JP2011003640A - Method for manufacturing thermoelectric conversion module and thermoelectric conversion module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently manufacture a thermoelectric conversion module with the high occupancy of a thermoelectric conversion material, low resistance, and an excellent characteristic.SOLUTION: A joint body 13 with a P-type thermoelectric conversion material 11 and an N-type thermoelectric conversion material 12 joined via an insulating material 14a is plated so as to form plated electrodes 16, each of which is constituted of a plated film, in other than the regions joined via the insulating material concerning the P-type thermoelectric conversion material and the N-type thermoelectric conversion material. Then, the joined body with the plated electrodes formed thereon is thermally processed under an oxidizing atmosphere. Besides, the plated electrode formed on the P-type thermoelectric conversion material and the plated electrode formed on the N-type thermoelectric conversion material are electrically connected via metallic plates 15. The joined body with the plated electrodes formed thereon is thermally processed at the temperature of 400-500°C. The thermoelectric conversion material made of an oxide is used as the P-type thermoelectric conversion material and the N-type thermoelectric conversion material.

Description

  The present invention relates to a method for manufacturing a thermoelectric conversion module and a thermoelectric conversion module, and more particularly to a method for manufacturing a thermoelectric conversion module having a high occupation ratio of a thermoelectric conversion material and a thermoelectric conversion module manufactured by the manufacturing method.

  In recent years, the reduction of carbon dioxide has become an important issue in order to prevent global warming, and thermoelectric conversion elements that can directly convert heat into electricity have attracted attention as an effective waste heat utilization technology. ing.

  As a conventional thermoelectric conversion element, for example, as shown in FIG. 8, a structure including a P-type thermoelectric conversion material 51, an N-type thermoelectric conversion material 52, a low temperature side electrode 56, and a high temperature side electrode 58 is provided. A thermoelectric conversion element 50 is known.

In this thermoelectric conversion element 50, the two types of thermoelectric conversion materials 51 and 52 are energy conversion materials of heat and electricity, and are connected to the low temperature side electrode 56 at the low temperature side junction portion 53b which is the end surface of each low temperature side. ing. Further, the thermoelectric conversion materials 51 and 52 are connected via a high temperature side electrode 58 at a high temperature side joint portion 53a which is an end surface on the high temperature side.
And in this thermoelectric conversion element 50, when a temperature difference is given to the high temperature side junction part 53a and the low temperature side junction part 53b, an electromotive force will arise by Seebeck effect and electric power will be taken out.

  By the way, the power generation capability of the thermoelectric conversion element is determined by the thermoelectric conversion characteristics of the material and the temperature difference applied to the element, but the occupation rate of the thermoelectric conversion material (thermoelectric conversion in a plane perpendicular to the direction of the temperature difference occurring in the thermoelectric conversion element) The influence of the ratio of the area occupied by the material portion is also great, and the power generation capacity per unit area of the thermoelectric conversion element can be increased by increasing the occupation ratio of the thermoelectric conversion material.

  However, in the case of the structure of the conventional thermoelectric conversion element 50, since an insulating gap layer is provided between the two types of thermoelectric conversion materials 51 and 52, the occupation ratio of the thermoelectric conversion material is increased. Is naturally limited.

  Therefore, for example, as shown in FIGS. 9A and 9B, the P-type thermoelectric conversion material 51 and the N-type thermoelectric conversion material 52 are joined via the insulating layer 61, and on the upper surface side and the lower surface side, A thermoelectric conversion module in which a P-type thermoelectric conversion material 51 and an N-type thermoelectric conversion material 52 are electrically joined via an electrode 62 has been proposed (see Patent Document 1).

  Specifically, as shown in FIG. 9B, the side surfaces (bonding surfaces) of the P-type thermoelectric conversion material 51 and the N-type thermoelectric conversion material 52 are bonded via an insulating layer 61, and the upper surface A carbon electrode 71 is arranged on the side, and a nickel-based braze 72 and a plate-like molybdenum electrode 73 are arranged in this order on the carbon electrode 71, and the electrode 62 made of these and the P-type thermoelectric conversion material 51. An N-type thermoelectric conversion material 52 is electrically connected. That is, in this thermoelectric conversion module, a P-type thermoelectric conversion material 51 made of a Si—Ge semiconductor and an N-type thermoelectric conversion material 52 are joined via a vitreous insulating layer 61, and then the P-type thermoelectric conversion material 51. In order to connect the N-type thermoelectric conversion material 52 in series, a plate-like molybdenum electrode 73 is brazed to the carbon electrode 71 with a nickel-based braze 72. In addition, as a material constituting the insulating layer 61, an electrically insulating material in which ceramic particles are dispersed in a glass matrix is used.

  In the thermoelectric conversion module configured as described above, the P-type thermoelectric conversion material 51 and the N-type thermoelectric conversion material 52 are joined via the insulating layer 61, and there is no gap between them. The occupation ratio of the conversion material is high, and the power generation capacity per unit area can be improved.

  However, as in the case of this thermoelectric conversion module, in order to connect the P-type thermoelectric conversion material and the N-type thermoelectric conversion material, a metal plate which is an electrode (for example, a plate-like molybdenum electrode) is brazed by the P-type method. When bonded to a thermoelectric conversion material and an N-type thermoelectric conversion material, depending on the type of P-type thermoelectric conversion material and N-type thermoelectric conversion material, an electrode (for example, a plate-like molybdenum electrode) and P-type and N-type thermoelectric conversion In some cases, the resistance between the material electrode and the thermoelectric conversion module having desired characteristics cannot be obtained.

  In addition, depending on the type of P-type and N-type thermoelectric conversion materials, it may not be possible to reliably bond an electrode (for example, a plate-like molybdenum electrode) to the P-type and N-type thermoelectric conversion materials by a brazing method. There is a problem that a thermoelectric conversion module having desired characteristics cannot be configured.

JP 2000-286467 A

  The present invention has been made in view of the above circumstances, and a metal plate (plate electrode) for electrically connecting a P-type thermoelectric conversion material and an N-type thermoelectric conversion material is suppressed to a low resistance at the joint. However, it is possible to reliably join the P-type and N-type thermoelectric conversion materials, and it is possible to efficiently manufacture a thermoelectric conversion module having a low resistance, a high occupation ratio of the thermoelectric conversion materials, and good characteristics. It is an object of the present invention to provide a method for manufacturing a thermoelectric conversion module and a thermoelectric conversion module having good characteristics manufactured by the method.

In order to solve the above problems, a method for manufacturing a thermoelectric conversion module of the present invention includes:
The P-type thermoelectric conversion material and the N-type thermoelectric conversion material are bonded via an insulating material, and the P-type thermoelectric conversion material and the N-type thermoelectric conversion material are electrically connected in a region other than the region bonded via the insulating material. A method for manufacturing a thermoelectric conversion module having an electrically connected structure,
Preparing a P-type thermoelectric conversion material and an N-type thermoelectric conversion material;
Bonding the P-type thermoelectric conversion material and the N-type thermoelectric conversion material via an insulating material to form a joined body;
A step of forming a plating electrode made of a plating film in a region other than a region of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material joined via the insulating material by plating the joined body. When,
And heat-treating the joined body on which the plating electrode is formed in an oxidizing atmosphere.

  Moreover, the manufacturing method of the thermoelectric conversion module of this invention electrically connects the said plating electrode formed in the said P-type thermoelectric conversion material and the said plating electrode formed in the said N-type thermoelectric conversion material through a metal plate. The method further includes a step of automatically connecting.

  Moreover, in the manufacturing method of the thermoelectric conversion module of this invention, it is preferable that the said oxidizing atmosphere at the time of heat-processing the said joined body in which the said plating electrode was formed is an air atmosphere.

  Moreover, it is preferable that the temperature at the time of heat-processing the said joined body in which the said plating electrode was formed is 400-500 degreeC.

  Further, the P-type thermoelectric conversion material and the N-type thermoelectric conversion material are thermoelectric conversion materials made of an oxide.

The thermoelectric conversion module of the present invention is
The P-type thermoelectric conversion material and the N-type thermoelectric conversion material are joined via an insulating material,
A region of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material other than the region joined via the insulating material is formed of a plating film, and a plating electrode having a specific resistance of 1 Ω · cm or less is formed. ,
The plating electrode formed on the P-type thermoelectric conversion material and the plating electrode formed on the N-type thermoelectric conversion material are electrically connected via a metal plate.

  In the method for manufacturing a thermoelectric conversion module of the present invention, a P-type thermoelectric conversion material and an N-type thermoelectric conversion material are joined via an insulating material to form a joined body, and then the joined body is plated, A plating electrode made of a plating film is formed in a region other than the region bonded via the insulating material, and the joined body of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material on which the plating electrode is formed is oxidized. Since the heat treatment is performed at a predetermined heat treatment temperature in the atmosphere, it is possible to form a plating electrode having a low interface resistance on the surfaces of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material.

  When the plating electrodes formed on the surfaces of the P-type and N-type thermoelectric conversion materials are heat-treated as in the present invention, the high resistance component at the interface between the thermoelectric conversion materials and the plating electrodes is removed, and the resistance is reduced. Although it is reduced, the mechanism is not necessarily clear.

  Moreover, when an electrode (plating electrode) is formed on the P-type thermoelectric conversion material and the N-type thermoelectric conversion material by a plating method, the plating film is applied to all regions other than the region joined via the insulating material. It becomes possible to form an electrode (plating electrode) to be formed, and it is possible to secure a wide area of a surface functioning as an electrically conductive surface and a heat transfer surface.

  Moreover, the plating electrode formed in the P-type thermoelectric conversion material and the plating electrode formed in the N-type thermoelectric conversion material are electrically connected through the metal plate, that is, the metal plate is connected to the P-type and the N-type. By arranging so as to be joined to each of the plating electrodes formed on the thermoelectric conversion material, the P-type thermoelectric conversion material and the N-type thermoelectric conversion material are connected in series via the plating electrode and the metal plate having a low interface resistance. It is possible to efficiently manufacture a connected thermoelectric conversion module with good characteristics.

  In the manufacturing method of the thermoelectric conversion module of the present invention, it is preferable that the oxidizing atmosphere when heat-treating the joined body on which the plating electrode is formed is an air atmosphere. By heat-treating in an air atmosphere, it is possible to efficiently remove the high resistance component at the interface between the thermoelectric conversion material and the plating electrode without using a special atmosphere gas, and to form a plating electrode with a low interface resistance. become.

In addition, by setting the heat treatment temperature when the bonded body on which the plating electrode is formed to 400 to 500 ° C., it is possible to reliably suppress and prevent the plating electrode from being oxidized, and to reduce the resistance of the plating electrode. It becomes possible to obtain.
Note that when the heat treatment temperature is less than 400 ° C., the effect of reducing the resistance by the heat treatment becomes insufficient. On the other hand, when the heat treatment temperature exceeds 500 ° C., the electrode (plating electrode) is oxidized and the resistance is increased. Therefore, the heat treatment temperature is desirably in the range of 400 to 500 ° C.

In addition, when the P-type thermoelectric conversion material and the N-type thermoelectric conversion material are oxide thermoelectric conversion materials, the conventional brazing method converts the metal plate into the P-type thermoelectric conversion material and the N-type thermoelectric conversion material. Although it is difficult to join, as in the present invention, a plating electrode made of a plating film and having a specific resistance of 1 Ω · cm or less is formed on the surface of the thermoelectric conversion material, and the metal is interposed through the plating electrode. By joining the plates, the metal plate is securely joined to the surfaces of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material, and the P-type thermoelectric conversion material and the N-type thermoelectric conversion material are connected in series. This makes it possible to reliably manufacture the thermoelectric conversion module, which is particularly meaningful.
In addition, the plating electrode whose specific resistance is 1 ohm * cm or less can be reliably formed by using the manufacturing method of the thermoelectric conversion module of this invention.

  In the thermoelectric conversion module of the present invention, the P-type thermoelectric conversion material and the N-type thermoelectric conversion material are joined via an insulating material, and the P-type and N-type thermoelectric conversion materials are joined via an insulating material. A plating electrode made of a plating film is formed in a region other than the region, and the plating electrode formed in the P-type thermoelectric conversion material and the plating electrode formed in the N-type thermoelectric conversion material are electrically connected via the metal plate. Therefore, it is possible to provide a thermoelectric conversion module with good characteristics in which a P-type thermoelectric conversion material and an N-type thermoelectric conversion material are connected in series with low resistance. This thermoelectric conversion module can be reliably and efficiently manufactured by the above-described method for manufacturing a thermoelectric conversion module of the present invention.

It is a figure which shows the state before forming a plating electrode of the thermoelectric conversion element which comprises the thermoelectric conversion module of this invention. It is a thermoelectric conversion element which comprises the thermoelectric conversion module of this invention, Comprising: It is a figure which shows the thermoelectric conversion element which is provided with the plating electrode but is not heat-processed. It is a figure which shows 1 process of the manufacturing method of the thermoelectric conversion module concerning the Example of this invention. It is a figure which shows the state which has arrange | positioned the ceramic spherical particle (zirconium oxide bead) on the glass paste apply | coated to the side surface of the thermoelectric conversion element at the manufacturing process of the thermoelectric conversion module concerning the Example of this invention. It is a figure which shows the state which joined each thermoelectric conversion element at the manufacturing process of the thermoelectric conversion module concerning the Example of this invention. It is a figure which shows the state which formed the plating electrode in the conjugate | zygote at the manufacturing process of the thermoelectric conversion module concerning the Example of this invention. It is a figure which shows the state which joined the metal plate (Cu board) to the joined body through the plating electrode and Cu paste at the manufacturing process of the thermoelectric conversion module concerning the Example of this invention. It is a figure which shows the conventional thermoelectric conversion module. It is a figure which shows the other conventional thermoelectric conversion module, (a) is a front view, (b) is a figure which expands and shows the principal part.

  Examples of the present invention will be described below to describe the features of the present invention in more detail.

  In Example 1, a thermoelectric conversion element on which a plating electrode was formed was produced by the following procedure, and its resistance was evaluated.

(1) First,
A) As a P-type thermoelectric conversion material, an oxide semiconductor having a composition of (La _1.98 Sr _0.02 ) CuO ₄ ;
B) The raw material powder was weighed so as to form an N-type thermoelectric conversion material and an oxide semiconductor having a composition of (Nd _1.98 Ce _0.02 ) CuO ₄ .
In addition, oxide powder was used as a raw material powder for La, Nd, Ce, and Cu. Further, carbonate powder was used as the raw material powder of Sr.
The starting material is not limited to the oxides and carbonates as described above, and other inorganic materials such as hydroxides, organometallic compounds such as acetylacetonate complexes, etc. can be used. It is.

  (2) Then, the raw material powder weighed so as to have each composition described above was pulverized and mixed in a wet ball mill using water as a solvent, and then water was evaporated to obtain a mixed powder.

  (3) Next, this mixed powder was heat-treated at 900 ° C. for 8 hours in an air atmosphere to obtain a target composition powder (thermoelectric oxide powder). In this composition powder, an unreacted portion may partially remain.

  (4) An organic binder is mixed in a proportion of 5% by weight with respect to each composition powder in each composition powder obtained by performing the heat treatment of (3) above, and a wet ball mill using water as a solvent is used. Crushed and mixed.

(5) Then, each composition powder mixed with an organic binder was sufficiently dried, and then a compact was produced using a uniaxial press at a pressure of 1 kN / cm ² .

  (6) The molded body was fired in the atmosphere at 1000 ° C. to 1100 ° C. for 2 hours to prepare sintered bodies of the respective composition powders. Here, the firing temperature varies depending on the composition of each composition powder, and is set so that the relative density is 80% or more (preferably 90% or more).

(7) Then, the sintered body was cut into a cube having a size of 5 mm × 5 mm × 5 mm with a tapping saw, and thermoelectric conversion elements serving as a P-type thermoelectric conversion material and an N-type thermoelectric conversion material in the present invention were obtained.
And the glass paste was apply | coated to four side surfaces other than the upper and lower surfaces (conductive surface) of this thermoelectric conversion element, and it was made to dry in 150 degreeC oven.

  (8) Next, the thermoelectric conversion element is introduced into a tunnel furnace set at 900 ° C. in the atmosphere to melt the glass component, and the four side surfaces excluding the upper and lower surfaces are covered with the glass 4 as shown in FIG. The thermoelectric conversion element 1 (1a) before forming the plating electrode was obtained.

  (9) The upper and lower surfaces, which are conductive surfaces not covered with glass, of this thermoelectric conversion element were polished to be flat.

(10) Then, Ni plating is applied to the thermoelectric conversion element 1, and as shown in FIG. 2, Ni plating films (plating electrodes) 6 having a film thickness of 4 to 11 μm are formed on the polished upper and lower surfaces of the thermoelectric conversion element 1. By forming, the thermoelectric conversion element 1 (1b) provided with the plating electrode 6 but not heat-treated was obtained.
The Ni plating film 6 may be formed by any method of electrolytic plating and electroless plating.
At this time, since the four side surfaces of the thermoelectric conversion element 1 are covered with the glass 4, no plating electrodes are formed at all, and the plating electrodes 6 are formed on the entire upper and lower surfaces not covered with the glass. .

  (11) Next, the thermoelectric conversion element 1 (1b) on which the plating electrode is formed is heat-treated in the atmosphere at 400 ° C. for 15 minutes to obtain a heat-treated thermoelectric conversion element (not shown). It was.

  Further, in order to confirm the influence of the heat treatment atmosphere, heat treatment was performed in a nitrogen atmosphere at 400 ° C. for 15 minutes to obtain a comparative thermoelectric conversion element.

And obtained,
(a) thermoelectric conversion element before heat treatment,
(b) a heat-treated thermoelectric conversion element that has been heat-treated in air at 400 ° C. for 15 minutes; and
(c) a thermoelectric conversion element for comparison, which was heat-treated in a nitrogen atmosphere at 400 ° C. for 15 minutes,
About, the resistance (element resistance) of the thermoelectric conversion element provided with the plating electrode was measured. The results are also shown in Table 1.

In addition, as an oxide thermoelectric conversion material having a composition other than the P-type thermoelectric conversion material ((La _1.98 Sr _0.02 ) CuO ₄ ) and the N-type thermoelectric conversion material ((Nd _1.98 Ce _0.02 ) CuO ₄ ), (Li _0.09 Ni _0.91 ) O and a thermoelectric conversion material (P-type thermoelectric conversion material) represented by Ca ₃ Co ₄ O ₇ , under the same conditions as in the above example, the thermoelectric conversion element before heat treatment, the atmosphere A thermoelectric conversion element heat-treated in an atmosphere and a thermoelectric conversion element heat-treated in a nitrogen atmosphere were prepared, and resistance (element resistance) was measured. The results are also shown in Table 1.

  As shown in Table 1, in the case of a thermoelectric conversion element that has been Ni-plated and then heat-treated in an air atmosphere, the resistance (element resistance) of the thermoelectric conversion element through the plating electrode is in the stage before the heat treatment. Compared to this, it was confirmed that it was greatly reduced.

In the case of a thermoelectric conversion element having a composition of (La _1.98 Sr _0.02 ) CuO _4, a significant reduction in element resistance was observed.

Further, in the case of thermoelectric conversion elements having compositions of (Li _0.09 Ni _0.91 ) O and Ca ₃ Co ₄ O ₇ , the degree of decrease in element resistance was small, but a decrease in element resistance of about 40% was still observed.

  Furthermore, it was confirmed that the effect of reducing element resistance when heat treatment was performed in a nitrogen atmosphere (that is, non-oxidizing atmosphere) was significantly inferior to that when heat treatment was performed in an air atmosphere. .

In this Example 2, it was produced in the above Example 1,
A) a P-type thermoelectric conversion material (P-type thermoelectric conversion element) made of an oxide semiconductor whose composition is (La _1.98 Sr _0.02 ) CuO ₄ ;
(B) A thermoelectric conversion module was prepared by using the N-type thermoelectric conversion material (N-type thermoelectric conversion element) made of an oxide semiconductor having a composition of (Nd _1.98 Ce _0.02 ) CuO _{4 according} to the procedure described below.

(1) First, a P-type thermoelectric conversion material (P-type thermoelectric conversion element) made of an oxide semiconductor represented by (La _1.98 Sr _0.02 ) CuO ₄ in (a) above and (Nd _1.98 Ce _0.02 ) in (b) above. An N-type thermoelectric conversion material (N-type thermoelectric conversion element) made of an oxide semiconductor represented by CuO ₄ is prepared. Both the P-type and N-type thermoelectric conversion elements have a cubic shape with dimensions of 5 mm × 5 mm × 5 mm.

  (2) Then, as shown in FIG. 3, a glass paste 14a is applied to four side surfaces of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 other than the upper and lower surfaces (conductive surface). Before the 14a is dried, as shown in FIG. 4, one or more ceramic spherical particles (insulating material particles) (zirconium oxide beads in this Example 2) 10 are distributed at the four corners of the coated surface of the glass paste 14a. Arranged.

(3) Then, as shown in FIG. 5, the surface of one thermoelectric conversion element 11 (or 12) on which ceramic spherical particles (zirconium oxide beads) 10 are arranged has another thermoelectric conversion element 12 (or 11). The joined surface to which the glass paste 14a was applied was joined (temporary joining).
In this way, as shown in FIG. 5, the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 were alternately combined and provisionally joined, and then dried in an oven at 150 ° C.
The diameter of the ceramic spherical particles (zirconium oxide beads) 10 is preferably in the range of 50 to 600 μm. Further, the variation in particle diameter is preferably 20% or less at 3 CV.
Moreover, the glass component which comprises the glass paste 14a should just have the ceramic spherical particle fixed, The composition and density | concentration are suitably selected with the kind, magnitude | size, shape, etc. of the ceramic spherical particle 10. FIG.

  (4) Next, this joined body is introduced into a tunnel furnace set at 900 ° C. in the atmosphere to melt the glass component constituting the glass paste 14a, and the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 A joined body 13 was formed.

(5) Then, after polishing the joined body 13 in which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are joined so that the upper and lower surfaces as the conductive surfaces become flat, the joined body 13 is put in a plating bath. Plating. Thereby, as shown in FIG. 6, the plating electrode 16 which consists of Ni plating film with a film thickness of 4-11 micrometers is formed in the upper and lower surfaces where the joined body 13 was grind | polished. In FIG. 6, only the plating electrode 16 on the upper surface side of the joined body 13 is shown, but a plating electrode is also formed in a symmetrical region on the lower surface side of the joined body 13. Moreover, the glass paste 14a in the stage of FIG. 5 becomes the glass 14 after baking in the stage after FIG. 6, and functions as an insulating material.
Here, as a method of forming the Ni plating film (plating electrode) 16, any method of an electrolytic plating method and an electroless plating method may be used.

  (6) The joined body 13 on which the plating electrode 16 was formed was heat-treated in the atmosphere at 400 ° C. for 15 minutes. Thereby, the high resistance component at the interface between the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 and the plating electrode 16 is removed, and the plating electrode 16 formed on the surfaces of the P-type and N-type thermoelectric conversion materials 11 and 12. Becomes low resistance.

  (7) Next, after applying the Cu paste to the region where the metal plate (copper plate in this embodiment) on the plating electrode 16 is to be joined, as shown in FIG. 7, P-type thermoelectric conversion constituting the joined body 13 The metal plate (Cu plate) 15 having a thickness of 0.5 mm is arranged in a pattern in which the element 11 and the N-type thermoelectric conversion element 12 are connected in series, and heat treatment is performed in nitrogen at 860 ° C. for 15 minutes. Went. Thereby, the Cu plate 15 is fixed to the joined body 13 via the Cu paste, and the thermoelectric conversion module 20 in which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are connected in series is obtained.

  For comparison, in the step (6), a heat treatment was performed at 400 ° C. for 15 minutes in a nitrogen atmosphere, and the other steps were the same, and a thermoelectric conversion module of a comparative example was manufactured.

  And resistance of the thermoelectric conversion module 20 produced as mentioned above and the thermoelectric conversion module of a comparative example was measured.

  As a result, in the above step (6), the heat treatment in the nitrogen atmosphere (reducing atmosphere) was 2650Ω, whereas the heat treatment in the air atmosphere had a low resistance of 65Ω, so It was confirmed that a low-resistance thermoelectric conversion module can be obtained by heat treatment at

  From this result, when heat-treating the joined body on which the plating electrode is formed in the air, the resistance is lower than that heat-treated in a nitrogen atmosphere, and the electric energy generated by thermoelectric conversion is efficiently transferred to the outside. It turns out that the thermoelectric conversion module which can be taken out is obtained.

  In Example 2 described above, glass paste (glass) is used as an insulating material interposed between the P-type thermoelectric conversion material and the N-type thermoelectric conversion material. It is also possible to use an adhesive ceramic paste or the like.

  Moreover, in the said Example 2, although Cu board was used as a metal plate, it is also possible to use Ag board, Mo board, etc. instead of Cu board.

  Further, in the above embodiment, the heat treatment is performed in the air atmosphere when heat-treating the joined body on which the plating electrode is formed. However, the heat treatment is not limited to the air, but should be performed in another oxidizing atmosphere. Is also possible.

  In addition, the present invention is not limited to the above-described embodiments in other points. The composition of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material, the raw material thereof, the specific structure and production of the thermoelectric conversion module. Various applications and modifications can be made within the scope of the invention with respect to specific conditions (for example, dimensions, firing conditions, the number of thermoelectric conversion elements constituting the thermoelectric conversion module, etc.).

As described above, according to the present invention, the metal plate for electrically connecting the P-type thermoelectric conversion material and the N-type thermoelectric conversion material can be used while the resistance at the joint is kept low, and the P-type and N-type thermoelectric conversions. A thermoelectric conversion module that can be reliably bonded to the material, has a high occupation ratio of the thermoelectric conversion material, has low resistance, and has good characteristics can be efficiently manufactured.
Therefore, the present invention can be widely applied to the technical field of thermoelectric conversion modules that require high element occupancy and high thermoelectric conversion efficiency.

DESCRIPTION OF SYMBOLS 1 Thermoelectric conversion element 1a Thermoelectric conversion element before forming a plating electrode 1b Thermoelectric conversion element before heat processing 4 Glass 6 Plating electrode (plating film)
10 Ceramic spherical particles (zirconium oxide beads)
11 P-type thermoelectric conversion material (P-type thermoelectric conversion element)
12 N-type thermoelectric conversion material (N-type thermoelectric conversion element)
13 Joints
14a Glass paste 14 Glass 15 Metal plate (Cu plate)
16 Plating electrode 20 Thermoelectric conversion module

Claims (6)

The P-type thermoelectric conversion material and the N-type thermoelectric conversion material are bonded via an insulating material, and the P-type thermoelectric conversion material and the N-type thermoelectric conversion material are electrically connected in a region other than the region bonded via the insulating material. A method for manufacturing a thermoelectric conversion module having an electrically connected structure,
Preparing a P-type thermoelectric conversion material and an N-type thermoelectric conversion material;
Bonding the P-type thermoelectric conversion material and the N-type thermoelectric conversion material via an insulating material to form a joined body;
A step of forming a plating electrode made of a plating film in a region other than a region of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material joined via the insulating material by plating the joined body. When,
And a step of heat-treating the joined body on which the plating electrode is formed in an oxidizing atmosphere.   The method further comprises a step of electrically connecting the plating electrode formed on the P-type thermoelectric conversion material and the plating electrode formed on the N-type thermoelectric conversion material via a metal plate. The manufacturing method of the thermoelectric conversion module of Claim 1 to do.   The method for manufacturing a thermoelectric conversion module according to claim 1 or 2, wherein the oxidizing atmosphere when heat-treating the joined body on which the plating electrode is formed is an air atmosphere.   The method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 3, wherein a temperature when the joined body on which the plating electrode is formed is heat-treated is 400 to 500 ° C.   The method for manufacturing a thermoelectric conversion module according to claim 1, wherein the P-type thermoelectric conversion material and the N-type thermoelectric conversion material are thermoelectric conversion materials made of oxide. The P-type thermoelectric conversion material and the N-type thermoelectric conversion material are joined via an insulating material,
A region of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material other than the region joined via the insulating material is formed of a plating film, and a plating electrode having a specific resistance of 1 Ω · cm or less is formed. ,
The thermoelectric conversion characterized in that the plating electrode formed on the P-type thermoelectric conversion material and the plating electrode formed on the N-type thermoelectric conversion material are electrically connected via a metal plate. module.

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