JP2018018916A - Thermoelectric conversion module and manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoelectric conversion module having excellent external insulation. SOLUTION: A first thermoelectric material layer A', a first thermoelectric material layer A', is formed between a base film having a first thermoelectric material layer A formed on the front surface and a base film having a second thermoelectric material layer B formed on the back surface. (2) It has a laminated portion composed of an insulating layer composed of a thermoelectric material layer B'and a vapor deposition polymer film, and 1) a first insulating layer portion and a second insulating layer located on both sides of the insulating layer with a margin portion in between. It is composed of layers, 2) the first thermoelectric material layer A'and the second thermoelectric material layer B'are arranged at a portion on the surface of the insulating layer located directly below each layer except for the peripheral edge, and 3) the insulating layer. By introducing the first thermoelectric material or the second thermoelectric material into the margin portion in the above, the thermoelectric so as to electrically connect the adjacent first thermoelectric material layer and the second thermoelectric material layer via the insulating layer. The conversion module was configured. [Selection diagram] Fig. 1

Description

  The present invention relates to a thermoelectric conversion module and a manufacturing method thereof.

  In recent years, expectations for technologies related to energy saving aimed at reducing fossil fuel consumption, and technologies for efficiently using energy that has not been used or have not been fully utilized, have become very high. Yes. Among these various technologies, in particular, a thermoelectric conversion technology capable of directly converting heat energy into electric energy has attracted attention. Here, thermoelectric conversion technology uses a phenomenon (Seebeck effect) in which an electromotive force is generated between both ends of a material having a temperature gradient or between different materials having a temperature difference, and is used as a part of a circuit. It is a technology that extracts electrical energy. Such thermoelectric conversion technology leads to effective use of unused heat (exhaust heat), and has attracted increasing attention as contributing to higher efficiency in energy use.

  Here, in the thermoelectric conversion technology, research and development of a new thermoelectric conversion material having an excellent figure of merit (ZT) is underway, while thermoelectric conversion is made by unitizing thermoelectric conversion elements, insulating plates and electrodes. Module improvements are also underway. As a thermoelectric conversion module, a combination of a plurality of thermoelectric conversion elements in a plate shape or a cylindrical shape is widely known. For example, from a thin film layer made of one thermoelectric conversion material and another thermoelectric conversion material There is known a thermoelectric conversion module having a laminated body in which thin film layers formed are alternately laminated via thin film layers made of an insulator (see Patent Document 1 and Patent Document 2).

  However, as disclosed in Patent Document 1 and Patent Document 2, in a conventional thermoelectric conversion module having a laminate composed of two types of thin film layers of thermoelectric conversion materials and an insulating thin film layer, the lamination In general, a protective layer (see FIG. 2 of Patent Document 1) made of an insulating material is separately provided after the laminated body is manufactured in order to ensure insulation from the outside on the body side. Since such a protective layer is required to be formed according to a process different from the manufacturing process of the laminated body after the laminated body is manufactured, the manufacturing process of the thermoelectric conversion module becomes complicated and it is difficult to reduce the cost. The problem is inherent.

JP 2008-205181 A Japanese Patent No. 5067352

  Here, the present invention has been made against the background of such circumstances, and a problem to be solved is to provide a thermoelectric conversion module excellent in external insulation. Another object of the present invention is to provide a method by which such a thermoelectric conversion module can be advantageously manufactured.

  In order to solve such problems, the present invention provides a first thermoelectric material layer composed of a first thermoelectric material and a second thermoelectric material composed of a second thermoelectric material between a pair of planar rectangular substrate films. A thermoelectric conversion module in which material layers are alternately stacked via insulating layers, and a first thermoelectric material layer and a second thermoelectric material layer adjacent to each other are connected via insulating layers is used. The first thermoelectric material layer A made of the first thermoelectric material, formed on the surface of the base film facing the other base film, and the other base film The first thermoelectric material layer A made of the first thermoelectric material between the second thermoelectric material layer B made of the second thermoelectric material and formed on the surface on the side facing the one base film. ', The second thermoelectric material layer B made of the second thermoelectric material, and the vapor-deposited polymer film. 2) The first thermoelectric material layer A is composed of a main body portion A1 and an external connection portion A2, and includes a laminated portion composed of at least one of the insulating layers. The main body A1 is disposed at a portion excluding the peripheral edge on the surface of the one base film, and the external connection portion A2 is an end on one side on the surface of the one base film. 3) The second thermoelectric material layer B is composed of a main body part B1 and an external connection part B2, and the main body part B1 is arranged in a form extending continuously from the main body part A1. The external connection portion B2 is disposed at a portion excluding the peripheral portion on the surface of the other base film, and the outer connection portion B2 is an end on one side on the surface of the other base film. In a form extending continuously from the main body B1. And 4) the laminated portion includes the one base film and the external connection portion A2 of the first thermoelectric material layer A and the external connection portion B2 of the second thermoelectric material layer B exposed to the outside. 5) The insulating layer constituting the laminated portion is arranged between the other base film and the first insulating layer portion and the second insulating layer located on both sides with a margin portion in between 6) The first thermoelectric material layer A ′ constituting the laminated portion is located at a portion excluding the peripheral edge portion on the surface of the insulating layer located immediately below the first thermoelectric material layer A ′. 7) The second thermoelectric material layer B ′ constituting the laminated portion is arranged at a portion excluding the peripheral portion on the surface of the insulating layer located immediately below the second thermoelectric material layer B ′. 8) In a margin portion between the first insulating layer portion and the second insulating layer portion in the insulating layer The first thermoelectric material layer or the second thermoelectric material layer is connected to the first thermoelectric material layer and the second thermoelectric material layer adjacent to each other through the insulating layer by introducing the first thermoelectric material or the second thermoelectric material. The gist of the thermoelectric conversion module is characterized by this.

  In a preferred embodiment of such a thermoelectric conversion module according to the present invention, 1) the first thermoelectric material layer A further includes an appendix A3, and the appendage A3 On the surface of the base film, in a state opposite to the extending direction from the main body part A1 to the external connection part A2, a margin part is interposed between the main body part A1 and The side surface of the attachment portion A3 opposite to the side surface facing the main body portion A1 is disposed so as to be located inward from the end surface of the one base film, and 2) the second thermoelectric material layer B further includes an attachment B3, and the attachment B3 extends in the direction from the main body B1 to the external connection B2 on the surface of the other base film. A margin part is provided between the body part B1 and the opposite part. And the side surface of the appendage B3 opposite to the side facing the main body B1 is positioned inward from the end surface of the other base film. 3) the first thermoelectric material layer A ′ is formed in a portion excluding the peripheral edge portion on the surface of the insulating layer located immediately below the first thermoelectric material layer A ′; The attachment portion A′2 is configured such that the attachment portion A′2 has a margin portion interposed between the attachment portion A′2 and the main body portion A′1 on the peripheral edge portion of the surface of the insulating layer. In addition, the side surface of the attachment portion A′2 opposite to the side surface facing the main body portion A′1 is disposed so as to be located inward from the end surface of the insulating layer. The peripheral portion of the surface of the insulating layer where the second thermoelectric material layer B ′ is located immediately below the second thermoelectric material layer B ′ A body portion B′1 formed at a portion to be removed and an attachment portion B′2 are formed, and the attachment portion B′2 is formed on the peripheral edge portion on the surface of the insulating layer. And a side surface opposite to the side surface facing the main body portion B′1 of the attachment portion B′2 is located inward from the end surface of the insulating layer. To be arranged.

On the other hand, the present invention is a method that can advantageously manufacture the thermoelectric conversion module of the above-described embodiment, that is, 1) according to a manufacturing method having the following steps 1 to 5 or manufacturing having the following steps 1 to 3. According to the method, the first thermoelectric material layer A is formed on one base film, and the outermost surface layer is the first thermoelectric material layer A ′ made of the first thermoelectric material or the second thermoelectric material. A step of preparing a laminate I which is one of the second thermoelectric material layers B ′ made of a material, and 2) a manufacturing method having the following steps 1 ′ to 5 ′ or a manufacturing method having the following step 1 ′ The second thermoelectric material layer B is formed on the other base film, and the outermost surface layer is composed of the same thermoelectric material as that constituting the outermost surface layer of the laminate I. A step of preparing the laminated body II, and 3) the laminated body I The gist of the present invention is also a method of manufacturing a thermoelectric conversion module including a step of superimposing and integrating the laminate II so that the outermost surface layers of the laminate are in contact with each other.
Step 1: A first thermoelectric material layer A made of a first thermoelectric material and composed of a main body portion A1 and an external connection portion A2 is formed on one surface of one base film according to a vapor phase growth method. The main body part A1 is formed on a part excluding the peripheral part on the surface of the one base film, and the external connection part A2 is on an end on one side of the surface of the base film. It forms in the form extended continuously from this main-body part A1.
Step 2: After forming the first thermoelectric material layer A, on the portion of the base film surface on which the first thermoelectric material layer A is formed, excluding the end on the external connection portion A2 side, The insulating layer C1 composed of the first insulating layer portion and the second insulating layer portion is subjected to a vapor deposition polymerization method so that the first insulating layer portion and the second insulating layer portion are located on both sides with a margin portion interposed therebetween. Form.
Step 3: After forming the insulating layer C1, a second thermoelectric material layer B ′ made of the second thermoelectric material is formed on the insulating layer C1 surface excluding the peripheral edge according to the vapor phase growth method. The second thermoelectric material is introduced into the marginal portion existing between the first insulating layer portion and the second insulating layer portion of the insulating layer C1.
Step 4: After forming the second thermoelectric material layer B ′, the first insulation is formed on the second thermoelectric material layer B ′ and on the non-formation portion of the second thermoelectric material layer B ′ in the insulating layer C1. The insulating layer C2 composed of the layer portion and the second insulating layer portion is formed according to the vapor deposition polymerization method so that the first insulating layer portion and the second insulating layer portion are located on both sides with the margin portion interposed therebetween.
Step 5: After the insulating layer C2 is formed, a first thermoelectric material layer A ′ made of the first thermoelectric material is formed on the insulating layer C2 surface excluding the peripheral portion according to the vapor phase growth method. The first thermoelectric material is introduced into the marginal portion existing between the first insulating layer portion and the second insulating layer portion of the insulating layer C2.
Step 1 ′: The second thermoelectric material layer B made of the second thermoelectric material and composed of the main body portion B1 and the external connection portion B2 is formed on one surface of the other base film by vapor deposition. Accordingly, the main body B1 is formed on a portion excluding the peripheral edge on the surface of the other base film, and the external connection portion B2 is formed on the surface of the other base film. It is formed in a form extending continuously from the main body B1 on one side end.
Step 2 ′: After forming the second thermoelectric material layer B, the portion excluding the end on the external connection portion B2 side on the surface of the other base film on which the second thermoelectric material layer B is formed On top, the insulating layer C1 ′ composed of the first insulating layer portion and the second insulating layer portion is arranged so that the first insulating layer portion and the second insulating layer portion are located on both sides with the margin portion interposed therebetween. It is formed according to the vapor polymerization method.
Step 3 ′: After forming the insulating layer C1 ′, a first thermoelectric material layer A ′ made of the first thermoelectric material is formed on the insulating layer C1 ′ surface excluding the peripheral edge according to the vapor phase growth method. At the same time, the first thermoelectric material is introduced into a margin portion existing between the first insulating layer portion and the second insulating layer portion of the insulating layer C1 ′.
Step 4 ′: After forming the first thermoelectric material layer A ′, on the first thermoelectric material layer A ′ and on the non-formation portion of the first thermoelectric material layer A ′ in the insulating layer C1 ′. The vapor deposition polymerization method is used to form the insulating layer C2 ′ composed of the first insulating layer portion and the second insulating layer portion so that the first insulating layer portion and the second insulating layer portion are located on both sides with the margin portion interposed therebetween. Form according to.
Step 5 ′: After forming the insulating layer C2 ′, a second thermoelectric material layer B ′ made of the second thermoelectric material is formed on the portion excluding the peripheral edge on the surface of the insulating layer C2 ′ according to the vapor phase growth method. At the same time, the second thermoelectric material is introduced into a margin portion existing between the first insulating layer portion and the second insulating layer portion of the insulating layer C2 ′.

  As described above, in the thermoelectric conversion module according to the present invention, the first thermoelectric material layer A ′ made of the first thermoelectric material and the second thermoelectric material layer B ′ made of the second thermoelectric material constituting the laminated portion. Are formed in a portion excluding the peripheral portion on the surface of the insulating layer disposed immediately below each of the layers, so that the first thermoelectric material layer A ′ and the second The end face of the two thermoelectric material layer B ′ is not exposed. Therefore, in the thermoelectric conversion module of the present invention, the conventional thermoelectric conversion module having a laminate composed of a thin film layer of two types of thermoelectric conversion materials and a thin film layer of an insulator is required. Therefore, it is not necessary to separately form a protective layer or the like for ensuring insulation with respect to the conventional structure. It is.

In the thermoelectric conversion module of the present invention, since the insulating layer constituting the laminated portion is a vapor-deposited polymer film that is a thin film made of synthetic resin having insulating properties, a conventional insulating layer made of an inorganic material such as SiO ₂ It is possible to easily reduce the weight as compared with a thermoelectric conversion module having Furthermore, by using the vapor deposition polymer film as an insulating layer, the thermal conductivity of the entire module can be effectively suppressed, and the figure of merit (ZT) as a module is advantageously improved.

  In addition, in the method for producing a thermoelectric conversion module according to the present invention, the first thermoelectric material layer and the second thermoelectric material layer are formed according to the vapor phase growth method, and the insulating layer is formed according to the vapor deposition polymerization method, respectively. Since the thinning of each of these layers is easy, the thermoelectric conversion module can be easily reduced in size, and a thermoelectric conversion module having excellent volume efficiency (thermoelectric conversion efficiency per unit volume) can be manufactured. In addition, since it is easy to make a thin film, it is possible to increase the number of series of two types of thermoelectric material layers (the number of stacked layers) as compared with the conventional manufacturing method. Thermoelectric conversion modules can be manufactured by selecting general-purpose materials because they can be used as thermoelectric materials even in the case of metal materials and alloy materials with a small Seebeck coefficient compared to P-type semiconductors and N-type semiconductors. Cost reduction can be advantageously achieved.

It is a perspective view showing one embodiment of a thermoelectric conversion module concerning the present invention. It is a front view of the thermoelectric conversion module shown in FIG. It is a left view of the thermoelectric conversion module shown in FIG. It is a right view of the thermoelectric conversion module shown in FIG. It is a top view of the thermoelectric conversion module shown in FIG. FIG. 6 is an enlarged explanatory diagram of a cross section taken along the line I-I ′ of FIG. 5. 6A is a cross-sectional view taken along the line II-II ′ of FIG. 6, FIG. 6B is a cross-sectional view taken along the line III-III ′ of FIG. 6, FIG. -V 'sectional drawing, (e) is VI-VI' sectional drawing of FIG. 6, (f) is VII-VII 'sectional drawing of FIG. It is a top view of the thermoelectric conversion module which concerns on other one Embodiment of this invention. FIG. 9 is an enlarged explanatory view of a section taken along i-i ′ in FIG. 8. 9A is a cross-sectional view taken along line ii-ii ′ in FIG. 9, FIG. 9B is a cross-sectional view taken along line iii-iii ′ in FIG. 9, FIG. 9C is a cross-sectional view taken along line iv-iv ′ in FIG. -V 'sectional drawing, (e) is VI-VI' sectional drawing of FIG. 9, (f) is VII-VII 'sectional drawing of FIG. It is a schematic explanatory drawing which shows an example of the manufacturing apparatus used advantageously when manufacturing the thermoelectric conversion module of this invention. FIG. 12A is a cross-sectional explanatory view showing an internal structure and FIG. 12B is a bottom view of one thermoelectric material layer forming apparatus in the manufacturing apparatus shown in FIG. FIG. 12A is a cross-sectional explanatory view showing an internal structure and FIG. 12B is a bottom view of one insulating layer forming apparatus in the manufacturing apparatus shown in FIG. It is a bottom view about the other thermoelectric material layer forming apparatus in the manufacturing apparatus shown in FIG. It is a bottom view about the other insulating layer forming apparatus in the manufacturing apparatus shown in FIG. It is explanatory drawing which shows the state after completion | finish of each process in the manufacturing apparatus shown in FIG. It is explanatory drawing which shows the process at the time of manufacturing the thermoelectric conversion module of this invention from two laminated bodies. It is explanatory drawing which shows one of the usage aspects of the thermoelectric conversion module which concerns on this invention. (A) is a right view of the wound body of the thermoelectric conversion module which concerns on this invention, (b) is explanatory drawing which shows the use aspect.

  Hereinafter, in order to clarify the present invention more specifically, representative embodiments of the present invention will be described in detail with appropriate reference to the drawings. It should be understood that the drawings referred to in the following description are all exaggerated for the purpose of facilitating the understanding of the present invention. Should.

  1 to 5 show a thermoelectric conversion module 10 according to an embodiment of the present invention in a perspective view in FIG. 1, a front view in FIG. 2, a left side view in FIG. Are shown in a right side view and in FIG. 5 in a plan view. As is clear from these drawings, the thermoelectric conversion module 10 is configured by a laminated portion 14 interposed between two base film 12a and 12b having a planar rectangular shape. The laminated portion 14 has three side surfaces (the front surface, the left side surface, and the back surface in FIGS. 1 to 5) that are flush with the end surfaces of the base films 12a and 12b, while the remaining one side surface (same as above). , The right side surface) has a slightly recessed shape toward the opposite side surface. With such a configuration, the external connection portion 16b of the first thermoelectric material layer 16 made of the first thermoelectric material provided on the surface (upper surface) of the base film 12a and the back surface (lower surface) of the base film 12b. The external connection portion 18b of the second thermoelectric material layer 18 made of the second thermoelectric material is exposed to the outside.

  As the base films 12a and 12b, any material can be adopted as long as it is made of an insulating material, but a resin film made of a synthetic resin material is preferably used. It is done. Specifically, a resin film having a thickness of about 1 to 10 μm made of polyimide, polyphenylene sulfide (PPS), polyethylene terephthalate, polyethylene naphthalate, or the like is advantageously used. The synthetic resin materials constituting the base films 12a and 12b may be different as a matter of course when they are the same.

  FIG. 6 shows a cross-sectional view of the thermoelectric conversion module 10 shown in a plan view in FIG. 5 taken along the I-I ′ plane. 7A to 7F, the II-II ′ plane, the III-III ′ plane, the IV-IV ′ plane, the VV ′ plane, the VI-VI ′ plane, and the VII-VII plane in FIG. 'Cross sections on each side of the plane are shown. Each layer constituting the thermoelectric conversion module 10 will be described in detail with reference to FIGS. 6 and 7.

  First, the first thermoelectric material layer 16 made of the first thermoelectric material is composed of a main body portion 16a formed on a surface (upper surface) of the base film 12a except a peripheral portion, and one end portion from the main body portion. It is comprised from the external connection part 16b which exhibits the form continuously extended toward (right end part in FIG.6 and FIG.7 (a)) (refer FIG.7 (a)).

  Moreover, the insulating layer 20 arrange | positioned on the 1st thermoelectric material layer 16 is comprised by the vapor deposition polymerization film | membrane of insulating synthetic resin. The insulating layer 20 has a first portion 20a and a second portion 20b located on both sides with the margin portion 21 therebetween, and the external connection portion 16b of the first thermoelectric material layer 16 on the base film 12 is It is formed in such a form that the end portion on the formed side is exposed (see FIG. 7B). The margin portion 21 is disposed on the end portion of the first thermoelectric material layer 16 opposite to the external connection portion 16b. And the 2nd thermoelectric material which comprises the 2nd thermoelectric material layer 22 mentioned later invades the site | part corresponding to the 2nd thermoelectric material layer 22 in the margin part 21, and forms the connection part 22a, This connection Since the part 22a is in contact with the first thermoelectric material layer 16 (the main body part 16a), the first thermoelectric material layer 16 and the second thermoelectric material layer 22 are connected (FIGS. 6 and 7). (See (b)). In the present specification and claims, the connection between the first thermoelectric material layer and the second thermoelectric material layer means that a current can flow due to an electromotive force generated by the Seebeck effect. This means that it is in an electrically connected state.

  Further, a second thermoelectric material layer 22 made of the second thermoelectric material is disposed on the insulating layer 20. The second thermoelectric material layer 22 is formed at a portion of the insulating layer 20 excluding the peripheral edge. That is, the second thermoelectric material layer 22 is formed in such a form that each end face is not exposed on any of the four side faces of the laminated portion 14. In addition, the peripheral part of the 2nd thermoelectric material layer 22 is covered with the vapor deposition polymerization film which comprises the insulating layer 24 mentioned later (refer FIG.7 (c)).

  Furthermore, an insulating layer 24 made of a vapor-deposited polymer film of an insulating synthetic resin is formed on the second thermoelectric material layer 22. Similarly to the insulating layer 20 described above, the insulating layer 24 also includes a first portion 24a and a second portion 24b located on both sides of the margin portion 25, and the insulating layer 20 including the margin portion 21 is included. Is formed in a size (range) corresponding to. In addition, a first thermoelectric material constituting the first thermoelectric material layer 26, which will be described later, penetrates into a portion corresponding to the first thermoelectric material layer 26 in the margin portion 25 to form a connection portion 26a. Since the portion 26 a is in contact with the second thermoelectric material layer 22, electrical connection between the second thermoelectric material layer 22 and the first thermoelectric material layer 26 is ensured. In addition, the margin part 25 of the insulating layer 24 is disposed at the end of the insulating layer 20 opposite to the side where the margin part is provided. Thus, by providing the two margin portions interposing the thermoelectric material layer alternately in the opposing direction of the heating source (or heated body) and the cooling source (or cooled body), the first thermoelectric material layer and An inter-series distance with the second thermoelectric material layer: l (see FIG. 6) can be advantageously ensured.

  In addition, a first thermoelectric material layer 26 made of the first thermoelectric material is disposed on the insulating layer 24. Even in the first thermoelectric material layer 26, the insulating layer 24 is formed at a portion excluding the peripheral edge. That is, the first thermoelectric material layer 26 is formed in such a form that each end face is not exposed on any of the four side faces of the laminated portion 14. Note that the thermoelectric conversion module 10 shown in FIG. 6 and the like is manufactured according to a manufacturing method described later, and is formed as a thermoelectric conversion module 10 that is an integrated object by integrating two laminated bodies. is there. Therefore, the first thermoelectric material layer 26 includes the first thermoelectric material layer provided on the outermost surface of one laminate (the laminate on the substrate film 12a side) and the other one laminate (the substrate film 12b side). The first thermoelectric material layer provided on the outermost surface of the laminate is integrally formed.

  On the first thermoelectric material layer 26, an insulating layer 28 made of a vapor-deposited polymer film of an insulating synthetic resin is disposed. The insulating layer 28 has the same size and shape as the insulating layer 20 described above, and the arrangement thereof is the same as that of the insulating layer 20. A first thermoelectric material constituting the first thermoelectric material layer 26 penetrates into a margin portion 29 interposed between the two portions of the insulating layer 28 to form a connection portion 26b. With the connection portion 26b, Electrical connection between the first thermoelectric material layer 26 and the second thermoelectric material layer 30 is ensured.

  Furthermore, a second thermoelectric material layer 30 made of the second thermoelectric material is disposed on the insulating layer 28. The second thermoelectric material layer 30 has the same size and shape as the second thermoelectric material layer 22 described above, and the arrangement thereof is the same as that of the second thermoelectric material layer 22.

  In addition, an insulating layer 32 made of a vapor-deposited polymer film of an insulating synthetic resin is disposed on the second thermoelectric material layer 30. The insulating layer 32 has the same size and shape as the insulating layer 24 described above, and the arrangement thereof is the same as that of the insulating layer 24. A second thermoelectric material constituting the second thermoelectric material layer 30 enters the margin portion 33 interposed between the two portions of the insulating layer 32 to form a connection portion 30a. The electrical connection between the second thermoelectric material layer 30 and the first thermoelectric material layer 34 is ensured.

  A first thermoelectric material layer 34 made of the first thermoelectric material is disposed on the insulating layer 32. The first thermoelectric material layer 34 has the same size and shape as the first thermoelectric material layer 26 described above.

  Furthermore, an insulating layer 36 made of a vapor-deposited polymer film of insulating synthetic resin is disposed on the first thermoelectric material layer 34. The insulating layer 36 has the same size and shape as the insulating layer 20 described above, and the arrangement thereof is the same as that of the insulating layer 20. A first thermoelectric material constituting the first thermoelectric material layer 34 enters the margin portion 37 interposed between the two partial buildings of the insulating layer 36 to form a connection portion 34a. The electrical connection between the first thermoelectric material layer 34 and the second thermoelectric material layer 18 is ensured.

  In addition, the second thermoelectric material layer 18 made of the second thermoelectric material is disposed on the insulating layer 36. The second thermoelectric material layer 18 includes a main body portion 18a formed on a portion of the back surface (lower surface) of the base film 12b excluding the peripheral portion, and one end portion from the main body portion (FIGS. 6 and 7 (f). ) Is formed of an external connection portion 18b that continuously extends toward the right end portion), and the external connection portion 18b is exposed to the outside (see FIG. 7 (f)). .

  As described above, in the thermoelectric conversion module 10 according to the present invention, the end surfaces of the first thermoelectric material layer and the second thermoelectric material layer are not exposed to the outside at all except for the external connection portions 16b and 18b. The insulation from the outside is advantageously ensured. Therefore, a protective layer for ensuring insulation from the outside, which is required in the conventional thermoelectric conversion module in which different thermoelectric material layers are laminated, is not necessary. Cost reduction by reducing the production process of the protective layer and the like is advantageously achieved.

Further, in the thermoelectric conversion module of the present invention, since a vapor-deposited polymer film, which is a thin film made of an insulating synthetic resin, is used as an insulating layer, a conventional thermoelectric module having an insulating layer made of an inorganic material such as SiO ₂ is used. Compared with the conversion module, the weight can be easily reduced, and in addition, the thickness in the stacking direction can be reduced. Furthermore, by using a vapor-deposited polymer film as an insulating layer, it is possible to effectively keep the thermal conductivity of the entire module low, and the figure of merit (ZT) as a module is advantageously improved. .

Here, as the thermoelectric material used in the thermoelectric conversion module of the present invention, it is possible to appropriately select and use a conventionally-known thermoelectric material according to the target thermoelectric conversion module. is there. In addition, by following the manufacturing method described later, it is possible to increase the number of two types of thermoelectric material layers in series (the number of stacked layers). Therefore, a metal with a small Seebeck coefficient compared to a P-type semiconductor or N-type semiconductor. Even materials and alloy materials can be used. Specific examples of thermoelectric materials that can be used in the present invention include tellurium compound systems such as Bi ₂ Te ₃ , PbTe, AgSbTe ₂ / GeTe, Bi ₂ Te ₃ / Sb ₂ Te ₃ , NaCo ₂ O ₄ , CaCoO _3. SrTiO ₃ / SrTiO ₃ : Metal oxides such as Nb, SiGe, β-FeSi ₂ , Ba ₈ Si ₄₈ , Mg ₂ Si, MnSi _{1.73 and} other silicon compounds, ZnSb, InSb, Zn ₄ Sb ₃ , CeFe ₃ CoSb ₁₂ , antimony compounds such as LaFe ₃ CoSb ₁₂ , alloys such as constantan, chromel, alumel, platinum rhodium, and metals such as Au, Al, Cu, Fe, Pt, Ni, Cr, W, Ta it can.

  As the synthetic resin material constituting the insulating layer, any material can be used as long as it can produce a thin film by vapor deposition polymerization. Examples of such a synthetic resin material include polyimide, polyurea, polyamide, polyazomethine and the like. As a raw material monomer for polyimide, 1) a combination of an amine compound having two or more amino groups and 2) a carboxylic acid anhydride, 2) a carboxylic acid anhydride and 3) an isocyanate compound having two or more isocyanate groups As a raw material monomer for polyurea, 1) a combination of an amine compound having two or more amino groups and 3) an isocyanate compound having two or more isocyanate groups, and further a raw material monomer for polyamide 1) A combination of an amine compound having two or more amino groups and 4) an acyl compound having two or more acyl halide groups, and, as a raw material monomer for polyazomethine, 1) two or more A combination of an amine compound having an amino group of 5) and an aldehyde compound having two or more aldehyde groups, , It can be mentioned. Here, 1) As an amine compound having two or more amino groups, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, methylenebis (4-cyclohexyl) Amine), 1,3-bis (aminomethyl) cyclohexane, tris (2-aminomethyl) amine, 1,3-diamino-2-propanol, etc. 2) As the carboxylic acid anhydride, tetracarboxylic dianhydride 3) Diisyl ether-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, m-phenylene Diisocyanate, m-xylene diisocyanate 4) Two or more of nate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, 1,3,5-triisocyanatehexane, 1,3,5-trimethylisocyanatecyclohexane, etc. Examples of the acyl compound having a halogenated acyl group include terephthalic acid dichloride, isophthalic acid dichloride, adipic acid dichloride, sebacic acid dichloride, and the like. , Naphthalenedialdehyde and the like can be exemplified.

  On the other hand, FIGS. 8 to 10 show a thermoelectric conversion module (thermoelectric conversion module 40) according to another embodiment of the present invention. Specifically, FIG. 8 shows the thermoelectric change module 40 in a plan view, and FIG. 9 is a cross-sectional view taken along the line i-i ′ in FIG. 8. 10 (a) to 10 (f) show the ii-ii 'plane, iii-iii' plane, iv-iv 'plane, vv' plane, vi-vi 'plane and vii-vii in FIG. 'Cross sections on each side of the plane are shown. Since the thermoelectric conversion module 40 has the same appearance as the thermoelectric conversion module 10 described above, a perspective view, a front view, a left side view, and a right side view of the thermoelectric conversion module 40 are omitted. Further, in the thermoelectric change module 40 shown in FIG. 8 to FIG. 10, the same reference numerals as those of the thermoelectric conversion module 10 are given to the portions related to the same configuration as the thermoelectric conversion module 10 described above, and the detailed description is omitted. The characteristic configuration unique to the thermoelectric conversion module 40 will be described in detail below.

  As apparent from FIGS. 8 to 10, in the thermoelectric conversion module 40 shown in these drawings, each layer of the first thermoelectric material layer made of the first thermoelectric material and the second thermoelectric material made of the second thermoelectric material. Each of the layers also has an appendage.

  First, the 1st thermoelectric material layer 42 arrange | positioned at the surface (upper surface) of the base film 12a is comprised including the attachment part 42c in addition to the main-body part 42a and the external connection part 42b. The attachment portion 42c is in a state in which a margin portion is interposed between the attachment portion 42c and the side surface opposite to the side surface facing the main body portion 42a is located inward from the end surface of the base film 12a. (See FIG. 10A).

  On the other hand, the second thermoelectric material layer 44 disposed on the back surface (lower surface) of the base film 12b is also attached to the main body portion 44a and the external connection portion 44b in the same manner as the first thermoelectric material layer 42 described above. 44c is also included. The attachment portion 44c is in a state where a margin portion is interposed between the attachment portion 44c and the side surface opposite to the side surface facing the main body portion 44a is located inward from the end surface of the base film 12b. It arrange | positions so that it may do (refer FIG.10 (f)).

  Moreover, the thermoelectric material layer arrange | positioned between two insulating layers is each comprised from the main-body part and two attachment parts, and any thermoelectric material layer is FIG.10 (b)-( As shown in e), they are configured in the same form. Specifically, the second thermoelectric material layer 46 disposed between the insulating layer 20 and the insulating layer 24 includes a main body portion 46a and two attachment portions 46b and 46c. The attachment portions 46b and 46c are respectively disposed on both sides of the main body portion 46a in the direction in which the heating source (or heated body) and the cooling source (cooled body) are arranged when the thermoelectric conversion module 40 is used. Are arranged with a margin between them. Further, of the side surfaces of the attachment portions 46b and 46c, the side opposite to the side surface facing the main body portion 46a is disposed so as to be located inward from the end surface of the insulating layer 24 (FIG. 10). (See (b)).

  In the same form as the second thermoelectric material layer 46, a first thermoelectric material layer 48 including a main body portion 48 a and two attachment portions 48 b and 48 c is disposed between the insulating layer 24 and the insulating layer 28. (See FIG. 10C in particular.) Also, between the insulating layer 28 and the insulating layer 32, a second thermoelectric material layer 50 comprising a main body portion 50a and two attachment portions 50b and 50c is disposed (particularly FIG. 10 (d)) is disposed, and a first thermoelectric material layer 52 including a main body portion 52a and two attachment portions 52b and 52c is disposed between the insulating layer 32 and the insulating layer 36. (See particularly FIG. 10 (e)).

  As described above, in the thermoelectric conversion module 40 shown in FIGS. 8 to 10, the first thermoelectric material layer and the second thermoelectric material layer include the main body portion (and the external connection portion) and the main body portion (and the external portion). Insulating synthetic resin formed on the upper surface of the thermoelectric material layer while securing the same external insulation as the above-described thermoelectric conversion module 10 from having a separate and independent accessory portion from the connection portion) It is easy to make the thickness of the insulating layer made of the vapor-deposited polymer film of the material uniform, and thus the thermoelectric conversion module has excellent dimensional accuracy.

  In addition, the attachment part of each thermoelectric material layer has both sides in the direction in which the heating source (or heated body) and the cooling source (cooled body) are arranged when the thermoelectric conversion module 40 is used in the main body portion of the thermoelectric material layer. In addition, the thermal conductivity in the vicinity thereof is advantageously improved by the presence of the accessory portion, which contributes to the improvement of the thermoelectric conversion efficiency in the thermoelectric conversion module 40. To do. Furthermore, compared with the case where an attachment part does not exist, the intensity | strength of a lamination | stacking part edge part improves effectively, and the mechanical strength as the whole module will also improve advantageously.

  The thermoelectric conversion module according to the present invention described above can be manufactured by appropriately combining various conventionally known methods. For example, when the thermoelectric conversion module 40 shown in FIGS. 8 to 10 is manufactured, two types of stacking are performed using the stack manufacturing apparatus 60 (simply referred to as a manufacturing apparatus in this specification) shown in FIG. After the bodies 54 ′ and 56 ′ are manufactured, the two kinds of laminates 54 ′ and 56 ′ are superposed so that the outermost surface layers (first thermoelectric material layers 48) of the laminates 54 ′ and 56 ′ are in contact with each other. It can be manufactured by integrating 56 'and cutting the integrated product appropriately. Hereinafter, the structure of the manufacturing apparatus 60 used when manufacturing the laminated body 54 'will be described in detail.

  As is clear from FIG. 11, the manufacturing apparatus 60 includes a vacuum chamber 62 having a predetermined size, and the vacuum chamber 62 includes a main chamber 64 and a sub chamber 66. The main chamber 64 is surrounded by the first peripheral wall portion 68, and the sub chamber 66 is surrounded by a part of the first peripheral wall portion 68 and the second peripheral wall portion 70. The main chamber 64 and the sub chamber 66 communicate with each other through the window portion 72 formed in the first peripheral wall portion 68 surrounding the sub chamber 66 together with the second peripheral wall portion 70.

  Note that a vacuum forming means (not shown) is attached to the vacuum chamber 62. By operating the vacuum forming means, the degree of vacuum inside the main chamber 64 and the sub chamber 66 can be adjusted. Yes.

  A can roller 74 as a rotating drum is installed at the center of the main chamber 64. The can roller 74 is made of a cylindrical body made of metal such as iron, and is driven to rotate in one direction (direction indicated by an arrow: α in FIG. 11) by an electric motor (not shown). .

  In the sub chamber 66, an unwinding roller 76 serving as an unwinding machine and a winding roller 78 serving as a winding machine are parallel to the rotation axis of the can roller 74 at a position spaced apart from each other by a predetermined distance. It is installed so that it can rotate around the rotation axis. A film roll 80 around which the base film 12a is wound is attached to the unwinding roller 76, and the film roll 80 can be unwound along with its rotation. On the other hand, the take-up roller 78 is configured such that the tip portion of the base film 12a unwound by the unwind roller 76 is detachably attached, and is driven to rotate by an electric motor (not shown) or the like. It has become. Then, as will be described later, the base film 12a unwound from the film roll 80 is formed by laminating a thermoelectric material layer and an insulating layer to form a laminated body 54 ′, and then by the rotational driving of the winding roller 78. The take-up roller 78 is wound up.

  In the main chamber 64, the air outlets of the thermoelectric material layer forming unit 82, the insulating layer forming unit 84, the thermoelectric material layer forming unit 86, the insulating layer forming unit 88, and the thermoelectric material layer forming unit 90 are disposed around the can roller 74. The members are arranged side by side in the rotation direction of the can roller 74 according to this order.

  As is clear from FIGS. 11 and 12A, the thermoelectric material layer forming unit 82 includes a thermoelectric material vapor generation part 92 and a blowout member 94. In the steam generation unit 92, an electron gun 96 and a container 97 containing a first thermoelectric material are respectively positioned in a rectangular parallelepiped housing portion 95 whose surface on the side of the can roller 74 is an opening surface. It is arranged in a fixed manner.

  On the other hand, the outlet member 94 is formed of a cylindrical body that is open upward (upper in FIG. 12A) and lower (lower in FIG. 12A) as a whole. The opening part of the housing | casing part 95 is assembled | attached, and the lower opening part is made into the blower outlet 98. As shown in FIG. The outlet member 94 has a quadrangular pyramid-shaped upper cylindrical wall portion 100 that gradually increases in cross-sectional area toward the can roller 74 side, and a lower cylindrical portion 102 that exhibits a horizontally long rectangular parallelepiped shape. Yes. In the lower cylindrical portion 102, the lower end surfaces of the two first side wall portions 104, 104 extending in the width direction (the direction perpendicular to the paper surface in FIG. 12A and the vertical direction in FIG. 12B) are flat. On the other hand, the lower end surfaces of the two second side wall portions 106 and 106 extending in the length direction (the left-right direction in FIGS. 12A and 12B) are convex upward. Arc-shaped lower end surfaces 107 and 107 are formed. The diameter of the arc-shaped lower end surface 107 in the second side wall 106 is slightly larger than the diameter of the outer peripheral surface of the can roller 74 (indicated by a two-dot chain line in FIG. 12A). As a result, the size of the gap formed between the air outlet 98 and the outer peripheral surface of the can roller 74 is substantially constant over the entire periphery of the air outlet 98.

  In addition, at the air outlet 98 of the air outlet member 94, two deposition bars 108a and 108b are arranged. In FIG. 12 (b), the protection bars 108a and 108b are hatched for easy understanding. Each of the adhesion preventing bars 108a and 108b has substantially the same inner diameter as the diameter of the arc-shaped lower end surface 107 in the lower cylindrical portion 102 and the distance between the opposing surfaces of the two first side wall portions 104 and 104. It is made of an arcuate curved member having a string. And, in the prevention bar 108b, it is predetermined at the upper end in the width direction (vertical direction in FIG. 12 (b)) of the lower cylindrical portion 102, and in the prevention bar 108a, it is below the prevention bar 108a. It arrange | positions so that it may extend in the length direction in the position away from the distance, and it is being fixed to the lower end part of the mutually opposing surface in the two 1st side wall parts 104 and 104. FIG.

  In the thermoelectric material layer forming unit 82 having the above-described configuration, when an electron beam is emitted from the electron gun 96, the electron beam is deflected by a deflection coil (not shown), and the deflected electron beam is converted into the container 97. The first thermoelectric material is irradiated. The vapor | steam of the 1st thermoelectric material generated by irradiation of this electron beam is sprayed on the base film 12 from the blower outlet 98 of the blower outlet member 94, and, thereby, the 1st thermoelectric material layer 42 which consists of a 1st thermoelectric material. Is formed.

Note that, in the thermoelectric material layer forming unit 82 of the manufacturing apparatus 60, the thermoelectric material vapor generating unit 92 employs a configuration for generating a thermoelectric material vapor according to an electron beam (EB) vapor deposition method. The formation of the thermoelectric material layer when producing the thermoelectric conversion module of the present invention can also be carried out according to a vapor phase growth method other than the EB vapor deposition method. Specifically, not only vapor deposition methods such as resistance heating vapor deposition method and high frequency induction heating vapor deposition method, but also various sputtering methods such as RF sputtering method, DC sputtering method, magnetron sputtering method and ion beam sputtering method, pulse laser deposition. A vapor generation unit 92 has a configuration (for example, a sputtering chamber) corresponding to the selected method, appropriately selected from the known vapor phase growth methods such as the (PLD) method, according to the thermoelectric material used. Can be replaced. The gas species required in various sputtering methods and PLD methods are appropriately selected from Ar, N ₂ , O ₂ , He, and the like depending on the type of thermoelectric material. The same applies to each steam generation section in the thermoelectric material layer forming unit 86 and the thermoelectric material layer forming unit 90 described later.

  As shown in FIG. 11, the insulating layer forming unit 84 includes a monomer vapor supply unit 112 and a blowout member 114.

  The monomer vapor supply means 112 has storage pots 116a and 116b, and the raw material monomer of the synthetic resin material constituting the vapor deposition polymerization film is stored in a liquid state in each of the storage pots 116a and 116b. For example, when adopting a vapor deposition polymerized film made of polyimide as an insulating layer in the thermoelectric conversion module of the present invention, one accommodation pot contains a carboxylic acid anhydride such as pyromellitic dianhydride, and the other In one storage pot, an amine compound having two or more amino groups such as 4,4′-diaminodiphenyl ether is stored. Each of the storage pots 116a and 116b has a heater (not shown) for evaporating the stored raw material monomer. In addition, one end of the steam supply pipe 117 a is connected to the accommodation pot 116 a, and the other end is connected to the outlet member 114. Similarly, one end of the steam supply pipe 117b is connected to the storage pot 116b, and the other end is connected to the outlet member 114.

  As shown in FIGS. 13A and 13B, the outlet member 114 constituting the insulating layer forming unit 84 has a bottom on one side that opens downward as a whole (downward in FIG. 13A). It consists of a cylinder and the opening part below is made into the blower outlet 118. FIG. Further, the air outlet member 114 has a quadrangular pyramid-shaped upper cylindrical wall portion 120 that gradually increases in cross-sectional area toward the can roller 74 side, and a lower cylindrical portion 122 that exhibits a horizontally long rectangular parallelepiped shape. Yes.

  More specifically, the lower cylindrical portion 122 of the outlet member 114 has two first side wall portions 124 extending in the width direction (the direction perpendicular to the paper surface of FIG. 13A and the vertical direction of FIG. 13B), While the lower end surface of 124 is a flat surface, the lower end surfaces of the two second side wall portions 126 and 126 extending in the length direction (the left-right direction in FIGS. 13A and 13B) are upward. It is made into the circular-arc-shaped lower end surface 127, 127 which exhibits convex shape toward it. The diameter of the arc-shaped lower end surface 127 in the second side wall 126 is slightly larger than the diameter of the outer peripheral surface of the can roller 74 (indicated by a two-dot chain line in FIG. 13A). As a result, the size of the gap formed between the air outlet 118 and the outer peripheral surface of the can roller 74 is set to a substantially constant size over the entire circumference of the air outlet 118.

  In addition, a partition wall 128 a that protrudes from one surface side of the upper cylindrical wall portion 120 to the opposite surface side is provided inside the air outlet member 114 from the one surface side of the lower cylindrical portion 122 to the opposite surface side. The protruding partition walls 128b and 128c are arranged so that the openings formed by the partition walls are staggered in the vertical direction (vertical direction in FIG. 13A). By arranging these partition walls, the vapors of the two types of raw material monomers supplied through the steam supply pipes 117a and 117b are effectively mixed by colliding with the partition walls, thereby mixing the raw material monomers. Steam is sprayed onto the base film 12.

  In addition, two deposition bars 130a and 130b are arranged at the outlet 118 of the outlet member 114. In FIG. 13 (b), the protection bars 130a and 130b are hatched for easy understanding. Each of the adhesion preventing bars 130a and 130b has an inner diameter that is substantially the same as the diameter of the arc-shaped lower end surface 127 of the lower cylindrical portion 122 and a distance that is substantially the same as the distance between the opposing surfaces of the two first side wall portions 124 and 124. It is made of an arcuate curved member having a string. And in the prevention bar 130a, it is predetermined at the lower end in the width direction (the vertical direction in FIG. 13 (b)) of the lower cylindrical portion 122, and in the prevention bar 130b, above the adhesion bar 130a. It arrange | positions so that it may extend in the length direction in the position away from distance, and is fixed to the lower end part of the mutually opposing surface in the two 1st side wall parts 124 and 124. FIG.

  On the other hand, as shown in FIG. 11, the thermoelectric material layer forming unit 86 has a thermoelectric material vapor generating part 92 having the same configuration as that of the thermoelectric material layer forming unit 82 described above, and an outlet member 132. doing. However, in the steam generation part 92 in the thermoelectric material layer formation unit 86, the 2nd thermoelectric material is accommodated in the container inside.

  Here, the air outlet member 132 of the thermoelectric material layer forming unit 86 has the same configuration as the air outlet member 94 in the thermoelectric material layer forming unit 82 described above, except for the adhesion prevention bar. As shown in FIG. 14, the outlet member 132 of the thermoelectric material layer forming unit 86 has four prevention bars 134 a, 134 b, 134 c, and 134 d. In addition, also in FIG. 14, each protection bar is hatched. Further, an anti-adhesion bar 134a is arranged at the lower end in the width direction (vertical direction in FIG. 14) of the lower cylindrical portion of the air outlet member 132, and 134d is arranged at the upper end. Each of the bars 134b and 134c is disposed at a position separated by a predetermined distance.

  Further, as shown in FIG. 11, the insulating layer forming unit 88 includes monomer vapor supply means 112 having a configuration similar to that in the above-described insulating layer forming unit 84, and an outlet member 138. As shown in FIG. 15, the air outlet member 138 of the insulating layer forming unit 88 has two prevention bars 140 a and 140 b. In addition, also in FIG. 15, each protection bar is hatched. And in the adhesion prevention bar 140a, it exists in the lower end of the width direction (up-down direction of FIG. 15) of the lower side cylinder part in the blower outlet member 138, and in the adhesion prevention bar 140b above the adhesion prevention bar 140a. It is arranged at a predetermined distance away.

  In addition, as shown in FIG. 11, the thermoelectric material layer forming unit 90 has the same configuration as the above-described thermoelectric material layer forming unit 86, and includes a thermoelectric material vapor generation unit 92 and an outlet member 132. And have. However, in the steam generation part 92 in the thermoelectric material layer formation unit 90, the 1st thermoelectric material is accommodated in the container inside.

  And when manufacturing the laminated body 54 shown by FIG. 9 using the manufacturing apparatus 60 which has the above structures, the operation is advanced according to the following procedures, for example.

  First, as shown in FIG. 11, the film roll 80 is extrapolated to the unwinding roller 76 and set. Next, after the base film 12 a is unwound from the film roll 80 and wound around the can roller 74, the leading end is attached to the take-up roller 78. Thereafter, the vacuum forming means (not shown) is operated to adjust the degree of vacuum in the vacuum chamber 62 (in the main chamber 64 and the sub chamber 66).

  After the degree of vacuum in the vacuum chamber 62 is stabilized to a desired level, an electric motor attached to the can roller 74 is driven to rotate, and the can roller 74 is rotated in the arrow: α direction in FIG. . At the same time, the winding roller 78 is also driven to rotate. As a result, the base film 12a is fed from the sub chamber 66 into the main chamber 64 and travels on the can roller 74 in the arrow: α direction, while the base film 12a wound from the can roller 74 is wound. Winding by the take-up roller 78 is enabled. Then, the following steps a to e are performed in that order. FIGS. 16A to 16E show the state of the surface of the base film 12a after the steps a to e are performed.

-Step a-
The first thermoelectric material layer made of the first thermoelectric material is formed by operating the thermoelectric material layer forming unit 82 to generate vapor of the first thermoelectric material and blowing this vapor onto the base film 12a. . At the air outlet 98 of the thermoelectric material layer forming unit 82, the deposition bars 108a and 108b are disposed (see FIG. 12B). From the position a on the base film 12 in the transport direction of the film. An extended non-formation portion of the first thermoelectric material layer is formed. Further, in this step, the thermoelectric material layer forming unit 82 is operated intermittently, that is, the thermoelectric material layer forming unit 82 is operated for a predetermined time and then stopped for a predetermined time. The non-formation site | part of the 1st thermoelectric material layer extended in the direction orthogonal to the conveyance direction of the material film 12a is formed for every predetermined space | interval in a conveyance direction. In accordance with this step, the first thermoelectric material layer formed on the base film 12a is a hatched portion in FIG.

-Step b-
The insulating layer forming unit 84 is operated to generate a raw material monomer vapor, and this vapor is sprayed onto the base film 12a on which the first thermoelectric material layer has been formed in step a, thereby depositing an insulating synthetic resin. An insulating layer made of a polymer film is formed. At the air outlet 118 of the insulating layer forming unit 84, the anti-adhesion bars 130a and 130b are arranged (see FIG. 13B), so that the base film 12a extends in the transport direction of the film. A non-formed portion of the insulating layer is formed. According to this process, the insulating layer formed on the base film 12a is a hatched portion in FIG.

-Process c-
The thermoelectric material layer forming unit 86 is operated to generate a vapor of the second thermoelectric material, and this vapor is blown onto the base film 12a on which the insulating layer has been formed in step b, whereby the second thermoelectric material A second thermoelectric material layer is formed. The anti-adhesion bars 134a, 134b, 134c, and 134d are disposed at the outlet of the thermoelectric material layer forming unit 86 (see FIG. 14), and thus extend on the base film 12a in the transport direction of the film. The non-formation site | part of the 2nd thermoelectric material layer is formed. In addition, the thermoelectric material layer forming unit 86 used in this step is also intermittently operated in the same manner as the thermoelectric material layer forming unit 82 used in step a described above, thereby conveying the base film 12a. The non-formation site | part of the 2nd thermoelectric material layer extended in the direction orthogonal to is formed for every predetermined space | interval in a conveyance direction. According to this process, the second thermoelectric material layer formed on the base film 12a is a hatched portion in FIG. Note that the second thermoelectric material penetrates into the portion corresponding to the portion where the second thermoelectric material layer is formed by this step among the non-insulating portion of the insulating layer in the previous step c. A connection portion with the first thermoelectric material layer formed in this way is formed.

-Step d-
The insulating layer forming unit 88 is operated to generate a raw material monomer vapor, and this vapor is sprayed onto the base film 12a on which the second thermoelectric material layer has been formed in step c, thereby depositing an insulating synthetic resin. An insulating layer made of a polymer film is formed. At the air outlet 138 of the insulating layer forming unit 88, the anti-adhesion bars 140a and 140b are disposed (see FIG. 15), and thus the insulating layer extending in the transport direction of the film is formed on the base film 12a. Non-formed sites are formed. According to this process, the insulating layer formed on the base film 12a is a hatched portion in FIG.

-Process e-
The thermoelectric material layer forming unit 90 is operated to generate a vapor of the first thermoelectric material, and this vapor is blown onto the base film 12a on which the insulating layer has been formed in step d, whereby the first thermoelectric material A first thermoelectric material layer is formed. Since the adhesion prevention bars 134a, 134b, 134c, and 134d are arranged at the outlet of the thermoelectric material layer forming unit 90 in the same manner as the outlet of the thermoelectric material layer forming unit 86, on the base film 12a, The non-formation site | part of the 1st thermoelectric material layer extended in the conveyance direction of this film is formed. Also, the thermoelectric material layer forming unit 90 used in this step is intermittently operated in the same manner as the thermoelectric material layer forming unit 82 used in step a described above, so that the base film 12a is conveyed in the transport direction. The non-formation site | part of the 1st thermoelectric material layer extended in the direction orthogonal to is formed for every predetermined space | interval in a conveyance direction. According to this step, the first thermoelectric material layer formed on the base film 12a is a hatched portion in FIG. In addition, in the part where the insulating layer is not formed in the previous step d, the first thermoelectric material enters the portion corresponding to the portion where the first thermoelectric material layer is formed by this step, so that the step c is entered. A connection portion with the second thermoelectric material layer formed in this way is formed.

  By following the above steps, as shown in FIG. 17, a laminated body 54 ′ having the first thermoelectric material layer disposed on the base film 12a and having the first thermoelectric material layer as the outermost surface layer is manufactured. It is.

  On the other hand, the process b ′ and the process c ′ are further performed on the base film 12b in the processes a ′ to e ′ in which the first thermoelectric material and the second thermoelectric material are replaced among the above processes. In other words, by carrying out in the order of step a ′ → step b ′ → step c ′ → step d ′ → step e ′ → step b ′ → step c ′, a base film as shown in FIG. It is possible to manufacture the laminated body 56 ′ having the second thermoelectric material layer disposed on 12b and having the first thermoelectric material layer as the outermost surface layer.

  Then, the laminates 54 ′ and 56 ′ obtained as described above are overlapped and integrated so that the outermost surface layers are in contact with each other, and then cut at a portion where the thermoelectric material is not formed. Thus, the thermoelectric conversion module 40 as shown in FIG. 9 is advantageously obtained.

  As described above, the manufacturing method of the thermoelectric conversion module 40 using the manufacturing apparatus 60 shown in FIG. 11 has been described in detail. However, when manufacturing the thermoelectric conversion module 40, an apparatus in which a further configuration is added to the manufacturing apparatus 60. Even so, it can be used advantageously. For example, a thermoelectric material adhesion prevention layer composed of an oil layer having a predetermined width is formed on the film immediately before each thermoelectric material layer forming unit in the manufacturing apparatus 60 (upstream in the film transport direction) in a direction perpendicular to the film transport direction. An apparatus in which possible mask portion forming units (also referred to as pattern rolls or the like) are disposed can be used advantageously. By using a manufacturing apparatus using such a mask portion forming unit, the intermittent operation of each thermoelectric material layer forming unit, which is required in the manufacturing method using the manufacturing apparatus 60 described above, is no longer necessary. Continuous operation is possible. In addition, the thermoelectric material adhesion prevention layer which consists of an oil layer formed by this mask part formation unit disappears (volatilizes) effectively from the film while the thermoelectric material layer is formed by the thermoelectric material layer formation unit. However, it does not hinder the subsequent formation of the insulating layer by the insulating layer forming unit.

  On the other hand, the above-described thermoelectric conversion module 10 shown in FIG. 6 and the like can be manufactured by using an apparatus in which the configuration of the manufacturing apparatus 60 is partially changed. Specifically, an apparatus that does not include the deposition preventing bar 108a in the outlet member 94 of the thermoelectric material layer forming unit 82 and the deposition bars 134b and 134c in the outlet member 132 of the thermoelectric material layer forming units 86 and 90 is provided. 1) Producing a laminated body in which the first thermoelectric material layer is arranged on the base film 12a and having the first thermoelectric material layer as the outermost surface layer in accordance with the steps a to e described above, and 2) Step b ′ and step c ′ are further performed in steps a ′ to e ′ in which the first thermoelectric material and the second thermoelectric material are replaced with respect to the base film 12b (step a ′ → step b). The second thermoelectric material layer is disposed on the base film 12b, and the outermost surface layer is formed in the order of '→ step c' → step d '→ step e' → step b '→ step c'). Producing a laminate having a first thermoelectric material layer; ) After stacking the two laminated bodies so obtained so that the outermost surface layers are in contact with each other and then integrating them, by cutting at a portion where the thermoelectric material is not formed, FIG. A thermoelectric conversion module 10 as shown is advantageously obtained.

  The thermoelectric conversion module according to the present invention can be used alone, for example, as shown in FIG. 18, a plurality (two in FIG. 18) of thermoelectric conversion modules are connected in series with different thermoelectric material layers. It can also be used by connecting to be connected to. Further, the thermoelectric conversion module according to the present invention has a longitudinal band shape as a whole, and is produced so that the external connection portion on the base film protrudes in the width direction, and the wound body obtained by winding the wound body. Even in (see FIG. 19A), as shown in FIG. 19B, it can be used as a thermoelectric conversion module.

  In order to confirm the performance of the thermoelectric conversion module according to the present invention, the following experiment was conducted.

  First, a polyimide film (Toray Dupont Co., Ltd., thickness: 25 μm) as a base film, constantan as a first thermoelectric material, and chromel as a second thermoelectric material were prepared. At the same time, pyromellitic dianhydride and 4,4'-diaminodiphenyl ether were prepared as raw material monomers so that the insulating layer was composed of a vapor deposition polymer film of polyimide.

-Production of laminate i-
After implementing the above-mentioned process a-process e, the laminated body i was produced by repeating the process b-process e four times further. In addition, the distance between series in the laminated body i is 5 mm, and the outermost surface layer is the first thermoelectric material layer.

-Production of laminate ii-
Step a 'to step e' described above, in which the first thermoelectric material and the second thermoelectric material are interchanged, and after performing step a 'to step e', step b 'to step e' are repeated three times. Furthermore, the layered product ii was produced by carrying out the steps b ′ to c ′. Note that the series distance and the outermost surface layer in the laminate ii are the same as those in the laminate i.

  The laminated body i and the laminated body ii were overlapped so that the outermost surface layers were in contact with each other, and the laminated body was wound up 100 times by a winding roll. The wound product was cut at a portion where the thermoelectric material layer was not formed, and the external connection portions adjacent to each other were electrically connected to obtain a thermoelectric conversion module. The obtained thermoelectric conversion module has 1000 pairs of constantan-chromel, the height in the stacking direction: 15 mm, the length in the longitudinal direction: 100 mm, and the length in the width direction (direction in which the temperature difference is provided). : 8 mm.

  About the obtained thermoelectric conversion module, it was 0.68 W / (m * K) when the heat conductivity was measured according to the optical alternating current method. In addition, the thermoelectric conversion characteristic was that a current of 3 V and 15 mA was obtained with a temperature difference of 50K.

DESCRIPTION OF SYMBOLS 10 Thermoelectric conversion module 12 Base film 14 Lamination | stacking part 16, 26, 34 1st thermoelectric material layer 18, 22, 30 2nd thermoelectric material layer 40 Thermoelectric conversion module 42, 48, 52 1st thermoelectric material layer 44, 46, 50 Second thermoelectric material layer 60 Manufacturing apparatus 82, 86, 90 Thermoelectric material layer forming unit 84, 88 Insulating layer forming unit

Claims (3)

The first thermoelectric material layer made of the first thermoelectric material and the second thermoelectric material layer made of the second thermoelectric material are alternately stacked via the insulating layer between the pair of planar rectangular base film. And a thermoelectric conversion module in which a first thermoelectric material layer and a second thermoelectric material layer adjacent to each other are connected via an insulating layer,
The first thermoelectric material layer A made of the first thermoelectric material, formed on the surface of the one base film facing the other base film, and the other base film The first thermoelectric material layer made of the first thermoelectric material between the second thermoelectric material layer B made of the second thermoelectric material and formed on the surface on the side facing the one base film. A ′, a second thermoelectric material layer B ′ made of the second thermoelectric material, and a laminated part composed of at least one layer of an insulating layer made of a vapor deposition polymerized film,
Said 1st thermoelectric material layer A is comprised from main-body part A1 and external connection part A2, and this main-body part A1 is arrange | positioned in the site | part except the peripheral part on the surface of said one base film. In addition, the external connection portion A2 is arranged in a form continuously extending from the main body portion A1 to an end on one side on the surface of the one base film,
Said 2nd thermoelectric material layer B is comprised from main-body part B1 and external connection part B2, and this main-body part B1 is arrange | positioned in the site | part except the peripheral part on the surface of said another base film. In addition, the external connection portion B2 is arranged in a form continuously extending from the main body portion B1 at an end portion on one side on the surface of the other base film,
The one base film and the other one of the laminated portions are exposed so that the external connection portion A2 of the first thermoelectric material layer A and the external connection portion B2 of the second thermoelectric material layer B are exposed to the outside. It is arranged between the base film and
The insulating layer constituting the stacked portion is composed of a first insulating layer portion and a second insulating layer portion located on both sides with a margin portion interposed therebetween,
The first thermoelectric material layer A ′ constituting the laminated portion is disposed at a portion excluding the peripheral edge portion on the surface of the insulating layer located immediately below the first thermoelectric material layer A ′.
The second thermoelectric material layer B ′ constituting the laminated portion is disposed at a portion excluding the peripheral edge portion on the surface of the insulating layer located immediately below the second thermoelectric material layer B ′.
By introducing the first thermoelectric material or the second thermoelectric material into a margin portion between the first insulating layer portion and the second insulating layer portion in the insulating layer, the insulating layer is interposed through the insulating layer. The adjacent first thermoelectric material layer and the second thermoelectric material layer are connected,
A thermoelectric conversion module characterized by that. The first thermoelectric material layer A further includes an attachment portion A3, and the attachment portion A3 extends from the main body portion A1 to the external connection portion A2 on the surface of the one base film. In a state where a margin portion is interposed between the body portion A1 and a portion on the opposite side of the extending direction, and the side surface opposite to the side surface facing the body portion A1 in the attachment portion A3, It is arranged so as to be located inward from the end face of the one base film,
The second thermoelectric material layer B further includes an appendage B3, and the appendage B3 is connected to the external connection portion from the main body B1 on the surface of the other base film. In a state where a margin portion is interposed between the main body B1 and a portion opposite to the extending direction to B2, and a side surface opposite to the side surface facing the main body portion B1 in the attachment portion B3 Is arranged so as to be located inward from the end face of the other base film,
The first thermoelectric material layer A ′ has a main body portion A′1 formed at a portion excluding the peripheral edge portion on the surface of the insulating layer located immediately below the first thermoelectric material layer A ′, and an attachment portion A′2. The attachment portion A′2 is formed on the peripheral portion of the surface of the insulating layer with a margin portion interposed between the attachment portion A′2 and the main body portion A′1. The side surface opposite to the side surface facing the main body A′1 in A′2 is disposed so as to be located inward from the end surface of the insulating layer,
The second thermoelectric material layer B ′ has a main body portion B′1 formed at a portion excluding the peripheral edge portion on the surface of the insulating layer located immediately below the second thermoelectric material layer B ′, and an attachment portion B′2. The attachment portion B′2 is formed on the peripheral portion of the surface of the insulating layer with a margin portion interposed between the attachment portion B′2 and the body portion B′1. The side surface opposite to the side surface facing the main body B′1 in B′2 is disposed so as to be located inward from the end surface of the insulating layer.
The thermoelectric conversion module according to claim 1. In the manufacturing method of the thermoelectric conversion module according to claim 1,
The first thermoelectric material layer A is formed on one base film according to the manufacturing method having the following steps 1 to 5 or the manufacturing method having the following steps 1 to 3, and the outermost surface layer Preparing a laminate I that is either the first thermoelectric material layer A ′ made of the first thermoelectric material or the second thermoelectric material layer B ′ made of the second thermoelectric material;
According to the manufacturing method having the following steps 1 ′ to 5 ′ or the manufacturing method having the following step 1 ′, the second thermoelectric material layer B is formed on the other base film, and A step of preparing a laminate II, the surface layer of which is composed of the same thermoelectric material that constitutes the outermost surface layer of the laminate I;
Laminating the laminate I and the laminate II so that the outermost surface layers of the laminate are in contact with each other, and integrating them,
The manufacturing method of the thermoelectric conversion module containing this.
Step 1: A first thermoelectric material layer A made of a first thermoelectric material and composed of a main body portion A1 and an external connection portion A2 is formed on one surface of one base film according to a vapor phase growth method. The main body part A1 is formed on a part excluding the peripheral part on the surface of the one base film, and the external connection part A2 is on an end on one side of the surface of the base film. It forms in the form extended continuously from this main-body part A1.
Step 2: After forming the first thermoelectric material layer A, on the portion of the base film surface on which the first thermoelectric material layer A is formed, excluding the end on the external connection portion A2 side, The insulating layer C1 composed of the first insulating layer portion and the second insulating layer portion is subjected to a vapor deposition polymerization method so that the first insulating layer portion and the second insulating layer portion are located on both sides with a margin portion interposed therebetween. Form.
Step 3: After forming the insulating layer C1, a second thermoelectric material layer B ′ made of the second thermoelectric material is formed on the insulating layer C1 surface excluding the peripheral edge according to the vapor phase growth method. The second thermoelectric material is introduced into the marginal portion existing between the first insulating layer portion and the second insulating layer portion of the insulating layer C1.
Step 4: After forming the second thermoelectric material layer B ′, the first insulation is formed on the second thermoelectric material layer B ′ and on the non-formation portion of the second thermoelectric material layer B ′ in the insulating layer C1. The insulating layer C2 composed of the layer portion and the second insulating layer portion is formed according to the vapor deposition polymerization method so that the first insulating layer portion and the second insulating layer portion are located on both sides with the margin portion interposed therebetween.
Step 5: After the insulating layer C2 is formed, a first thermoelectric material layer A ′ made of the first thermoelectric material is formed on the insulating layer C2 surface excluding the peripheral portion according to the vapor phase growth method. The first thermoelectric material is introduced into the marginal portion existing between the first insulating layer portion and the second insulating layer portion of the insulating layer C2.
Step 1 ′: The second thermoelectric material layer B made of the second thermoelectric material and composed of the main body portion B1 and the external connection portion B2 is formed on one surface of the other base film by vapor deposition. Accordingly, the main body B1 is formed on a portion excluding the peripheral edge on the surface of the other base film, and the external connection portion B2 is formed on the surface of the other base film. It is formed in a form extending continuously from the main body B1 on one side end.
Step 2 ′: After forming the second thermoelectric material layer B, the portion excluding the end on the external connection portion B2 side on the surface of the other base film on which the second thermoelectric material layer B is formed On top, the insulating layer C1 ′ composed of the first insulating layer portion and the second insulating layer portion is arranged so that the first insulating layer portion and the second insulating layer portion are located on both sides with the margin portion interposed therebetween. It is formed according to the vapor polymerization method.
Step 3 ′: After forming the insulating layer C1 ′, a first thermoelectric material layer A ′ made of the first thermoelectric material is formed on the insulating layer C1 ′ surface excluding the peripheral edge according to the vapor phase growth method. At the same time, the first thermoelectric material is introduced into a margin portion existing between the first insulating layer portion and the second insulating layer portion of the insulating layer C1 ′.
Step 4 ′: After forming the first thermoelectric material layer A ′, on the first thermoelectric material layer A ′ and on the non-formation portion of the first thermoelectric material layer A ′ in the insulating layer C1 ′. The vapor deposition polymerization method is used to form the insulating layer C2 ′ composed of the first insulating layer portion and the second insulating layer portion so that the first insulating layer portion and the second insulating layer portion are located on both sides with the margin portion interposed therebetween. Form according to.
Step 5 ′: After forming the insulating layer C2 ′, a second thermoelectric material layer B ′ made of the second thermoelectric material is formed on the portion excluding the peripheral edge on the surface of the insulating layer C2 ′ according to the vapor phase growth method. At the same time, the second thermoelectric material is introduced into a margin portion existing between the first insulating layer portion and the second insulating layer portion of the insulating layer C2 ′.

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