25a is made of aluminum or an aluminum alloy, an aluminum oxide film naturally generated in the air is formed on the surface of the first aluminum layer 25a.
  • the lowermost layer of the first silver fired layer 25b is formed of a fired body of a glass-containing silver paste, the aluminum oxide film is removed by the glass component, and the first aluminum layer 25a and the first silver fired layer 25b is firmly joined.
  • the first heat radiation layer 26 is made of aluminum or an aluminum alloy.
  • the first heat dissipation layer 26 is formed by bonding a heat dissipation aluminum plate 46 to the other surface of the first insulating layer 21 as in the first aluminum layer 25 a.
  • the heat dissipation aluminum plate 46 is made of aluminum having a purity of 99 mass% or more and aluminum having a purity of 99.99 mass% or more.
  • the second heat transfer plate 30 includes a second insulating layer 31 and a second electrode portion 35 formed on one surface (a lower surface in FIG. 1) of the second insulating layer 31. It consists of In the present embodiment, in the second insulating circuit substrate to be the second heat transfer plate 30, as shown in FIG. 1, the second heat dissipation layer 36 is formed on the other surface (upper surface in FIG. 1) of the second insulating layer 31. Is formed.
  • the second insulating layer 31 is made of, for example, a highly insulating ceramic material such as aluminum nitride (AlN), silicon nitride (Si 3 N 4 ), alumina (Al 2 O 3 ), or an insulating resin.
  • the second insulating layer 31 is made of aluminum nitride (AlN).
  • the thickness of the second insulating layer 31 made of aluminum nitride is in the range of 100 ⁇ m to 2000 ⁇ m.
  • the second electrode portion 35 is opposite to the second aluminum layer 35 a disposed on one surface of the second insulating layer 31 and the second insulating layer 31 of the second aluminum layer 35 a. And a second silver fired layer 35b formed of a fired body of silver stacked on the side surface.
  • the second electrode portion 35 is formed in a pattern on one surface (the lower surface in FIG. 1) of the second insulating layer 31.
  • the thickness of the second aluminum layer 35a is in the range of 50 ⁇ m to 2000 ⁇ m. As shown in FIG. 3, the second aluminum layer 35 a is formed by bonding the second aluminum plate 55 a to one surface of the second insulating layer 31. In the present embodiment, the second aluminum plate 55a is made of aluminum having a purity of 99 mass% or more and aluminum having a purity of 99.99 mass% or more.
  • the second silver fired layer 35b is composed of a fired body of silver, and the lowermost layer in contact with one surface of the second aluminum layer 35a is composed of a fired body of a glass-containing silver paste containing a glass component .
  • the entire second silver fired layer 35 b is formed of a fired body of a glass-containing silver paste.
  • the thickness of the second silver fired layer 35 b is 5 ⁇ m or more at least in the region where the thermoelectric conversion element 11 is disposed.
  • the thickness of the second silver fired layer 35 b is preferably 20 ⁇ m or more. By setting the thickness of the second silver fired layer 35 b to 20 ⁇ m or more, the electrical resistance can be reliably reduced.
  • the thickness of the second silver fired layer 35 b is preferably 100 ⁇ m or less.
  • the thickness of the first silver fired layer 35b is preferably in the range of 20 ⁇ m to 100 ⁇ m.
  • the lower limit of the thickness of the second silver fired layer 35 b is more preferably 30 ⁇ m or more, and the upper limit of the thickness of the second silver fired layer 35 b is more preferably 60 ⁇ m or less.
  • the porosity P is less than 10% at least in the region where the thermoelectric conversion element 11 is disposed.
  • the porosity P of the second silver fired layer 35 b can be calculated by the same method as that of the first silver fired layer 25 b.
  • the second aluminum layer 35a is made of aluminum or an aluminum alloy, an aluminum oxide film naturally generated in the air is formed on the surface of the second aluminum layer 35a.
  • the lowermost layer of the second silver fired layer 35b is formed of a fired body of the glass-containing silver paste, the aluminum oxide film is removed by the glass component, and the second aluminum layer 35a and the second silver fired layer 35b is firmly joined.
  • the second heat radiation layer 36 is made of aluminum or an aluminum alloy.
  • the second heat dissipation layer 36 is formed by bonding a heat dissipation aluminum plate 56 to the other surface of the second insulating layer 31 as in the second aluminum layer 35 a.
  • the heat dissipation aluminum plate 56 is made of aluminum having a purity of 99 mass% or more and aluminum having a purity of 99.99 mass% or more.
  • the thermoelectric conversion element 11 has an n-type thermoelectric conversion element 11a and a p-type thermoelectric conversion element 11b, and these n-type thermoelectric conversion elements 11a and p-type thermoelectric conversion elements 11b are alternately arranged.
  • Metallized layers (not shown) are respectively formed on one end surface and the other end surface of the thermoelectric conversion element 11.
  • the metallized layer it is possible to use, for example, nickel, silver, cobalt, tungsten, molybdenum or the like, or a non-woven fabric or the like made of these metal fibers.
  • the outermost surface of the metallized layer (the bonding surface with the first electrode portion 25 and the second electrode portion 35) is preferably made of Au or Ag.
  • the n-type thermoelectric conversion element 11a and the p-type thermoelectric conversion element 11b are, for example, sintered bodies of tellurium compound, skutterudite, filled skutterudite, Heusler, half-Heusler, clathrate, silicide, oxide, silicon germanium, etc. It is configured.
  • a material of the n-type thermoelectric conversion element 11 a for example, Bi 2 Te 3 , PbTe, La 3 Te 4 , CoSb 3 , FeVAl, ZrNiSn, Ba 8 Al 16 Si 30 , Mg 2 Si, FeSi 2 , SrTiO 3 , CaMnO 3 , ZnO, SiGe and the like are used.
  • thermoelectric conversion module 10 Next, a method of manufacturing the thermoelectric conversion module 10 according to the above-described embodiment will be described with reference to FIGS. 2 to 4.
  • the first aluminum plate 45 a is joined to one surface of the first insulating layer 21 to form the first aluminum layer 25 a, and the second aluminum layer 25 a is formed on the one surface of the second insulating layer 31.
  • the aluminum plate 55a is joined to form a second aluminum layer 35a.
  • the heat dissipation aluminum plate 46 is joined to the other surface of the first insulation layer 21 to form the first heat dissipation layer 26, and the other side of the second insulation layer 31.
  • the second heat dissipation layer 36 is formed by bonding the heat dissipation aluminum plate 56 to the surface.
  • the bonding method of the first insulating layer 21 and the first aluminum plate 45 a and the heat radiating aluminum plate 46 and the bonding method of the second insulating layer 31 and the second aluminum plate 55 a and the heat radiating aluminum plate 56 are not particularly limited.
  • bonding using Al—Si based brazing material or solid phase diffusion bonding may be applied.
  • bonding may be performed by a transient liquid phase bonding method (TLP) in which an additive element such as Cu, Si or the like is fixed to the bonding surface and the additive element is diffused to melt and solidify.
  • TLP transient liquid phase bonding method
  • the first insulating layer 21, the first aluminum plate 45 a, the aluminum plate 46 for heat dissipation, and the second insulating layer 31 are formed using Al—Si brazing materials 48 and 58. And the second aluminum plate 55a and the heat radiation aluminum plate 56 are joined.
  • a silver paste containing silver is applied to one surface of the first aluminum layer 25a and one surface of the second aluminum layer 35a with a thickness of more than 5 ⁇ m.
  • the application method is not particularly limited, and various means such as screen printing method, offset printing method, photosensitive process and the like can be adopted.
  • a glass-containing silver paste having a glass component is applied to the lowermost layer in contact with at least the first aluminum layer 25a and the second aluminum layer 35a.
  • the application and drying of the paste may be repeated in order to make the application thickness exceed 5 ⁇ m.
  • a glass-containing paste may be applied to the lowermost layer in contact with the first aluminum layer 25a and the second aluminum layer 35a, and thereafter a silver paste containing no glass component may be applied.
  • the thickness of each of the glass-containing silver pastes 45b and 55b exceeds 5 ⁇ m on one side of the first aluminum layer 25a and on one side of the second aluminum layer 35a. It is applied with.
  • coating thickness shall be 7 micrometers or more.
  • the glass-containing silver paste for forming the first silver fired layer 25 b and the second silver fired layer 35 b will be described.
  • the glass-containing silver paste contains silver powder, glass powder, a resin, a solvent, and a dispersant, and the content of a powder component composed of silver powder and glass powder is glass-containing silver paste
  • the total amount is 60% by mass or more and 90% by mass or less, and the remaining portion is a resin, a solvent, or a dispersant.
  • the content of the powder component composed of the silver powder and the glass powder is 85% by mass of the entire glass-containing silver paste.
  • the viscosity of this glass-containing silver paste is adjusted to 10 Pa ⁇ s or more and 500 Pa ⁇ s or less, more preferably 50 Pa ⁇ s or more and 300 Pa ⁇ s or less.
  • the silver powder has a particle diameter of 0.05 ⁇ m or more and 1.0 ⁇ m or less, and in the present embodiment, one having an average particle diameter of 0.8 ⁇ m was used.
  • the glass powder contains, for example, any one or more of lead oxide, zinc oxide, silicon oxide, boron oxide, phosphorus oxide and bismuth oxide.
  • a glass powder consisting of lead oxide, zinc oxide and boron oxide as main components and having an average particle diameter of 0.5 ⁇ m was used.
  • the solvent one having a boiling point of 200 ° C. or higher is suitable, and in the present embodiment, diethylene glycol dibutyl ether is used.
  • the resin is used to adjust the viscosity of the glass-containing silver paste, and a resin that decomposes at 400 ° C. or higher is suitable.
  • ethyl cellulose is used.
  • a dicarboxylic acid-based dispersant is added. You may comprise a glass containing silver paste, without adding a dispersing agent.
  • this glass-containing silver paste a mixed powder obtained by mixing silver powder and glass powder and an organic mixture obtained by mixing a solvent and a resin are premixed together with a dispersant by a mixer, and the obtained preliminary mixture is milled by a roll mill. After mixing while being kneaded, the resulting kneaded product is produced by filtering with a paste filter.
  • the first silver fired layer 25 b and the second silver fired layer 35 b may be subjected to a blast process, as necessary.
  • a blast process for example, in the case where the thickness of the first silver baked layer 25 b and the second silver baked layer 35 b is 5 ⁇ m or more and less than 20 ⁇ m, it is preferable to carry out the blasting step S04.
  • the blasting step S04 is performed, irregularities are formed on the surfaces of the first silver fired layer 25b and the second silver fired layer 35b after the blasting process according to the blast abrasives to be collided.
  • the surface roughness Ra of the first silver fired layer 25 b and the second silver fired layer 35 b after the blast treatment may be 0.35 ⁇ m or more and 1.50 ⁇ m or less.
  • the surface roughness Ra after the blast treatment may be 0.35 ⁇ m or more, between the first silver fired layer 25b and the first aluminum layer 25a, and between the second silver fired layer 35b and the second aluminum layer 35a.
  • the electrical resistance between them can be sufficiently reduced.
  • the thermoelectric conversion element 11 can be joined favorably by setting surface roughness Ra after a blast process to 1.50 micrometers or less.
  • glass particles such as silica with a New Mohs hardness of 2 to 7, ceramic particles, metal particles, resin beads or the like can be used as blast particles.
  • glass particles are used.
  • grains is made into the range of 20 micrometers or more and 150 micrometers or less.
  • the blast pressure is in the range of 0.2 MPa to 0.8 MPa, and the processing time is in the range of 2 seconds to 60 seconds.
  • the thickness of the first silver fired layer 25 b and the second silver fired layer 35 b is less than 5 ⁇ m
  • a part of the first silver fired layer 25 b and the second silver fired layer 35 b is made by the first aluminum layer 25 a and the blast treatment. It is embedded in the 2nd aluminum layer 35a, and bondability falls between the thermoelectric conversion element 11 and the 1st electrode part 25, and the thermoelectric conversion element 11 and the 2nd electrode part 35.
  • a silver paste containing no glass may be applied, dried and fired to make the thicknesses of the first silver fired layer 25b and the second silver fired layer 35b 5 ⁇ m or more.
  • the presence or absence of the implementation of the blasting step S04 is preferably determined on the basis of the following criteria.
  • the first electrical resistance between the two thermoelectric conversion elements 11 connected is 1/10 or less of the electrical resistance of the thermoelectric conversion element 11 itself. It is preferable to constitute the silver fired layer 25 b and the second silver fired layer 35 b. Specifically, the electrical resistance between the two connected thermoelectric conversion elements 11 is preferably in the range of 1 m ⁇ or more and 1 ⁇ or less.
  • the blasting step S04 is performed. There is no need.
  • the blasting step S04 is performed.
  • the conductivity is ensured by the first silver baked layer 25b and the first aluminum layer 25a, and the second silver baked layer 35b and the second aluminum layer 35a.
  • blasting process S04 When blasting process S04 is implemented, when the cooling-heating cycle is loaded with respect to the thermoelectric conversion module 10, there exists a possibility that the effect of blasting process S04 may reduce. For this reason, it is preferable not to carry out the blasting step S04 in applications where a thermal cycle is applied.
  • the first insulating layer 21 is laminated on one end side (lower side in FIG. 4) of the thermoelectric conversion element 11 via the first electrode portion 25 and the other end side (upper side in FIG. 4) of the thermoelectric conversion element 11
  • the second insulating layer 31 is stacked on the second electrode portion 35.
  • thermoelectric conversion element bonding step S06 Next, the first insulating layer 21, the thermoelectric conversion element 11, and the second insulating layer 31 are pressurized and heated in the stacking direction, and the thermoelectric conversion element 11 and the first electrode portion 25, and the thermoelectric conversion element 11 and the first The two electrode parts 35 are joined.
  • the thermoelectric conversion element 11 is bonded to the first electrode unit 25 and the second electrode unit 35 by solid phase diffusion bonding.
  • the thickness is set to 5 ⁇ m or more, and the porosity P is set to less than 10% in a region where at least the thermoelectric conversion element 11 of the first silver fired layer 25 b is disposed.
  • the thickness is set to 5 ⁇ m or more and the porosity P is set to less than 10% in at least the region where the thermoelectric conversion element 11 of the second silver fired layer 35 b is disposed.
  • the pressure load is in the range of 20 MPa to 50 MPa
  • the heating temperature is in the range of 300 ° C. to 400 ° C.
  • the holding time at the above-mentioned heating temperature is 5 minutes or more and 60 minutes or less
  • the atmosphere is a vacuum atmosphere.
  • the pressure load in the thermoelectric conversion element bonding step S06 is less than 20 MPa, the porosity of the first silver fired layer 25b and the second silver fired layer 35b may not be less than 10%.
  • the pressure load in the thermoelectric conversion element bonding step S06 exceeds 50 MPa, there is a possibility that a crack may occur in the thermoelectric conversion element 11 and the first insulating layer 21 and the second insulating layer 31 made of aluminum nitride.
  • the pressure load in the thermoelectric conversion element bonding step S06 is set in the range of 20 MPa or more and 50 MPa or less.
  • thermoelectrical conversion element junction process S06 In order to make porosity P of the 1st silver calcination layer 25b and the 2nd silver calcination layer 35b certainly less than 10%, it is preferred to make the minimum of the pressurization load in thermoelectrical conversion element junction process S06 into 30 or more MPa. On the other hand, to reliably suppress the occurrence of cracks in the first insulating layer 21 and the second insulating layer 31 made of the thermoelectric conversion element 11 or aluminum nitride, the upper limit of the pressing load in the thermoelectric conversion element bonding step S06 is 40 MPa or less It is preferable to
  • thermoelectric conversion element bonding step S06 If the heating temperature in the thermoelectric conversion element bonding step S06 is less than 300 ° C., there is a possibility that the thermoelectric conversion element 11 can not be bonded to the first electrode portion 25 and the second electrode portion 35. On the other hand, when the heating temperature in the thermoelectric conversion element bonding step S06 exceeds 400 ° C., the first aluminum layer 25a and the second aluminum layer 35a are softened and deformed, and the first electrode portion 25 and the first electrode portion 25 formed in a pattern are There is a possibility that the 2 electrode part 35 may short-circuit. For this reason, in the present embodiment, the heating temperature in the thermoelectric conversion element bonding step S06 is set in the range of 300 ° C. or more and 400 ° C. or less.
  • the lower limit of the heating temperature in the thermoelectric conversion element bonding step S06 is preferably 330 ° C. or more.
  • the upper limit of the heating temperature in the thermoelectric conversion element bonding step S06 it is preferable to set the upper limit of the heating temperature in the thermoelectric conversion element bonding step S06 to 370 ° C. or less.
  • thermoelectric conversion module 10 As described above, the thermoelectric conversion module 10 according to the present embodiment is manufactured.
  • the first heat transfer plate 20 side is used as a low temperature portion
  • the second heat transfer plate 30 side is used as a high temperature portion. Conversion with electrical energy is performed.
  • thermoelectric conversion module 10 configured as described above, the first insulating layer 21 and one surface of the first insulating layer 21 are formed on one end side of the thermoelectric conversion element 11.
  • a first insulating circuit board including the first electrode portion 25 is disposed.
  • the first electrode portion 25 is formed of a first aluminum layer 25a made of aluminum or an aluminum alloy, and a sintered body of silver laminated on the surface of the first aluminum layer 25a opposite to the first insulating layer 21. And a silver fired layer 25b.
  • the thickness of the first aluminum layer 25a is in the range of 50 ⁇ m to 2000 ⁇ m.
  • the first silver fired layer 25 b has a thickness of 5 ⁇ m or more and a porosity P of less than 10% at least in a region where the thermoelectric conversion element 11 is disposed. Therefore, the first silver fired layer 25 b becomes dense, and the thickness of the entire first electrode portion 25 is secured, so that the electric resistance can be reduced. In addition, since the number of pores in the first silver fired layer 25 b is small, the deterioration of the thermoelectric conversion element 11 due to the gas of the pores can be suppressed.
  • the first electrode portion 25 is provided with the first aluminum layer 25 a made of aluminum or an aluminum alloy which is a relatively soft metal, when using a substrate in which silver or copper is joined to the first insulating layer 21. In comparison with the above, it is possible to suppress the breakage of the first insulating layer 21 due to the thermal expansion difference between the metal and the first insulating layer 21. Furthermore, since the first silver fired layer 25b is a fired body of silver paste, the bonding temperature (baking temperature) can be set to a relatively low temperature condition, and the deterioration of the thermoelectric conversion element 11 at the time of bonding is suppressed. be able to. Further, since the first silver baked layer 25b itself is made of silver, it can be stably operated even at an operating temperature of about 500.degree.
  • a second insulating layer 31 and a second electrode portion 35 formed on one surface of the second insulating layer 31 are provided on the other end side of the thermoelectric conversion element 11.
  • An insulating circuit board is provided.
  • the second electrode portion 35 is formed of a second aluminum layer 35 a made of aluminum or an aluminum alloy, and a second sintered body of silver stacked on the surface of the second aluminum layer 35 a opposite to the second insulating layer 31.
  • a silver fired layer 35 b The thickness of the second aluminum layer 35 a is in the range of 50 ⁇ m to 2000 ⁇ m.
  • the second silver fired layer 35 b has a thickness of 5 ⁇ m or more and a porosity P of less than 10% at least in a region where the thermoelectric conversion element 11 is disposed. Therefore, the second silver fired layer 35b becomes dense, and the thickness of the entire second electrode portion 35 is secured, so that the electric resistance can be reduced. Further, since the number of pores in the second silver fired layer 35 b is small, the deterioration of the thermoelectric conversion element 11 due to the gas of the pores can be suppressed.
  • the second electrode portion 35 is provided with the second aluminum layer 35 a made of aluminum or an aluminum alloy which is a relatively soft metal, when using a substrate in which silver or copper is joined to the second insulating layer 31 In comparison with the above, it is possible to suppress the breakage of the second insulating layer 31 due to the thermal expansion difference between the metal and the second insulating layer 31. Furthermore, since the second silver fired layer 35b is a fired body of silver paste, the bonding temperature (baking temperature) can be set to a relatively low temperature condition, and the deterioration of the thermoelectric conversion element 11 at the time of bonding is suppressed. be able to. Further, since the second silver baked layer 35b itself is made of silver, it can be stably operated even at an operating temperature of about 500.degree.
  • thermoelectric conversion module 10 when the thicknesses of the first silver fired layer 25 b and the second silver fired layer 35 b are 20 ⁇ m or more, the first silver fired layer 25 b and the second silver fired layer 35 b The conductivity is secured, and the electrical resistance between the plurality of thermoelectric conversion elements 11 can be suppressed to a low level.
  • the heating load is 300 ° C. or more and 400 ° C. or less in the range of 20 MPa to 50 MPa and the heating load in the thermoelectric conversion element bonding step S06.
  • the thickness can be 5 ⁇ m or more, and the porosity P can be less than 10%.
  • it is set as comparatively low temperature conditions, deterioration of the thermoelectric conversion element 11 at the time of joining (at the time of baking) can be suppressed.
  • the first aluminum layer is formed by the glass component of the glass-containing silver paste.
  • the oxide film formed on the surface of the second aluminum layer 35a can be removed, and the first aluminum layer 25a and the first silver fired layer 25b, and the second aluminum layer 35a and the second silver fired layer 35b can be removed. It can be joined reliably.
  • the first silver fired layer 25 b and the second silver fired layer 35 b are used.
  • the blasting step S04 for blasting is performed, the electrical resistance between the first silver fired layer 25b and the first aluminum layer 25a and between the second silver fired layer 35b and the second aluminum layer 35a The conductivity of the first electrode portion 25 and the second electrode portion 35 can be improved.
  • the thickness of the first silver baked layer 25b and the second silver baked layer 35b is 5 ⁇ m or more, the first silver baked layer 25b and the second silver are formed on the first aluminum layer 25a and the second aluminum layer 35a by blasting. A part of the baked layer 35b is not embedded, and the bonding property of the thermoelectric conversion element 11 and the first electrode portion 25 and the thermoelectric conversion element 11 and the second electrode portion 35 is not reduced.
  • the thickness of the first silver fired layer 25 b and the second silver fired layer 35 b is 20 ⁇ m or more, the conductivity is sufficiently ensured in the first silver fired layer 25 b and the second silver fired layer 35 b.
  • the above-mentioned blasting step S04 may not be performed.
  • thermoelectric conversion element 11 is directly stacked on the first electrode portion 25 and the second electrode portion 35 in the stacking step S05 and described as solid phase diffusion bonding, but the present invention is limited thereto
  • the thermoelectric conversion element 11 may be disposed and joined using the silver paste.
  • the first bonding layer 27 is formed between the first electrode portion 25 and the thermoelectric conversion element 11
  • the second bonding layer is formed between the second electrode portion 35 and the thermoelectric conversion element 11. 37 are formed.
  • the porosity of the first bonding layer 27 and the second bonding layer 37 is also less than 10%.
  • the second heat transfer plate 30 is disposed as the second heat transfer plate 30 on the other end side of the thermoelectric conversion element 11 in the present embodiment, the present invention is not limited to this.
  • the second heat transfer plate may be configured by disposing the second electrode portion on the other end side of the thermoelectric conversion element 11 and stacking the insulating substrate and pressing the insulating substrate in the stacking direction.
  • thermoelectric conversion module was produced by the method similar to embodiment mentioned above.
  • a 12 mm pair of PN pairs was used as a thermoelectric conversion element, using a half-Heussler element with a Ni base gold electrode of 3 mm ⁇ 3 mm ⁇ 5 mmt.
  • As the insulating layer aluminum nitride having a thickness of 0.635 mm was used.
  • the first aluminum layer and the second aluminum layer are formed by bonding a foil having a purity of 99.99 mass% and a thickness of 0.25 mm, and the thickness of the first silver fired layer, the thermoelectric conversion element and the first silver fired layer
  • the joining temperature and joining load were as described in Table 1.
  • the bonding atmosphere was as described in Table 1, and the thermoelectric conversion element and the first electrode portion were directly laminated and bonded in the bonding of the thermoelectric conversion element and the first electrode portion.
  • the second silver fired layer was similar to the first silver fired layer, and the second electrode portion was similar to the first electrode portion.
  • thermoelectric conversion module The temperature on the first heat transfer plate side of the thermoelectric conversion module produced was 450 ° C., the temperature on the second heat transfer plate side was 50 ° C., and the electrical resistance (internal resistance) was measured (initial resistance). In addition, the temperature difference was continuously applied to the thermoelectric conversion module, the rate of increase from the initial value of the internal resistance with respect to time elapsed was calculated, and the durability of the thermoelectric conversion module after 24 hours elapsed was evaluated (internal resistance increase rate). As for internal resistance, a variable resistance is installed between the output terminals of the thermoelectric conversion module with the temperature difference as described above, and the resistance is changed to measure the current value and the voltage value. Create a graph with the voltage value on the vertical axis.
  • thermoelectric conversion modules After mechanically polishing the cross section of the first silver baked layer of each of the obtained thermoelectric conversion modules, Ar ion etching (cross section polisher SM-09010 manufactured by Nippon Denshi Co., Ltd.) is performed, and a laser microscope (VKX-200 manufactured by Keyence Corporation) is performed. Cross-sectional observation was performed using. Then, the obtained image was subjected to a binarization treatment, and the white portion was made Ag, and the black portion was made pores. The area of the black part was determined from the binarized image, and the porosity was calculated by the following equation.
  • Comparative Example 1 in which the first silver fired layer was formed such that the thickness of the first silver fired layer was less than 5 ⁇ m, the first silver fired layer and the thermoelectric conversion element could not be joined. It is considered that this is because the first silver baked layer has been embedded in the first aluminum layer.
  • Comparative Example 2 where the heating temperature was low, the porosity was over 10%, so the rate of increase in internal resistance was high.
  • Comparative Example 3 in which the pressing load was less than 20 MPa, the porosity was high and the initial resistance was high. Therefore, the rate of increase in internal resistance was not measured.
  • Comparative Example 4 in which the bonding temperature exceeded 400 ° C., the first aluminum layer was crushed. Therefore, in Comparative Example 4, the porosity and the electrical resistance were not evaluated.
  • thermoelectric conversion module was obtained in which the thickness of the first silver fired layer is 5 ⁇ m or more, the porosity is less than 10%, and the internal resistance increase rate is also low.
  • Example 2 By the same method as in Example 1, the thickness of the first silver fired layer was changed as shown in Table 2, and the presence or absence of the blast treatment was changed to produce various thermoelectric conversion modules.
  • the bonding atmosphere was vacuum
  • the pressure load was 30 MPa
  • the heating temperature was 350 ° C.
  • the porosity of the first silver fired layer was measured in the same manner as in Example 1.
  • the cooling-heat cycle was loaded on the following conditions with respect to the obtained thermoelectric conversion module.
  • the cooling and heating cycle was performed under the atmosphere, giving 50 cycles of 150 ° C. ⁇ 5 minutes ⁇ ⁇ 450 ° C. ⁇ 5 minutes on the high temperature side and fixing the temperature on the low temperature side at 80 ° C.
  • the initial internal resistance and the rate of increase in internal resistance after the thermal cycle load were determined.
  • the evaluation results are shown in Table 2.
  • the internal resistance increase rate after cold thermal cycle load was evaluated as “A” when the increase rate was less than 1%, and “B” when the increase rate was 1% or more.
  • thermoelectric conversion module of Inventive Example 1 When a thermal cycle was loaded on the thermoelectric conversion module of Inventive Example 1, the rate of increase in internal resistance after the thermal cycle exceeded 1%. This is because the thermoelectric conversion module subjected to the blast treatment to the first silver fired layer can suppress the rate of increase in internal resistance low when used under a constant temperature, but high temperature and low temperature are repeated When used under environment, it means that internal resistance will rise.
  • thermoelectric conversion modules of the invention examples 11 to 14 in which the blast treatment was not performed on the first silver fired layer, the increase rate of the internal resistance could be suppressed low even if the cooling thermal cycle was loaded.
  • the thermoelectric conversion module which has not been subjected to blasting to the first silver fired layer is useful in an environment where high and low temperatures are repeated. It was also confirmed that by setting the thickness of the silver fired layer in the range of 20 ⁇ m to 100 ⁇ m, the initial internal resistance can be lowered, and the rate of increase in the internal resistance after cooling and heating cycles can be suppressed low.
  • the present invention provides a thermoelectric conversion module which has low electric resistance in the electrode portion and suppresses deterioration of the thermoelectric conversion element at the time of bonding, and which has excellent thermoelectric conversion efficiency, and a method of manufacturing the thermoelectric conversion module. can do.

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Abstract

L'invention concerne un module de conversion thermoélectrique 10 comprenant un élément de conversion thermoélectrique 11; et une première carte de circuit imprimé isolante, qui comprend une première couche isolante 21 et une première partie d'électrode 25 qui est formée sur une surface de la première couche isolante 21, est disposée à une extrémité de l'élément de conversion thermoélectrique 11. La première partie d'électrode 25 comprend : une première couche d'aluminium 25a qui est formée à partir d'aluminium ou d'un alliage d'aluminium; et une première couche d'argent calcinée 25b qui est formée sur une surface de la première couche d'aluminium 25a à partir d'un corps calciné d'argent, ladite surface étant sur le côté inverse de la surface latérale de la première couche isolante 21. La première couche d'aluminium 25a est configurée pour avoir une épaisseur dans la plage allant de 50 µm à 2000 µm (inclus). La première couche d'argent calcinée 25b est configurée pour avoir une épaisseur d'au minimum 5 µm et une porosité inférieure à 10 % au moins dans une région où l'élément de conversion thermoélectrique 11 est agencé.
PCT/JP2018/024828 2017-07-05 2018-06-29 Module de conversion thermoélectrique et procédé de production de module de conversion thermoélectrique WO2019009202A1 (fr)

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CN201880036600.XA CN110710008B (zh) 2017-07-05 2018-06-29 热电转换模块及热电转换模块的制造方法
KR1020197034156A KR20200026797A (ko) 2017-07-05 2018-06-29 열전 변환 모듈, 및, 열전 변환 모듈의 제조 방법
EP18828546.4A EP3651217A4 (fr) 2017-07-05 2018-06-29 Module de conversion thermoélectrique et procédé de production de module de conversion thermoélectrique
US16/608,469 US20210111327A1 (en) 2017-07-05 2018-06-29 Thermoelectric conversion module and method for producing thermoelectric conversion module

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