JP5134395B2 - Thermoelectric module, thermoelectric device using thermoelectric module, and method of manufacturing thermoelectric module - Google Patents

Description

  The present invention relates to a thermoelectric module capable of realizing power generation using a temperature difference and cooling or heating by applying a DC voltage, a thermoelectric device using the thermoelectric module, and a method of manufacturing the thermoelectric module.

  FIG. 7 shows a side sectional view of a conventional thermoelectric module 31. FIG. 7A shows the thermoelectric module 31 in a state immediately after the upper electrode is set to a high temperature and the lower electrode is set to a lower temperature than that in the drawing, and FIG. 7 shows a state of the thermoelectric module 31 after a certain period of time has elapsed with the temperature difference being higher than that in FIG.

  In the thermoelectric module 31, an n-type semiconductor 32, which is a thermoelectric material chip, is joined to the electrode 35 on the low temperature side by solder or the like, for example, and the opposite end of the n-type semiconductor 32 and the electrode 34 on the high temperature side are connected. Are also joined by solder or the like. Further, the same electrode 34 and a p-type semiconductor 33 which is a thermoelectric material chip are joined, and the opposite end of the p-type semiconductor 33 is joined to another electrode 35 to which another n-type semiconductor 32 is joined. With such a configuration, it can be electrically connected in series.

  When the thermoelectric module 31 is installed in an environment in which the electrode 34 is at a high temperature and the electrode 35 is at a lower temperature than that, and the end electrode is connected to an electric circuit or the like, a voltage is generated by the Seebeck effect, as indicated by an arrow The current flows through the electrode 35 → the n-type semiconductor 32 → the electrode 34 → the p-type semiconductor 33. This means that the electrons in the n-type semiconductor 32 obtain thermal energy from the high-temperature electrode 34 and move to the low-temperature electrode 35 where the thermal energy is released, whereas the holes in the p-type semiconductor 33 are hot. A current flows on the principle that heat energy is obtained from the electrode 34 and moved to the low temperature electrode 35 where the heat energy is released.

  If the temperature difference between the upper and lower electrodes 34 and 35 of the thermoelectric module 31 is further increased, there is a risk that the fracture 36 may occur near the bonding interface due to the difference in thermal expansion coefficient between the thermoelectric material chip and the electrode at the temperature difference. (FIG. 7B).

  In order to solve this, an elastic mesh metal wire network is disposed between the low temperature side electrode member and the thermoelectric material chip to prevent loss of elasticity of the metal wire network, and A technique that eliminates the need for solder bonding between the heat radiation side electrode and the thermoelectric material chip is disclosed (Patent Document 1). The difference in coefficient of thermal expansion is absorbed by sliding between the low-temperature side electrode member or thermoelectric material chip and the metal wire network. Furthermore, it is possible to absorb variations in the height of the thermoelectric material chip during assembly.

In addition, a technique is disclosed in which a conductive electrode material having a hole and a thermoelectric material are joined through a hole in the electrode material (Patent Document 2). Here, it is disclosed that the electrode material is a metal mesh.
JP-A-2005-277206 JP 2006-253343 A

  However, the thermoelectric module disclosed in Patent Document 1 has a large electric resistance and thermal resistance at the interface between the low-temperature electrode member and the thermoelectric material chip, and it is difficult to exhibit sufficient performance. In addition, the metal fine wire network is not used as an electrode member, and is disposed between the low temperature side electrode member and the thermoelectric material chip and is not completely joined. There was a risk of electrical short circuit.

  When the thermoelectric module disclosed in Patent Document 2 is used in an environment at a high temperature and a large temperature difference, there is a risk that stress concentrates on the joint between the thermoelectric material and the electrode material and breaks from the joint. was there.

  This invention is made | formed in view of the said subject, and makes it the subject which should be solved to provide the thermoelectric module which can make high durability and high performance compatible, and its manufacturing method. Another object to be solved is to provide a thermoelectric device using the thermoelectric module.

The structural feature of the thermoelectric module according to claim 1 for solving the above-described problem is that a plurality of low-temperature side electrode members and high-temperature side electrode members are interposed between the low-temperature side electrode members and the high-temperature side electrode members. A plurality of thermoelectric material chips that are arranged in electrical contact with one end side in contact with the high temperature electrode member and the other end side in contact with the low temperature side electrode member. A thermoelectric module that converts electrical energy into temperature difference or converts electrical energy into temperature difference,
The low temperature side electrode member is a stretchable fibrous member having electrical conductivity, the contact portion between the thermoelectric material chips is that they are fixed by bonding member.

The structural feature of the invention according to claim 2, in claim 1, wherein the low temperature side electrode member, by the fibrous member is woven diagonally to the thermal expansion direction of the electrode member is there.

The structural feature of the invention according to Claim 3 resides in that in Claim 1 or 2, wherein the low temperature side electrode member, by cloth-like body of the fibrous member is constituted by stacked two or more is there.

And the structural feature of the invention of the thermoelectric device according to claim 4 for solving the above-mentioned problems is a low temperature side substrate,
A high temperature side substrate facing the low temperature side substrate;
A plurality of low temperature side electrode members and high temperature side electrode members arranged so as to contact or adhere to respective opposing surfaces of the low temperature side substrate and the high temperature side substrate with a bonding member, the low temperature side electrode member, and the high temperature side electrode member A plurality of thermoelectric material chips, one end side of which is fixed to the high temperature electrode member and the other end side is fixed to the low temperature side electrode member, and is electrically arranged. A thermoelectric module that converts the electrical energy into a temperature difference or a temperature difference with the side, and converts the electrical energy into a temperature difference;
A thermoelectric device comprising:
The low temperature side electrode member is that it is a stretchable fibrous member with electrical conductivity.

The structural feature of the invention according to claim 5, in claim 4, wherein the low temperature side electrode member is that the fibrous member is woven diagonally to the thermal expansion direction of the electrode member .

The structural feature of the invention according to Claim 6 resides in that in Claim 4 or 5, wherein the low temperature side electrode member, by cloth-like body of the fibrous member is constituted by stacked two or more is there.

Further, the structural feature of the invention of the method of manufacturing a thermoelectric module according to claim 7 for solving the above-described problem is that a high temperature for joining one surface side of the plurality of high temperature side electrode members and one end side of the plurality of thermoelectric material chips. Side electrode bonding operation;
Low temperature side electrode fixing operation for fixing the other end side of the thermoelectric material chip and one surface side of a plurality of low temperature side electrode members through a bonding member,
The low temperature side electrode member is that it is a stretchable fibrous member with electrical conductivity.

The structural feature of the invention according to claim 8, in claim 7, wherein the low temperature side electrode member, by the fibrous member is woven diagonally to the thermal expansion direction of the electrode member is there.

The structural feature of the invention according to claim 9, in claim 7 or 8, wherein the low temperature side electrode member, by cloth-like body of the fibrous member is constituted by stacked two or more is there.

In the invention according to claim 1, and a low temperature side electrode member of the thermoelectric module, since it adopts a stretchable fibrous member having electrical conductivity, and one end and the other end of the thermoelectric module even if deformation caused by the temperature difference applied between the, because the fibrous member was used in the low temperature side electrode member stress is relieved by stretching, thermoelectric material chips, the electrode member and between them, Stress concentration is suppressed at the joint portion of the, and durability can be improved.

Then, on the low temperature side electrode member with expandable member, because they employ a structure for fixing the contact portion between the thermoelectric material chips, electrical short circuit due to reasons such as the electrode member is displaced suppression In addition, the electrical and thermal connection between the thermoelectric material chip and the electrode member can be sufficiently secured. In addition, since the bonding of the contact portion is realized by the joining member, it is possible to absorb the variation in the height of the thermoelectric material chip, the electrode member, etc. constituting the thermoelectric module and to reduce the occurrence of the variation in performance. Thermal connection can be realized.

In the invention according to claim 2, by adopting a configuration in which fibrous members to adopt the low temperature side electrode member is thermal expansion of the electrode member is woven diagonally to relatively large direction, heat The deformation generated in the electrode member due to the expansion can be effectively absorbed. That is, the stress concentration is further reduced by replacing the deformation generated in the electrode member with the change in the angle of the fibrous member knitted obliquely.

In the invention according to claim 3, as the fibrous member was used in the low temperature side electrode member, by employing a member cloth-like body is two or more discs, even if deformation caused by thermal expansion increases The displacement can be absorbed by shifting between the members of the overlapped cloth-like bodies. Since the overlapped cloth-like body is originally an integral member, there is a limit to the size of the generated displacement, and the possibility of occurrence of a short circuit between adjacent electrode members and the like can be minimized. Here, “two or more cloth-like bodies are overlapped” in this specification means that the cloth-like body originally formed integrally is formed by bending or when a fibrous member is knitted. It is meant to be formed as an integral member.

In the invention according to claim 4, in the low temperature side electrode member of the thermoelectric module, since it adopts a stretchable fibrous member having electrical conductivity, and one end and the other end of the thermoelectric module even if deformation caused by the temperature difference applied between the, because the fibrous member was used in the low temperature side electrode member stress is relieved by stretching, thermoelectric material chips, the electrode member and between them, Stress concentration is suppressed at the joint portion of the, and durability can be improved.

Then, on the low temperature side electrode member with expandable member, because they employ a structure for fixing the contact portion between the thermoelectric material chips, electrical short circuit due to reasons such as the electrode member is displaced is prevented In addition, the electrical and thermal connection between the thermoelectric material chip and the electrode member can be sufficiently secured. In addition, since the bonding of the contact portion is realized by the joining member, it is possible to absorb the variation in the height of the thermoelectric material chip, the electrode member, etc. constituting the thermoelectric module and to reduce the occurrence of the variation in performance. Thermal connection can be realized.

In the invention according to Claim 5, by employing a configuration in which fibrous members to adopt the low temperature side electrode member is thermal expansion of the electrode member is woven diagonally to relatively large direction, heat The deformation generated in the electrode member due to the expansion can be effectively absorbed. That is, the stress concentration is further reduced by replacing the deformation generated in the electrode member with the change in the angle of the fibrous member knitted obliquely.

In the invention according to claim 6, as the fibrous member was used in the low temperature side electrode member, by employing a member cloth-like body is two or more discs, even if deformation caused by thermal expansion increases The displacement can be absorbed by shifting between the members of the overlapped cloth-like bodies. Since the overlapped cloth-like body is originally an integral member, there is a limit to the size of the generated displacement, and the possibility of occurrence of a short circuit between adjacent electrode members and the like can be minimized.

In the invention according to claim 7, and a low temperature side electrode member of the thermoelectric module, since it adopts a stretchable fibrous member having electrical conductivity, and one end and the other end of the thermoelectric module even if deformation caused by the temperature difference applied between the, because the fibrous member was used in the low temperature side electrode member stress is relieved by stretching, thermoelectric material chips, the electrode member and between them, Stress concentration is suppressed at the joint portion of the, and durability can be improved.

Then, on the low temperature side electrode member with expandable member, because they employ a structure for fixing the contact portion between the thermoelectric material chips, electrical short circuit due to reasons such as the electrode member is displaced is prevented In addition, the electrical and thermal connection between the thermoelectric material chip and the electrode member can be sufficiently secured. In addition, since the bonding of the contact portion is realized by the joining member, it is possible to absorb the variation in the height of the thermoelectric material chip, the electrode member, etc. constituting the thermoelectric module and to reduce the occurrence of the variation in performance. Thermal connection can be realized.

In the invention according to claim 8, by adopting a configuration in which fibrous members to adopt the low temperature side electrode member is thermal expansion of the electrode member is woven diagonally to relatively large direction, heat The deformation generated in the electrode member due to the expansion can be effectively absorbed. That is, the stress concentration is further reduced by replacing the deformation generated in the electrode member with the change in the angle of the fibrous member knitted obliquely.

In the invention according to claim 9, as a fibrous member employing the low temperature side electrode member, by employing a member cloth-like body is two or more discs, even if deformation caused by thermal expansion increases The deformation | transformation can be absorbed by shifting | deviating between the piled cloth-like bodies. Since the overlapped cloth-like body is originally an integral member, there is a limit to the size of the generated displacement, and the possibility of occurrence of a short circuit between adjacent electrode members and the like can be minimized.

Hereinafter, the present invention will be specifically described using embodiments.
(Embodiment 1)
The structure and manufacturing process of the thermoelectric power generation module (thermoelectric module) 10 of this embodiment are shown in FIG.

  The thermoelectric power generation module 10 of this embodiment is a member having a flat appearance having a predetermined length and a predetermined width as a whole, and a high temperature side electrode member which is a flat member formed of a Ti—Cu alloy. 1, a p-type thermoelectric material chip 2 a and an n-type thermoelectric material chip 2 b that are prismatic members having the same height, and a low-temperature side electrode member 5. The low temperature side electrode member 5 is formed of a flat knitted copper wire electrode in which a metallic fibrous member is knitted, and is an electrically conductive and expandable member. The low temperature side electrode member 5 has a cylindrical appearance and is formed of a fibrous member. The fibrous member forms an electrode member by flat knitting, and the fibrous member is knitted in an oblique direction with respect to the length direction and the width direction of the low temperature side electrode member 5. In some cases, the low temperature side electrode member 5 may be a non-woven fabric or a round string that is a kind of braid. The high temperature side electrode member 1 is provided so as to straddle between the thermoelectric material chips 2a and 2b. When heated, the high temperature side electrode member 1 is thermally expanded in the direction in which the interval between the thermoelectric material chips 2a and 2b is opened. Are fibers obliquely to the length direction so that they can expand and contract in the direction connecting the thermoelectric material chips 2a and 2b (the length direction of the low temperature side electrode member 5) so as to absorb the deformation (stress) generated by the thermal expansion. The braided member is knitted.

  The high temperature side electrode member 1 appears on one side of the thermoelectric power generation module 10, and the low temperature side electrode member 5 appears on the other side. The thermoelectric material chips 2a and 2b are arranged side by side so that one end side faces the one surface side of the thermoelectric power generation module 10 and the other end side faces the other surface side.

  There are a plurality of thermoelectric material chips 2a and 2b in the same number, and one end side is electrically connected to one surface side of the high temperature side electrode member 1, and the other end side is electrically connected to the low temperature side electrode member 5. ing. Each of these thermoelectric material chips 2a and 2b is combined one by one, and one end thereof is bonded to one surface side of the high temperature side electrode member 1, and is combined and bonded so as to form a U-shape as a whole (assembled member) (High temperature side electrode joining operation: FIGS. 1A and 1B). That is, in the assembled member, the thermoelectric material chips 2a and 2b are arranged side by side so that the direction formed by the one end side and the other end side (the height direction of the prism) is arranged in parallel at a predetermined interval. This bonding can be performed by diffusion bonding.

  In this way, the assembled members are arranged side by side so that the high temperature side electrode members 1 are arranged in the same plane. As a method of arranging the assembled members, a predetermined number of assembled members are arranged side by side so that a predetermined number of assembled members are arranged side by side so that a predetermined width is obtained. A member having a flat appearance having a length and a predetermined width is formed to form the thermoelectric power generation module 10 of the present embodiment. The p-type thermoelectric material chip 2a and the n-type thermoelectric material chip 2b are adjacent to each other between the adjacent assembled members, and one surface side of the low temperature side electrode member 5 is connected to the other end side of each of the thermoelectric material chips 2a and 2b. To electrically connect between them. In this connection, the other end side of the thermoelectric material chips 2a and 2b is plated (FIG. 1 (c)), and after forming the plating layer 3, the bonding member formed between the low temperature side electrode member 5 is used. The solder layer 4 is used for bonding. The solder layer 4 is first formed by screen-printing solder on one surface side of the low temperature side electrode member 5. The thickness and area of the solder layer formed on each low temperature side electrode member 5 are managed by the thickness and opening area of the mask used for screen printing. Thereafter, bonding is performed by heating the plated layer 3 on the other end side of the thermoelectric material chips 2a and 2b of the assembled member in contact with the solder layer 4 formed on one surface side of the low temperature side electrode member 5 (low temperature). Side electrode fixing operation: In FIGS. 1D and 1E, the thermoelectric power generation module 10 of the present embodiment is obtained. When joining by soldering, the lead wire take-out portion 6 is also joined at the same time.

  In the obtained thermoelectric power generation module 10, the p-type thermoelectric material chip 2a, the high temperature side electrode member 1, the n type thermoelectric material chip 2b, the low temperature side electrode member 5, the p type thermoelectric material chip 2a,. The thermoelectric material chips 2a and the n-type thermoelectric material chips 2b are connected alternately and continuously. The combination of the p-type thermoelectric material chip 2a and the n-type thermoelectric material chip 2b corresponds to a predetermined electromotive force, and is connected in series according to the required electromotive force.

  As shown in FIG. 2, the thermoelectric power generation module 10 is provided with a high temperature side substrate 20 on one side and a low temperature side substrate 21 on the other side to form a thermoelectric power generation device (thermoelectric device). To do. The low temperature side substrate 21 and the high temperature side substrate 20 are arranged side by side with a predetermined interval corresponding to the thickness of the thermoelectric power generation module 10 in their thickness direction. The low temperature side substrate 21 and the high temperature side substrate 20 and the thermoelectric power generation module 10 are heat exchangers, and are connected to an external high temperature source and a low temperature source, respectively. For example, the high temperature source is a muffler through which vehicle exhaust gas passes, and the low temperature source is a pipe-like member through which a cooling material flows. The low temperature side substrate 21 and the high temperature side substrate 20 and the thermoelectric power generation module 10 are connected so as to exhibit sufficient thermal conductivity. For example, they can be connected in contact with each other via heat conductive grease, or can be connected in a state of being integrally fixed using diffusion bonding, welding, soldering, or the like. When fixing together, it is desirable that the coefficient of thermal expansion between the members to be fixed is approximate. In this embodiment, an adhesive layer 8 made of a heat-resistant adhesive is provided between the high temperature side electrode member 1 and the high temperature side substrate 20, and a bonding layer made of heat conductive grease is provided between the low temperature side electrode member 5 and the low temperature side substrate 21. 9 is connected. In this embodiment, the thermally conductive grease penetrates and fills the inside of the low temperature side electrode member 5, thereby increasing the contact area and improving the thermal conductivity, and using the thermally conductive grease on the outside. There is less risk of spilling and reducing thermal conductivity.

  Since the thermoelectric power generation module 10 of the present embodiment has the above configuration, the following operational effects are exhibited.

  That is, with respect to the thermoelectric generator, the low temperature side substrate 21 is brought into contact with the low temperature source, and the high temperature side substrate 20 is brought into contact with the high temperature source, whereby the thermoelectric material is passed through the low temperature side electrode member 5 and the high temperature side electrode member 1, respectively. A temperature difference is generated between one end side and the other end side of the chips 2a and 2b. Due to the generated temperature difference, holes move in the p-type thermoelectric material chip 2a and electrons move in the direction of the low temperature side electrode member 5 in the n-type thermoelectric material chip 2b, and an electromotive force is generated.

  Due to the temperature difference thus generated, the high-temperature side electrode member 1 and the low-temperature side electrode member 5 have different thermal expansion. In particular, the elongation in the spreading direction of the thermoelectric power generation module 10 is different between the one side and the other side. Specifically, the elongation in the plane spreading direction on the one surface side where the high temperature side electrode member 1 is disposed and brought to a high temperature is larger than the elongation in the plane spreading direction on the other surface side where the low temperature side electrode member 5 is placed and the temperature is lowered. Also grows. In this case, since the low temperature side electrode member 5 is composed of a flat knitted copper wire member which is a cylindrical member, it has excellent stretchability, and the high temperature side electrode regardless of the magnitude of thermal expansion derived from itself. It expands and contracts according to the elongation of the member 1. In particular, as shown in FIG. 3, since the low temperature side electrode member 5 can move independently in the vertical direction of the drawing, the low temperature side electrode member 5 absorbs the difference in the magnitude of thermal expansion. For example, the distortion applied to the thermoelectric material chips 2a and 2b and the high temperature side electrode member 1 or the low temperature side electrode member 5 is reduced, and the occurrence of inconvenience is suppressed. For example, in FIG. 3, when stress is applied to the thermoelectric material chips 2 a and 2 b and the low temperature side electrode member 5 in a direction deviating from the front and back of the paper surface due to the thermal expansion of the high temperature side electrode member 1, The stress applied when the upper side (I) of the side electrode member 5 is shifted from the lower side (II) of the drawing can be absorbed. Further, when stress is applied to the thermoelectric material chips 2a and 2b and the low temperature side electrode member 5 in the direction deviating in the horizontal direction of the drawing due to the thermal expansion of the high temperature side electrode member 1, as shown in FIG. Furthermore, the stress applied when the upper side (I) and the lower side (II) of the low temperature side electrode member 5 are shifted in the directions of the arrows L and R can be absorbed. In this case, the low temperature side electrode member 5 is a cylindrical member, and the respective portions (I and II) are connected at both end portions in the width direction in FIGS. When the chips 2a and 2b are displaced from the low temperature side electrode member 5 and the low temperature side substrate 21, the possibility of contact / short circuit with the adjacent thermoelectric material chips 2a and 2b is reduced.

  Moreover, in this embodiment, the solder layer 4 which joins between the low temperature side electrode member 5 and the thermoelectric material chip | tips 2a and 2b is located in the surface vicinity of the upper side part (I) of the low temperature side electrode member 5 drawing further. Therefore, the relative movement between the fibrous members entangled in the low temperature side electrode member 5 is not hindered by the solder layer 4, and the stretchability of the low temperature side electrode member 5 can be sufficiently exhibited. That is, since the low temperature side electrode member 5 is a member formed by weaving a fibrous member, the joining member can penetrate into the inside, but when the joining member penetrates deeply into the inside and is fixed, the low temperature side electrode member 5 Therefore, it is desirable to fix the bonding member only at the contact portion near the surface as much as possible. Therefore, it is desirable to fix the low temperature side electrode member 5 and the other end side of the thermoelectric material chip only at the contact portion.

(Modification)
-As the above-mentioned low temperature side electrode member 5, the member by which the cloth-like body by which the fibrous member was knitted was piled 2 or more is employable. By adopting a configuration in which two or more cloth-like bodies are stacked in place of the low temperature side electrode member 5, the stretchability of the low temperature side electrode member can be improved. For example, even if a mode in which the other surface side of the low temperature side electrode member is fixed to the low temperature side substrate 21 is adopted, the low temperature side substrate 21 can be slid within the two or more stacked low temperature side electrode members. Regardless of the size, the low temperature side electrode member of the thermoelectric power generation module 10 can be expanded and contracted independently. In particular, by adopting a member obtained by bending a single cloth-like body, as in the first embodiment in which a fibrous member is knitted into a tubular shape, the overlapped members are arranged. There is an advantage that it does not easily fall apart.

Further, as the low-temperature side electrode member, a flat hammered article obtained by combining a plurality of aggregate members composed of fibrous members into a flat shape can be adopted. Then, by providing a solder layer 4 in the vicinity of the surface and bonding it to the thermoelectric material chips 2a and 2b, a flexible material that imparts relative movement and stretchability between the one surface side and the other surface side of the low temperature side electrode member is provided. It can be a member.
・ The bonding between the high-temperature side electrode member and the thermoelectric material chip is performed by diffusion bonding. However, other bonding methods such as soldering and brazing can be used as long as the durability at the assumed operating temperature can be maintained. Can also be adopted. Moreover, the member formed from a flat knitted copper wire electrode like the low temperature side electrode member mentioned above can also be employ | adopted about a high temperature side electrode member.

(Embodiment 2)
The structure of the thermoelectric power generation module 11 of this embodiment is shown in FIG.

  The thermoelectric power generation module 11 of the present embodiment has the same configuration as the thermoelectric power generation module 10 described above except that a low temperature side electrode member 5 ′ is adopted instead of the low temperature side electrode member 5 in the first embodiment.

  The low temperature side electrode member 5 ′ is formed of a flat knitted copper wire electrode like the low temperature side electrode member 5. The low temperature side electrode member 5 ′ is integrally formed by joining the fibrous members constituting the portion to be joined to the other end side of the thermoelectric material chips 2a and 2b by welding such as percussion welding, resistance welding, or ultrasonic welding. It is what has been made. As shown in FIG. 6, percussion welding is performed by pressing a flat knitted copper wire electrode A, which is a stretchable member formed by weaving a fibrous member, with an upper die 50 and a lower die 60. This is an operation of welding and joining between the fibrous members in the part. A capacitor in which a predetermined amount of electric power is stored before pressing is connected between the upper mold 50 and the lower mold 60, and is discharged simultaneously with pressing by the upper mold 50 and the lower mold 60, and the arc heat generated at that time is discharged. Joining is completed with energy. Therefore, since discharge and pressing occur simultaneously, the fibrous members can be instantaneously joined. By cutting the processed flat knitted copper wire electrode B into a predetermined length, the low temperature side electrode member 5 'can be obtained. The low-temperature side electrode member 5 'has a portion 5'a that is fixed to the thermoelectric material chips 2a and 2b, in which the fibrous members are joined and integrated, so that the low-temperature side electrode member can be used during the joining process and at the time of use. Since 5 ′ can be prevented from being decomposed, workability, yield, durability, and the like can be improved. And since the part 5'b between the adhering parts 5'a keeps the flat knitted state, the relative movement between the fibrous members is not restricted, and the stretchability is maintained. Therefore, it becomes possible to expand and contract in accordance with the thermal expansion of the high temperature side electrode member 1, and concentration of stress can be prevented.

(Example)
-Manufacture of thermoelectric power generation module for evaluation A thermoelectric power generation module was manufactured as a thermoelectric power generation module for evaluation by the manufacturing method disclosed in the first embodiment. The thermoelectric material chips 2a and 2b used were quadrangular prisms and were cubes each having a side of 4 mm. And the size of the high temperature side electrode member 1 made of Ti—Cu alloy is 4 mm × 9 mm × thickness 1 mm, flat knitted copper wire electrode (Futaba Electric Wire Co., Ltd. flat knitted copper wire, JCS 1236: 2001 compliant, fibrous member The size of the low temperature side electrode member 5 made of a strand diameter of 0.08 mm was 4 mm × 9 mm × thickness 0.6 mm. Using 17 of these (18 only for the low temperature side electrode member 5), a square flat thermoelectric power generation module 10 having a side of 30 mm was manufactured.

  The other surface side of each thermoelectric material chip 2a and 2b and the one surface side of each low temperature side electrode member 5 were joined by soldering. The joining state was controlled by changing the amount of solder used for joining. The amount of solder is controlled by changing the thickness of the solder printing plate used when forming the solder layer on one surface side of the low-temperature side electrode member 5 by printing and the size of one side of the opening portion. And the thermoelectric power generation module of Comparative Examples 1-3 was manufactured. The actual values are shown in Table 1.

The both sides of the manufactured thermoelectric power generation module were sandwiched between the low temperature side substrate 21 and the high temperature side substrate 20 to manufacture the corresponding thermoelectric power generation devices of the respective examples and comparative examples. The low temperature side electrode member 5 and the low temperature side substrate 21 are joined with heat conductive grease (silicone grease: KS613, manufactured by Shin-Etsu Chemical Co., Ltd.), and between the high temperature side electrode member 1 and the high temperature side substrate 20. Bonded with a heat-resistant adhesive.
・ Evaluation test About the thermoelectric power generator of each example and comparative example, the temperature of the high temperature side electrode member of the thermoelectric power generation module was kept at 600 ° C., the temperature of the low temperature side electrode member was kept at 100 ° C., and the inside measured at room temperature before and after holding The rate of change in resistance magnitude was evaluated. The results are shown in Table 1. Here, a non-defective product having a rate of change in internal resistance of less than 10% was determined. Moreover, the joining state of the low temperature side electrode member and the other end side of the thermoelectric material chip was visually evaluated.

  As is apparent from Table 1, the change rate of internal resistance of the device of Example 1 is 4%, which shows sufficient performance, whereas the devices of Comparative Examples 1 to 3 all have a change rate of internal resistance. However, it was found that sufficient performance cannot be demonstrated. In particular, with the apparatus of Comparative Example 1, it was difficult to measure the internal resistance.

  And the joining state between the low temperature side electrode member and the thermoelectric material chip | tip was a sufficient state about the apparatus of Example 1, Comparative Example 2 and 3. FIG. However, in the apparatus of Example 1, since the applied solder stayed only at the bonding interface between the low temperature side electrode member and the thermoelectric material chip, the low temperature side electrode member maintained sufficient elasticity and flexibility, but Comparative Example 2 The devices of No. 3 and No. 3 have a large amount of solder, and the solder is impregnated into the inside of the low temperature side electrode member formed from the flat knitted copper wire electrode, so that the flexibility is impaired.

  From the above results, a flat knitted copper wire electrode, which is a member formed by weaving a fibrous member as the low temperature side electrode member so as to be stretchable, is employed without loss of stretchability, and thus the thermoelectric power generation module and its thermoelectric It was found that the durability of thermoelectric generators using power generation modules can be improved. It has been found that a method for maintaining the stretchability of the flat knitted copper wire electrode can be achieved by limiting the solder for bonding with the thermoelectric material chip to the vicinity of the surface which is the bonding interface of the flat knitted copper wire electrode.

It is a figure which shows the structure of the thermoelectric power generation module 10 of this Embodiment 1, and its manufacturing process. It is a side view which shows the structure of the thermoelectric generator of this Embodiment 1. It is the schematic diagram which represented typically the cross section of the junction part of the thermoelectric material chip | tip of the thermoelectric power generating apparatus of this Embodiment 1, an electrode member, and a board | substrate. It is the schematic diagram which represented typically the cross section of the junction part of the thermoelectric material chip | tip of the thermoelectric power generating apparatus of this Embodiment 1, an electrode member, and a board | substrate. It is a figure which shows the structure of the thermoelectric generation module 11 of this Embodiment 2, and its manufacturing process. It is a figure which shows the manufacturing process of the low temperature side electrode member 5 'of the thermoelectric generation module 11 of this Embodiment 2. FIG. It is a sectional side view of the conventional thermoelectric power generation module.

1: high temperature side electrode member, 10, 11: thermoelectric power generation module,
20: Low temperature side substrate, 21: High temperature side substrate, 2a: p-type thermoelectric material chip, 2b: n-type thermoelectric material chip,
3: Plating layer,
4: Solder layer,
5, 5 ′: low temperature side electrode member,
6: Lead wire takeout part,
8: adhesive layer,
9: bonding layer,
31: Thermoelectric power generation module, 32: n-type semiconductor, 33: p-type semiconductor, 34, 35: electrode, 36: destruction.

Claims (9)

A plurality of low temperature side electrode members and high temperature side electrode members, provided between the low temperature side electrode member and the high temperature side electrode member and having one end in contact with the high temperature electrode member and the other end being the low temperature side electrode member A thermoelectric module that has a plurality of thermoelectric material chips that are electrically arranged in contact with each other, and converts the electrical energy into electrical energy due to a temperature difference between one end side and the other end side, or converts electrical energy into a temperature difference. ,
The low temperature side electrode member is a stretchable fibrous member having electrical conductivity, thermoelectric modules, wherein a contact portion between the thermoelectric material chip is fixed by bonding member. According to claim 1, wherein the low temperature side electrode member is a thermoelectric module, wherein the fibrous member is woven diagonally to the thermal expansion direction of the electrode member. According to claim 1 or 2, wherein the low temperature side electrode member is a thermoelectric module, characterized in that the cloth-like material of the fibrous member is constituted by stacked two or more. A low temperature side substrate,
A high temperature side substrate facing the low temperature side substrate;
A plurality of low temperature side electrode members and high temperature side electrode members arranged so as to contact or adhere to respective opposing surfaces of the low temperature side substrate and the high temperature side substrate with a bonding member, the low temperature side electrode member, and the high temperature side electrode member A plurality of thermoelectric material chips, one end side of which is fixed to the high temperature electrode member and the other end side is fixed to the low temperature side electrode member, and is electrically arranged. A thermoelectric module that converts the electrical energy into a temperature difference or a temperature difference with the side, and converts the electrical energy into a temperature difference;
Have
The low temperature side electrode member is a thermoelectric device using a thermoelectric module, which is a stretchable fibrous member with electrical conductivity. According to claim 4, wherein the low temperature side electrode member thermoelectric device, wherein the fibrous member is woven diagonally to the thermal expansion direction of the electrode member. According to claim 4 or 5, wherein the low temperature side electrode member is a thermoelectric device using a thermoelectric module, characterized in that the cloth-like material of the fibrous member is constituted by stacked two or more. A high temperature side electrode joining operation for joining one surface side of the plurality of high temperature side electrode members and one end side of the plurality of thermoelectric material chips;
Low temperature side electrode fixing operation for fixing the other end side of the thermoelectric material chip and one surface side of a plurality of low temperature side electrode members through a bonding member,
The low temperature side electrode member The manufacturing method of the thermoelectric module, which is a stretchable fibrous member with electrical conductivity. According to claim 7, wherein the low temperature side electrode member The manufacturing method of the thermoelectric module, wherein the fibrous member is woven diagonally to the thermal expansion direction of the electrode member. According to claim 7 or 8, wherein the low temperature side electrode member The manufacturing method of the thermoelectric module, wherein a cloth-like body of the fibrous member is constituted by stacked two or more.