JP5598138B2 - Method for manufacturing pipe-type thermoelectric power generation device, and method for manufacturing the laminate - Google Patents

Description

  The present invention relates to a thermoelectric power generation device that converts thermal energy into electrical energy.

  Thermoelectric power generation is a technology that directly converts thermal energy into electrical energy using the Seebeck effect in which an electromotive force is generated in proportion to the temperature difference applied to both ends of a substance. This technology has been put to practical use in remote power supplies, space power supplies, military power supplies, and the like.

  A conventional thermoelectric power generation device has a plate-like structure called a π-type structure that combines a P-type semiconductor and an N-type semiconductor with different carrier codes, and is connected in parallel and electrically in series. ing. By making one surface of the flat device contact a heat source and cooling the other surface, a temperature difference is generated in the device to generate power.

  In addition, in the device utilizing the anisotropy of thermoelectric properties in a laminated structure of different materials composed of a metal and Bi, which is a thermoelectric material, the inventors of the present invention have a thickness ratio of each material in a laminated body (hereinafter referred to as a laminated material). We have found that excellent power generation performance is realized by appropriately selecting the inclination angle in the stacking direction and invented a thermoelectric power generation device using this (Patent Document 1).

  However, the conventional π-type structure and the device structure described in Patent Document 1 all have a flat plate structure. Therefore, in order to collect heat from a heat source such as hot water or high-temperature exhaust gas and generate electric power, a process for filling the gap formed between the pipe through which the fluid heat source flows and the thermoelectric power generation device in some form, or pipes There was a big restriction that the surface of the machine had to be flat. Furthermore, heat conductive grease, adhesive, double-sided tape, etc. must be used for connection between the heat source and the thermoelectric generator device, and heat cannot be efficiently collected from the heat source. The same applies to the heat dissipating part that performs cooling.

Japanese Patent No. 4078392

  As described above, in the conventional thermoelectric conversion device, heat collection and heat dissipation structure are largely restricted, and heat collection cannot be performed efficiently. Therefore, thermoelectric power generation sufficient for practical use cannot be performed in many applications.

  The present invention solves the above-mentioned conventional problems, and in order to achieve high power generation characteristics, a pipe-type thermoelectric power generation device having a simple structure that enables good heat transfer with a fluid heat source, and It aims at providing the manufacturing method of a laminated body.

  In order to solve the above-described conventional problems, a method for manufacturing a pipe-type thermoelectric power generation device according to the present invention includes a step of alternately laminating members made of metal and a member made of a thermoelectric material, and a step of joining the laminated members. And the step of connecting the electrodes.

  By the method for manufacturing a pipe-type thermoelectric power generation device of the present invention, a pipe-type thermoelectric power generation device having good heat transfer with a fluid heat source and a laminate thereof can be manufactured.

The figure which showed the manufacturing method of the pipe type thermoelectric power generation device in Embodiment 1 of this invention The figure which showed the manufacturing method of the pipe type thermoelectric power generation device in Embodiment 1 of this invention The perspective view of the pipe-type thermoelectric power generation device in Embodiment 1 of this invention Sectional drawing of the pipe-type thermoelectric power generation device in Embodiment 1 of this invention Sectional drawing of the pipe-type thermoelectric power generation device in Embodiment 1 of this invention Sectional drawing of the pipe-type thermoelectric power generation device in Embodiment 1 of this invention The perspective view of the pipe-type thermoelectric power generation device in Embodiment 1 of this invention The perspective view of the pipe-type thermoelectric power generation device in Embodiment 1 of this invention The figure which showed an example of the manufacturing method of the laminated body which consists of a metal and the thermoelectric material in Embodiment 1 of this invention Sectional drawing of the cup-shaped member in Embodiment 1 of this invention The figure which showed the manufacturing method of the pipe type thermoelectric power generation device in Embodiment 2 of this invention The figure which showed the preparation methods of the laminated body in Embodiment 2 of this invention The figure which showed the preparation methods of the pipe-type thermoelectric power generation device in Embodiment 3 of this invention The figure which showed the method of plastic working of the laminated body in Embodiment 3 of this invention The figure which showed the manufacturing method of the pipe type thermoelectric power generation device in Embodiment 4 of this invention The figure at the time of arranging the member which consists of metals in Embodiment 4 of this invention on a straight line The figure at the time of arranging the member which consists of metals in curve shape in Embodiment 4 of this invention The figure at the time of arranging the member which consists of metals in Embodiment 4 of this invention using a mandrel

  Embodiments of the present invention will be described below with reference to the drawings.

(Embodiment 1)
FIG. 1 shows a manufacturing process of a pipe-type thermoelectric power generation device in the present embodiment. The manufacturing process of the thermoelectric power generation device in the present embodiment includes a step (S1) of preparing an inclined laminated body made of a metal and a thermoelectric material, a step (S2) of joining the metal and the thermoelectric material, A step of producing one electrode and a second electrode (S3).

  More specifically, for example, as shown in FIG. 3, a step of manufacturing a cup-shaped member made of a metal or a thermoelectric material (S11), a member made of a metal and a member made of a thermoelectric material are alternately laminated, Through the joining step (S12), an inclined laminate made of a metal and a thermoelectric material can be manufactured. In order to generate thermoelectric power using a thermoelectric power generation device, electrodes are required at both ends of the device, and thus a step (S13) of producing the first electrode and the second electrode so as to sandwich the laminate is necessary. However, the step of creating the first electrode and the second electrode may not be performed at the time of creating the laminate. Moreover, when only a laminated body is manufactured, it is sufficient to perform the steps S1 and S2. A more detailed manufacturing configuration will be described later.

  The pipe-type thermoelectric power generation device realized by the method for manufacturing a pipe-type thermoelectric power generation device of the present invention is a pipe-like structure in which the metal 11 and the thermoelectric material 12 are alternately laminated at a constant lamination ratio as shown in FIG. In this structure, both ends of the laminate are sandwiched between the first electrode 15 and the second electrode 16. Moreover, it has a through hole inside. As shown in the sectional view of FIG. 4, the laminated surface of the metal 11 and the thermoelectric material 12 is inclined at a constant angle θ with respect to the axial direction 23 of the through hole. Further, the laminated surface is difficult to form a gap at the laminated interface when laminated. The cross-sectional shape of the through-hole is not limited to a circle as long as it has a penetrating structure, and may be an ellipse as shown in FIG. 5, a polygon as shown in FIG. 6, or an irregular shape.

  A suitable range of the angle θ varies depending on the combination of the metal 11 and the thermoelectric material 12. For example, in the case of a combination of Cu and Bi, θ is preferably in the range of 5 ° to 45 °.

  By laminating the metal 11 and the thermoelectric material 12 so that there is no gap between the metal 11 and the thermoelectric material 12, the fluid flowing inside (through hole) and outside of the thermoelectric device is prevented from mixing with each other. be able to. In FIG. 3, when the inner fluid 21 is a high-temperature fluid, the outer fluid 22 is a low-temperature fluid, and when the inner fluid 21 is a low-temperature fluid, the outer fluid 22 is a high-temperature fluid.

  Thereby, a temperature difference arises between the inner side and the outer side of the device, and power generation can be performed. The generated electric power can be taken out by connecting an electric load to the first electrode 15 and the second electrode 16 provided at both ends of the pipe-type thermoelectric power generation device.

  Further, as shown in FIG. 7, a groove portion 19 can be provided in the laminated body of the metal 11 and the thermoelectric material 12. The groove portion 19 is preferably filled with an electrical insulator so that the laminate is not electrically short-circuited. If the groove portion 19 is filled with an elastic resin or the like, the thermal stress applied to the laminate can be relaxed. Of course, the groove portion 19 can be simply cut out and hollow. Furthermore, if the ends of the first electrode 15 and the second electrode 16 are formed in a pipe shape as shown in FIG. 8, it becomes easy to introduce a fluid into the inner cylindrical portion of the laminate, and a more practical pipe-type heat A power generation device is realized.

  The metal 11 is not particularly limited as long as it is a material having good electrical conduction and thermal conduction. Specifically, Cu, Ag, Al, Au, etc. are good.

The thermoelectric material 12 may be Bi, Bi ₂ Te ₃ or Bi doped with Sb, Se, Bi ₂ Te ₃ , YbAl ₃ , PbTe, etc., but is not limited to these, and various thermoelectric materials Can be used.

  The first electrode 15 and the second electrode 16 are not particularly limited as long as they are materials having good electrical conductivity. If the metal 11 is disposed at both ends of the pipe structure, the first electrode 15 and the second electrode 16 can be omitted.

  The manufacturing process of the pipe-type thermoelectric power generation device according to the first embodiment will be described in more detail. First, as shown in FIG. 9, a necessary number of members 81 made of cup-type metal and members 82 made of cup-type thermoelectric material are respectively produced (S1 in FIG. 1). The cross section of the cup-shaped member is composed of two tapered surfaces having a constant inclination angle θ with respect to the inner side surface 92, the outer side surface 93 and the through-hole axis 91 as shown in FIG.

  Various methods can be used for producing the cup-shaped member. For example, methods such as cutting, electric discharge machining, casting, plastic working, and putting raw material powder into a mold and sintering can be used. Of these, plastic working such as press working is preferable because it is suitable for mass production.

  Next, a process of alternately laminating and joining metal members and thermoelectric material members (S2 in FIG. 1) will be described. First, cup-shaped metal members and thermoelectric material members produced in the step S1 are alternately laminated so that a pipe-like laminated structure is obtained as a whole. Since the cup-shaped member has a through-hole inside, a large number of members can be easily laminated by passing a rod or wire serving as a guide through the through-hole. For the joining of the members thus laminated, a method such as hot pressing in which pressure is applied in a high temperature atmosphere, or discharge plasma sintering in which the laminated body itself is energized and heated and pressure is applied at the same time can be used. In addition, a joint can be formed simultaneously with the step of laminating the metal and thermoelectric material members using silver paste or solder.

  The first electrode 15 and the second electrode 16 can be produced in various ways (S3 in FIG. 1), such as vapor deposition such as vapor deposition and sputtering, as well as application of conductive paste, plating, thermal spraying, and soldering. The method can be used. Further, if both ends of the laminate are terminated with a member 81 made of metal, this can be used as the first electrode 15 and the second electrode 16 and the step S3 can be omitted. In order to facilitate the production of the electrode, a treatment such as pre-grinding and planarizing both ends of the laminate may be performed. Note that the step S3 may be created independently of the laminate production.

  In the method for manufacturing a pipe-type thermoelectric power generation device of the present invention, after a sufficiently long laminate is produced in the step S2, it is divided into a plurality of laminates having a required length, and each of the divided laminates is divided. On the other hand, the first electrode and the second electrode can also be produced.

(Embodiment 2)
In the method for manufacturing a pipe-type thermoelectric power generation device of the present invention, part of the step S1 and part of the step S2 in FIG. 1 can be performed simultaneously. For example, as shown in FIG. 11, first, a member made of a flat metal having an opening inside and a member made of a thermoelectric material are respectively produced (S21 in FIG. 11). Next, as shown in FIG. 12, members 101 made of metal and members 102 made of a thermoelectric material are alternately laminated, and plastic working by pressing using a punch 103 and a die 104 and jointing of the laminated body are performed at the same time. A body is prepared (S22 in FIG. 11). In FIG. 12, a part of the die 104 shows a cross section. Thereafter, the first electrode and the second electrode are produced (S23 in FIG. 11).

  In step S22 in which the member made of metal and the member made of thermoelectric material are laminated and joined, if the number of members to be laminated is too large, the variation in the magnitude of plastic deformation of each layer becomes significant. Therefore, it is preferable that the number of members processed at a time is not so large. A suitable range of the number of members used in one processing varies depending on the dimensions of the members, but is preferably 20 or less, more preferably 10 or less. If a laminate with a desired length cannot be obtained by a single process, it is necessary to repeat step S22 a plurality of times and separately provide a step of joining the resulting laminates together (S24 in FIG. 11). .

  Various methods such as casting can be used for the production of the flat plate member having the opening in step S21, but the desired member can be easily and accurately produced by shearing such as punching a plate material. This is preferable.

  In the plastic working in step S22, it is preferable to use a die made of carbon or the like to which the metal and the thermoelectric material do not adhere. In addition, when the thermoelectric material is brittle at room temperature, cracking of the member can be prevented by performing plastic working while heating. The heating temperature during the plastic working is preferably equal to or lower than the melting point of the thermoelectric material in order to prevent an extreme dimensional shift after the working. Further, a cored bar such as a mandrel may be inserted into the laminated body during plastic working.

  The first electrode 15 and the second electrode 16 can be produced in various ways (S23 in FIG. 1), such as vapor deposition such as vapor deposition and sputtering, as well as application of conductive paste, plating, thermal spraying, and soldering. The method can be used. Further, if both ends of the laminate are terminated with a member 81 made of metal, this can be used as the first electrode 15 and the second electrode 16 and the step S3 can be omitted. In order to facilitate the production of the electrode, a treatment such as pre-grinding and planarizing both ends of the laminate may be performed. Note that the step S3 may be created independently of the laminate production.

  Moreover, when only a laminated body is manufactured, it is sufficient to perform the steps S1 and S2.

(Embodiment 3)
FIG. 13 shows the steps of the method for manufacturing the pipe-type thermoelectric power generation device in the present embodiment. First, a member made of a flat metal having an opening inside and a member made of a thermoelectric material are respectively produced (S31 in FIG. 13). Next, a member made of a metal and a member made of a thermoelectric material are alternately laminated and joined to produce a pipe-shaped laminate (S32 in FIG. 13). Thereafter, the laminated surface of the metal and the thermoelectric material is processed into a pipe-shaped laminate in which the laminated surface of the metal and the thermoelectric material is inclined with respect to the axis of the opening by plastic working such as extrusion or drawing (S33 in FIG. 13). Next, the first electrode and the second electrode are produced (S34 in FIG. 13).

  Various methods such as casting can be used to produce a flat plate member having an opening in step S31, but a desired member can be easily and accurately produced by shearing such as punching a plate material. This is preferable.

  In the step S32 for producing the pipe-shaped laminate, the plate-shaped laminated structure having the openings formed in the step S31 is laminated alternately with the plate-like metal member and the thermoelectric material member as a whole. To be. Since the flat plate member has a through hole inside, a large number of members can be easily laminated by passing a rod or a wire serving as a guide through the through hole. For the joining of the members thus laminated, a method such as hot pressing in which pressure is applied in a high temperature atmosphere, or discharge plasma sintering in which the laminated body itself is energized and heated and pressure is applied at the same time can be used. A material such as silver paste or solder can be inserted between the metal and the thermoelectric material to strengthen the bonding, or the stress at the bonding interface can be relaxed.

  An example of plastic working in step S33 is shown in FIG. FIG. 14 shows a cross section of a part of the laminated body 111 before processing and a part of the laminated body 112 after processing, and a cross section of the die 113. The pipe-shaped laminate made of the metal and thermoelectric material produced in step S32 is sent to the die 113 along the traveling direction 114. The laminated surface of the metal and the thermoelectric material in the laminated body 111 before processing is perpendicular to the axis of the pipe, but in the laminated body 112 after processing, the laminated surface has an inclination angle shallower than perpendicular to the axis of the pipe. . Moreover, the thickness of the laminate is reduced. This step may be an extruding process in which the laminated body 111 before processing is pushed in the advancing direction, or may be a drawing process in which the laminated body 112 after processing is pulled in the advancing direction. Moreover, you may perform extrusion and extraction simultaneously. In order to control the inner diameter of the laminated body after processing, it is preferable to perform processing while inserting a mandrel or other metal core (not shown in FIG. 14) into the laminated body.

  There are various methods for producing the first electrode 15 and the second electrode 16 (S34 in FIG. 13), such as vapor deposition such as vapor deposition and sputtering, as well as application of conductive paste, plating, thermal spraying, and soldering. The method can be used. Further, if both ends of the laminate are terminated with a member 81 made of metal, this can be used as the first electrode 15 and the second electrode 16 and the step S3 can be omitted. In order to facilitate the production of the electrode, a treatment such as pre-grinding and planarizing both ends of the laminate may be performed. Note that the step S3 may be created independently of the laminate production.

  Moreover, when only a laminated body is manufactured, it is sufficient to perform the steps S1 and S2.

(Embodiment 4)
FIG. 15 shows the steps of the method for manufacturing the pipe-type thermoelectric power generation device in the present embodiment. The manufacturing process of the thermoelectric generator in the present embodiment includes a step of producing a cup-shaped metal member (S41), a step of arranging metal members (S42), and the arranged metal members. Filling a fluid made of a thermoelectric material to produce a laminate (S43). In order to generate thermoelectric power using a thermoelectric power generation device, electrodes are required at both ends of the device, and therefore a step (S44) of producing the first electrode and the second electrode so as to sandwich the laminate is necessary. However, the step of creating the first electrode and the second electrode may not be performed at the time of creating the laminate. A more detailed manufacturing configuration will be described later.

  Various methods can be used for the step (S42) of producing a member made of a cup-shaped metal. For example, methods such as cutting, electric discharge machining, casting, plastic working, and putting raw material powder into a mold and sintering can be used. Of these, plastic working such as press working is preferable because it is suitable for mass production.

  In the step of arranging the metal members (S42), it is preferable to align the cup-shaped metal member 81 so as to finally form the intended pipe-shaped laminate. Specifically, they can be arranged in a straight line as shown in FIG. 16 or a curved line as shown in FIG. As shown in FIG. 18, a mandrel 171 passed through the inside can be used for positioning the member 81 made of cup-shaped metal. Moreover, the member 81 made of a cup-shaped metal can be aligned at a predetermined position by providing a groove or the like that serves as a positioning guide in a mold used in a later process.

  In the step (S43) of filling a fluid made of a thermoelectric material between metal members and producing a laminate (S43), a member 81 made of a cup-type metal arranged in a mold that forms the outer shape of the laminate. And a fluid made of a thermoelectric material is filled in the gap. The material used for the mold is preferably a thermoelectric material or a material that does not adhere to the metal. Specifically, carbon, ceramic, or a metal coated with these can be used. Moreover, it is preferable to arrange | position a mandrel inside so that a laminated body may become a hollow structure. The mold and mandrel are basically removed after the laminate is manufactured, but may be left as they are if the mandrel has a pipe-like hollow structure. In that case, the mandrel and the laminate must be electrically insulated.

  There are various methods for producing the first electrode 15 and the second electrode 16 (S44 in FIG. 15), such as vapor deposition such as vapor deposition and sputtering, as well as application of conductive paste, plating, thermal spraying, and soldering. The method can be used. Of course, if both ends of the laminate are terminated with a member 81 made of metal, this can be used as the first electrode 15 and the second electrode 16, and the step S3 can be omitted. In order to facilitate the production of the electrode, a treatment such as pre-grinding and planarizing both ends of the laminate may be performed. Note that the step S3 may be created independently of the laminate production.

  Moreover, when only a laminated body is manufactured, it is sufficient to perform the steps S1 and S2.

  Hereinafter, more specific examples of the present invention will be described.

A pipe-type thermoelectric power generation device of the present invention was fabricated using aluminum as the metal 11 and Bi _0.5 Sb _1.5 Te ₃ as the thermoelectric material 12. Aluminum and Bi _0.5 Sb _1.5 Te ₃ were previously formed into a cup shape as shown in FIG. 10 by casting and pressing. Parts made of cup-shaped aluminum have a maximum outer diameter of 7 mm, a minimum inner diameter of 4 mm, a height of 6.2 mm, a tilt angle of 20 °, and a cup-shaped part made of Bi _0.5 Sb _1.5 Te ₃ has a maximum outer diameter of 7 mm, a minimum inner diameter of 4 mm, The height was 5 mm and the inclination angle was 20 °. The thickness ratio in the stacking direction when these components are stacked is oxygen-free copper: Bi _0.5 Sb _1.5 Te ₃ = 7: 3. Further, the lamination surface when the cup-shaped components were laminated was set to an angle of 20 ° with respect to the lamination direction. 200 cup-shaped parts made of Bi _0.5 Sb _1.5 Te ₃ and 199 cup-shaped parts made of aluminum were alternately passed through a stainless steel round bar with an outer diameter of 4 mm and having threaded parts at both ends. Later, cup-shaped copper parts with copper pipes with an outer diameter of 6 mm, an inner diameter of 5 mm, and a length of 50 mm were attached to both ends, and both ends were fixed by tightening with nuts. At this time, a constant pressure was applied in the stacking direction of the cup-shaped parts by inserting an Inconel spring before assembling the nut at one end. The parts thus assembled were heated at 500 ° C. for 2 hours in an Ar-flow tubular furnace. After cooling to room temperature, take out the parts and remove the nut and round bar. From both aluminum and Bi _0.5 Sb _1.5 Te ₃ with an outer diameter of about 7mm, an inner diameter of about 4mm and a length of about 700mm with copper pipes at both ends A pipe-type thermoelectric power generation device is obtained.

  Two copper wires were connected to both ends of the pipe-type thermoelectric power device obtained by the above procedure using solder as the first electrode and the second electrode. Next, a silicone tube was connected to both ends of the pipe-type thermoelectric power generation device, 80 ° C hot water was circulated, and the entire pipe-type thermoelectric power generation device was submerged in a water tank maintained at a water temperature of 20 ° C. A maximum of 1530mW of power could be extracted from between.

A pipe-shaped thermoelectric power generation device with a similar fabrication method and a stacking angle of 5 °, 10 °, 20 °, 45 ° with a ratio of oxygen-free copper to Bi _0.5 Sb _1.5 Te ₃ thickness (7: 3), When the evaluation was performed under the same conditions, the generated power as shown in Table 1 was obtained.

  Using the oxygen-free copper as the metal 11 and Bi as the thermoelectric material 12, the pipe-type thermoelectric power generation device of the present invention was produced. Parts made of oxygen-free copper were flat plates with an outer diameter of 16 mm, an inner diameter of 10 mm, and a thickness of 1.5 mm, and parts made of Bi were made with an outer diameter of 16 mm, an inner diameter of 10 mm, and a thickness of 0.5 mm. Five pieces of these oxygen-free copper and Bi parts were laminated alternately, and a total of 10 parts were laminated and pressed using dies and punches as shown in FIG. The pressing was performed in a nitrogen atmosphere at 230 ° C. with a maximum load of 1000 kgf. The processed laminate had a cylindrical shape with an outer diameter of about 13 mm, an inner diameter of about 10 mm, and a length of about 20 mm. After the measurement to be described later, the laminate was cut and the laminated surface of oxygen-free copper and Bi was observed. The inclination angle formed by the laminated surface and the cylindrical shaft was about 30 °.

  5 layers of oxygen-free copper and Bi were prepared in the above procedure, stacked on a straight line, hot-pressed while heating to 250 ° C in a nitrogen atmosphere, and about 100 mm long Was made. Thereafter, two copper wires were connected to both ends of the laminate using indium. Next, a silicone tube was press-fitted into both ends of the pipe-type thermoelectric power generation device and connected, and the tube was fixed with an epoxy adhesive. Circulating 80 ° C hot water inside the pipe-type thermoelectric generator vise and submerging the entire pipe-type thermoelectric generator device in a water tank maintained at a water temperature of 20 ° C, taking out a maximum of 140mW of power from between the two copper wires I was able to.

  Using the oxygen-free copper as the metal 11 and PbTe as the thermoelectric material 12, the pipe-type thermoelectric generator of the present invention was produced. Parts made of oxygen-free copper were flat plates with an outer diameter of 20 mm, an inner diameter of 15 mm, and a thickness of 1.2 mm, and parts made of PbTe were made with an outer diameter of 20 mm, an inner diameter of 15 mm, and a thickness of 0.8 mm. A total of 100 of these oxygen-free copper and PbTe parts were stacked alternately and passed through a stainless steel rod with an outer diameter of 15 mm. This sample was hot pressed while being heated to 500 ° C. in an argon atmosphere containing 3% of hydrogen, and a bonded laminate having a length of about 100 mm was produced.

  Next, plastic working as shown in FIG. 14 was performed using a stainless steel die. At the time of processing, a stainless steel round bar with a 15 mm outer diameter coated with lubricating oil was inserted into the cylinder, and an extrusion load was applied to the laminate to perform plastic processing at a processing speed of about 3 mm per minute. The processing speed was maintained by adjusting the load by appropriately applying a drawing load during the processing. The same plastic working was repeated a total of 5 times to produce a cylindrical laminate of oxygen-free copper and PbTe having an outer diameter of about 17 mm, an inner diameter of 15 mm, and a length of about 270 mm. After the measurement to be described later, the laminate was cut and the laminated surface of oxygen-free copper and Bi was observed. The inclination angle formed by the laminated surface and the cylindrical shaft was about 25 °.

  Two copper wires were connected to both ends of the laminate using solder. Next, a silicone tube was press-fitted and connected to both ends of the pipe-type thermoelectric power generation device, and the tube was fixed with an epoxy adhesive. Circulating 80 ° C hot water inside the pipe-type thermoelectric power generation device and submerging the entire pipe-type thermoelectric power generation device in a water tank maintained at a water temperature of 20 ° C, taking out a maximum of 860mW of power from between the two copper wires I was able to.

  Using the oxygen-free copper as the metal 11 and Bi as the thermoelectric material 12, the pipe-type thermoelectric power generation device of the present invention was produced. Parts made of cup-type oxygen-free copper were produced by pressing and cutting, and had a maximum outer diameter of 7 mm, a minimum inner diameter of 4 mm, a height of 6.2 mm, and an inclination angle of 20 °. Next, 50 cup-type oxygen-free copper parts are linearly arranged in a first mold made of semi-cylindrical carbon with 1mm width and 0.5mm height protrusions arranged in a cycle of 3.5mm. Lined up. Next, an anodized aluminum pipe with an outer diameter of 4 mm, a wall thickness of 0.8 mm, and a length of 200 mm is inserted into the opening of the arranged parts, and a semi-cylindrical second hole with a hole for pouring Bi melt is provided. A mold made of 2 carbon was placed on top.

  The mold assembled as described above was transferred into a glove box filled with nitrogen and heated to 400 ° C. on a hot plate. Next, a separately melted Bi melt was poured to fill the gaps between the parts made of oxygen-free copper. Next, heating of the mold by the hot plate was stopped, and after waiting for the display temperature of the hot plate to reach 60 ° C., the mold was taken out from the glove box. When the contents were taken out from the mold and excess Bi was scraped off, a cylindrical pipe-type thermoelectric power generation device consisting of an oxygen-free copper and Bi laminate with an aluminum pipe inside was obtained.

  Next, two copper wires were connected to both ends of the laminate using indium. And the silicone tube was connected to the aluminum pipe of the both ends of a pipe type thermoelectric power generation device. Circulating 80 ° C hot water inside the pipe-type thermoelectric power generation device and submerging the entire pipe-type thermoelectric power generation device in a water tank maintained at a water temperature of 20 ° C, taking out a maximum of 750mW of power from between the two copper wires I was able to.

  As described above, the pipe-type thermoelectric power generation device capable of taking out the above-mentioned electric energy by the manufacturing method of the present invention and the laminate thereof can be manufactured.

  In order to create a pipe-type thermoelectric device from a conventional flat plate-type thermoelectric power generation device, for example, it is necessary to provide a process for filling a gap generated between the pipe through which the fluid heat source flows and the thermoelectric power generation device in some form. There was no effective way to create a pipe-type thermoelectric device.

  On the other hand, since the pipe-type thermoelectric device that can extract the above-mentioned electric power can be manufactured by the pipe-type thermoelectric power generation device of the present invention and the method for manufacturing the laminate, the manufacturing method of the present invention The technical significance of is high.

  The method for manufacturing a pipe-type thermoelectric power generation device according to the present invention is useful because a power generation device having a pipe-type shape utilizing the heat of fluid can be easily produced.

DESCRIPTION OF SYMBOLS 11 Metal 12 Thermoelectric material 15 1st electrode 16 2nd electrode 17 Pipe type thermoelectric power generation device 18 Through-hole 19 Groove part 21 Inner fluid 22 Outer fluid 23 Axial direction of through-hole 81 Member made of cup-type metal 82 Cup-type metal Member made of thermoelectric material 91 Opening shaft 92 Inner side surface 93 Outer side surface 101 Member made of metal 102 Member made of thermoelectric material 103 Punch 104 Dies 111 Laminated body before processing 112 Laminated body after processing 113 Dies 114 Advancing direction 171 Mandrel

Claims (12)

Metals and thermoelectric materials are alternately laminated so as to have through holes penetrating in the laminating direction, and in a cross section parallel to the through direction of the through holes, the metal and thermoelectric material laminated surface with respect to the through direction. A first step of preparing a laminated body having a slope;
A second step of joining the metal and the thermoelectric material;
A third step of disposing a first electrode and a second electrode at both ends of the laminate;
A method for manufacturing a thermoelectric power generation device. The method for manufacturing a thermoelectric power generation device according to claim 1, wherein the second step is performed together with the first step by performing plastic working of the laminated metal and the thermoelectric material. Metals and thermoelectric materials are alternately laminated so as to have through holes penetrating in the laminating direction, and in a cross section parallel to the through direction of the through holes, the metal and thermoelectric material laminated surface with respect to the through direction. There preparing a laminate which is inclined,
Bonding the metal and the thermoelectric material;
The manufacturing method of the laminated body of the thermoelectric power generation device which comprises this. A metal having a through hole penetrating in the laminating direction and having a laminating surface inclined with respect to the through direction in a cross section parallel to the through direction of the through hole is provided with a space in the laminating direction. Laminating steps;
Filling the space with a thermoelectric material;
Disposing a first electrode and a second electrode on both ends of the laminate;
A method for manufacturing a thermoelectric power generation device. A method for manufacturing a pipe-type thermoelectric power generation device, comprising:
A plurality of first cup-shaped members made of metal having a first through hole at the lower end and a cross-sectional area decreasing in the direction of the lower end, and a second through hole at the lower end and having a cross-sectional area in the direction of the lower end A pipe having an internal through-hole composed of a plurality of first through-holes and a plurality of second through-holes is formed by alternately and repeatedly arranging a plurality of second cup-shaped members made of thermoelectric materials. Step (a) to perform,
(B) forming a laminate by sintering the pipe while applying pressure in a direction in which the pipe is compressed along the longitudinal direction of the pipe;
(C) forming a pipe-type thermoelectric power generation device by disposing a first electrode on one end of the laminate and a second electrode on the other end;
A method for manufacturing a pipe-type thermoelectric power generation device. In step (a), the pipe is
A plurality of the first cup-shaped members having a first inner surface and a first outer surface; and a plurality of the second cup-shaped members having a second inner surface and a second outer surface;
Each first cup-shaped member is inserted into one adjacent second cup-shaped member such that the first outer surface of each first cup-shaped member is in contact with the second inner surface of one second cup-shaped member adjacent to each other,
The other adjacent second cup-shaped member is inserted into each first cup-shaped member such that the first inner surface of each first cup-shaped member is in contact with the second outer surface of the other adjacent second cup-shaped member. Formed by
The manufacturing method of the pipe type thermoelectric power generation device according to claim 5 . A method for manufacturing a pipe-type thermoelectric power generation device, comprising:
A plurality of first flat plate members having a first through hole and made of metal and a plurality of second flat plate members having a second through hole and made of a thermoelectric material are alternately arranged. A step (d) of preparing a pipe having an internal through hole composed of the first through hole and the plurality of second through holes;
While sintering the pipe, pressure is applied in the direction in which the center of the internal through hole is pushed out or pulled out along the longitudinal direction of the pipe, simultaneously with the direction in which the pipe is compressed along the longitudinal direction of the pipe. A step (e) of forming a laminate by applying
A step (f) of forming a pipe-type thermoelectric power generation device by disposing a first electrode on one end of the laminate and a second electrode on the other end;
A method for manufacturing a pipe-type thermoelectric power generation device. In the step (e), the laminated body is formed in which the joining surfaces of the first flat plate member and the second flat plate member constituting the pipe are inclined along the longitudinal direction of the pipe.
A method for manufacturing a pipe-type thermoelectric power generation device according to claim 7 . A method for manufacturing a pipe-type thermoelectric power generation device, comprising:
A plurality of first flat plate members having a first through hole and made of metal and a plurality of second flat plate members having a second through hole and made of a thermoelectric material are alternately arranged. A step (g) of preparing a pipe having an internal through-hole composed of the first through-hole and a plurality of second through-holes;
Forming a first laminate by applying pressure in a direction in which the pipe is compressed along the longitudinal direction of the pipe while the pipe is sintered (h);
A step of forming a second laminate by applying pressure in a direction in which the center of the internal through-hole is pushed out or pulled out along the longitudinal direction of the pipe during plastic processing of the first laminate (i) )When,
A step (j) of forming a pipe-type thermoelectric power generation device by disposing a first electrode on one end of the second laminate and a second electrode on the other end;
A method for manufacturing a pipe-type thermoelectric power generation device. In the step (i), the second laminate is formed in which the joining surfaces of the first flat plate member and the second flat plate member constituting the pipe are inclined along the longitudinal direction of the pipe.
A method for manufacturing a pipe-type thermoelectric power generation device according to claim 9 . A method for manufacturing a pipe-type thermoelectric power generation device, comprising:
By having a through hole at the lower end and arranging a plurality of cup-shaped members made of a metal whose cross-sectional area decreases in the direction of the lower end while providing a space, it has an internal through hole composed of a plurality of through holes. Forming a pipe (k);
A step (l) of forming a laminate by filling each space of the pipe with a fluid made of a thermoelectric material;
Forming a pipe-type thermoelectric power generation device by disposing a first electrode on one end of the laminate and a second electrode on the other end (m);
A method for manufacturing a pipe-type thermoelectric power generation device. In step (k), the pipe is
A plurality of the cup-shaped members having a first inner surface and a first outer surface,
Each cup-shaped member is inserted into one adjacent cup-shaped member such that a space is provided between the first outer surface of each cup-shaped member and the first inner surface of one cup-shaped member adjacent to each cup-shaped member,
The other adjacent cup-shaped member is inserted into each cup-shaped member such that a space is provided between the first inner surface of each cup-shaped member and the first outer surface of the other adjacent cup-shaped member. Formed by,
The manufacturing method of the pipe-type thermoelectric power generation device according to claim 11 .

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