JP2013062275A - Thermal power generation device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To achieve a low power generation amount per unit weight due to a heavy device.SOLUTION: A thermal power generation device has a device constitution where a laminate sandwiched between a first electrode 11 and a second electrode 12 is provided, the laminate includes porous metal and a thermoelectric material which are alternatively laminated, and the lamination plane of the metal and the thermoelectric material is tilted in the lamination direction of the laminate. Effective power generation can be performed by installing the device at a site where temperature difference is generated.

Description

  The present invention relates to a thermoelectric conversion technique for converting heat into electric power.

  In thermoelectric conversion technology that converts heat into electric power, thermoelectric conversion devices composed of thermoelectric conversion materials can convert heat at a relatively low temperature into electric power, and can also be used to maintain power generation equipment that is small and maintenance-free. It can be said that it is superior to other power generation technologies in that it can be maintained.

  Conventional devices using thermoelectric conversion materials mainly have a π-type structure. The π-type structure is a structure in which a P-type semiconductor and an N-type semiconductor, which are different from each other in the material of the element and have different electron carrier signs, are combined and are connected in parallel and electrically in series. This device is configured to generate power by bringing one surface of the device into contact with a heat source and cooling the other surface to cause a temperature difference in the device.

  In the non-diagonal thermoelectric conversion material using the anisotropy of thermoelectric properties in a laminated structure of different materials composed of a metal and a thermoelectric conversion material, the present inventors have determined the ratio of the thickness of each material in the laminate (hereinafter referred to as the thickness ratio). It was found that excellent power generation performance was realized by appropriately selecting the stacking ratio and the inclination angle in the stacking direction, and invented a thermoelectric power generation device using this (Patent Document 1). The thermoelectric power generation device including the non-diagonal thermoelectric conversion material is constructed with a completely different configuration from the conventional π-type structure.

  In order to improve the power generation performance using the non-diagonal thermoelectric conversion material, material design that requires dissimilarity between different materials, that is, thermoelectric properties of the thermoelectric conversion material and metal, based on the knowledge of the present inventors to date I know the guidelines. For example, in terms of thermal conductivity, it is necessary to combine the large thermal conductivity of metals and the small thermal conductivity of thermoelectric conversion materials, and the difference in thermal conductivity will produce higher power generation performance.

  The above-mentioned guideline for obtaining higher power generation performance as the dissimilarity between different materials is higher is pointed out from the result of simulation by Goldsmid et al. Goldsmid et al. In Non-Patent Document 1 cause dissimilarity between different materials by changing the thermoelectric properties of one thermoelectric conversion material, that is, the thermal conductivity, and changing the electric resistivity high in a combination of different thermoelectric conversion materials. It is reported that the power generation performance improves monotonously.

Japanese Patent No. 4078392 JP 2010-027895 A

Goldsmid, phys.stat.sol. 205, 2966 (2008)

  However, when power generation using the thermoelectric power generation device is considered, there is a problem that the thermoelectric conversion material or metal as a constituent material has a large specific gravity, and thus the weight of the device itself increases. For example, when considering application to in-vehicle equipment, the fuel efficiency of the vehicle is reduced.

  The present invention solves the above-described conventional problems, and provides a thermoelectric power generation device having a light weight and high power generation performance for a more general purpose by increasing the amount of power generation per mass of the thermoelectric power generation device. For the purpose.

  As a result of repeated research on anisotropic thermoelectric characteristics in a laminated structure of different materials, the inventors have made the thermoelectric device of the present invention lighter and have higher power generation performance by changing the thermoelectric properties by making the metal material porous. Found to have. Non-Patent Document 1 also points out a method of making the constituent material porous as a method of changing the thermoelectric properties. However, the purpose is to increase the dissimilarity between different materials as described in the guideline. On the other hand, the findings obtained by the present inventors that the power generation performance is improved by a measure of reducing the thermal conductivity of the metal, that is, reducing the dissimilarity close to the value of the thermoelectric material, contrary to the guideline. Is.

  With this configuration, a thermoelectric power generation device that is lighter and has higher power generation performance can be realized.

  According to the present invention, it is possible to provide a thermoelectric power generation device for a more general purpose use.

Sectional drawing of the thermoelectric power generation device in Embodiment 1 of this invention Sectional drawing of the thermoelectric generator unit in Embodiment 1 of this invention The figure of the molded object which comprises the thermoelectric power generation device in Embodiment 1 of this invention Front view of thermoelectric power generation device according to Embodiment 2 of the present invention Sectional drawing of the thermoelectric power generation device in Embodiment 2 of this invention The figure of the molded object which comprises the thermoelectric power generation device in Embodiment 2 of this invention

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

(Embodiment 1)
The cross-sectional view of the thermoelectric generator in Embodiment 1 is shown in FIG. 1 as an example, and both ends of the laminate in which the porous metal 11 and the thermoelectric material 12 are alternately laminated at a constant lamination ratio are connected to the first electrode 15 and the first electrode 15. It has a flat plate structure sandwiched between two electrodes 16. FIG. 2 is a cross-sectional view of the thermoelectric generator device according to the first embodiment. The laminated surface of the metal 11 and the thermoelectric material 12 has a certain angle θ with respect to the laminating direction 23, so that it is difficult to form a gap at the laminating interface when laminated.

  The porous metal 11 is not particularly limited as long as it is obtained from a material having good electrical and thermal conductivity. Specifically, Cu, Ag, Au, Ni, Fe, Co, and intermetallic compounds thereof are good, and the density of the porous metal is preferably about 5 to 50% as compared with the theoretical density of each material. The method for producing the porous metal 11 is not particularly limited as long as the density can be realized, and various methods can be used. For example, a method using a urethane template method or a method of foaming a slurry containing the metal can be considered.

A suitable range of the angle θ and the lamination ratio varies depending on the combination of the porous metal 11 and the thermoelectric material 12. For example, in the case of a combination of porous nickel and Bi _0.5 Sb _1.5 Te ₃ , θ is preferably in the range of 10 ° to 60 °, and the thickness ratio in the lamination of nickel and Bi _0.5 Sb _1.5 Te ₃ is 1: 4 to 4 : 1 is preferable.

  In FIG. 2, when the heat bath 21 at the upper part of the thermoelectric generator is high, the lower heat bath 22 is at a low temperature, and when the lower heat bath 21 is at a low temperature, the upper heat bath 22 is at a high temperature. A temperature difference occurs between the two and power generation can be performed. The obtained 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 thermoelectric generator of the present invention. Further, when the material of the heat bath portion has a metallic property, it is necessary to prevent an electrical short circuit by sandwiching an insulator with the thermoelectric generator device. In that case, it is desirable that the insulator is thin enough not to greatly impair the temperature difference between the upper and lower sides of the thermoelectric generator.

The thermoelectric material 12 may be Bi, Bi ₂ Te ₃ or those doped with Sb, Se, or the like, YbAl ₃ , PbTe, or the like, but is not limited thereto, and various thermoelectric materials are used. Can do.

  The first electrode 15 and the second electrode 16 are not particularly limited as long as the materials have good electrical conductivity. The first electrode 15 and the second electrode 16 can be omitted if both ends of the laminated structure are made of the porous metal 11, but the electrode is provided separately when the theoretical density ratio of the porous metal is small. Is desirable. Here, the theoretical density ratio is defined as the density of the obtained porous metal divided by the ideal density.

  The method is not particularly limited as long as the above structure can be realized, and various methods can be used. For example, the metal 11 and the thermoelectric material 12 previously processed into a molded body 30 having a shape as shown in FIG. 3 can be stacked and bonded by heating and pressurizing to produce a laminated structure. At that time, by making the width 31, the thickness 32, the angle θ33, and the height 34 uniform, the adhesion at the laminated interface of different materials can be improved, and the device can be created without a gap. It is also effective to form a device by bonding the metal 11 and the thermoelectric material 12 by thinly applying a conductive material such as solder or conductive paste.

  A device using this embodiment is sandwiched between a hot upper hot bath and a lower hot bath as shown in the device cross-sectional view of FIG. By realizing this configuration, it is possible to evaluate the power generation performance.

(Embodiment 2)
The thermoelectric generator in the second embodiment is not limited to the flat plate type, and as shown in the example in FIG. 4, a pipe-like laminate 41 in which the metal 11 and the thermoelectric material 12 are alternately laminated at a constant lamination ratio. But it is configurable. The thermoelectric generator in the present embodiment has a structure in which both ends of a laminate on a pipe are sandwiched between the first electrode 15 and the second electrode 16 and has a through hole 42 inside. 4 is a cross-sectional view of FIG. The laminated surface of the metal 11 and the thermoelectric material 12 has a certain angle θ with respect to the axial direction 53 of the through-hole, and it is difficult to form a gap at the laminated interface when laminated. If the through hole has a through structure, the cross-sectional shape is not limited to a circle, and may be an ellipse, a polygon, or an indeterminate shape.

  By laminating the metal 11 and the thermoelectric material 12 without any gaps and applying waterproofing treatment to the inside and outside of the pipe, it is possible to prevent the fluids flowing inside and outside from being mixed with each other. In FIG. 5, when the inner fluid 51 is a hot fluid, the outer fluid 52 is a cold fluid, and when the inner fluid 51 is a cold fluid, the outer fluid 52 is a hot fluid. A temperature difference occurs between the two 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.

  As long as the above structure can be realized, a method for stacking different materials is not particularly limited, and various methods can be used. For example, as shown in FIG. 6, the metal 11 and the thermoelectric material 12 previously processed into a cup shape are stacked and bonded together by heating and pressurization to produce a laminated structure. At that time, by uniformly forming the inner diameter 61, the outer diameter 62, the angle θ63, and the height 64, the adhesion at the laminated interface of different materials can be improved, and the device can be formed without a gap. Further, by using solder or conductive paste, the metal 11 and the thermoelectric material 12 can be joined relatively easily, and a device can be created.

  As in the previous period, in the case where a temperature difference is generated using a fluid, there is a problem regarding the seepage of hot and cold fluid inside and outside the pipe through the porous metal. Since such fluid seepage causes a decrease in temperature difference, it is necessary to stop water on the inner and outer surfaces of the device. For the water stop treatment, various methods such as installing a water stop layer 50 as shown in FIG. 5 are possible. In that case, it is important to make the temperature difference generated inside and outside the pipe as large as possible, and it is necessary to coat the material used for waterproofing as thinly as possible on the device surface. As a simple method, there is a method in which a waterproof gel is thinly applied to the inner and outer walls of a pipe and then dried to give a waterproof treatment. The method and configuration are not particularly limited as long as the above functions can be realized, and various methods can be used.

  When power generation is performed using the thermoelectric power generation device of the present invention, as shown in FIG. 5, the thermoelectric power generation unit uses the temperature difference that can be created inside and outside the pipe by filling the outside and inside of the pipe with low-temperature and high-temperature fluid, respectively. By realizing this configuration, it is possible to evaluate the power generation performance.

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

Example 1
The production method for Example 1-1 is described in detail below. The thermoelectric power generation device of the present invention was manufactured using nickel which was made porous as a porous metal and Bi _0.5 Sb _1.5 Te ₃ as a thermoelectric material. Nickel porosity was performed by the method described below. First, nickel fine powder having a particle size of 3 to 5 micrometers was charged into an 8 Wt% polyvinyl aqueous solution so as to have an amount of 20 vol%. Thereafter, 5 vol% of pentane serving as a blowing agent was added, and nickel was dispersed in an aqueous solution to prepare a slurry. A neutral detergent was used as a dispersant at that time. The resulting slurry is poured into a 50 × 50 × 20 mm plastic mold and kept in a cool box for 24 hours to gel the slurry. Next, the gelled slurry is inserted into a constant temperature bath at 55 ° C. and subjected to foaming treatment to produce a foam metal precursor. Finally, the foam metal precursor was placed in an alumina container and sintered in a vacuum furnace at 1000 ° C. for 30 minutes in a vacuum of 10 Pa to obtain a nickel porous metal. The obtained nickel porous body was molded into a 10 mm square cube and the density was measured. The density was 0.9 g / cm ^3, which is a theoretical density ratio compared to 8.9 g / cm ³ , which is the theoretical density of nickel. It was found that the porosity was increased to 10%. Subsequently, the nickel porous metal was molded using a wire saw so that the angle θ was 30 ° as shown in FIG. The size of the molded body was 30 mm wide, 2 mm high, and 2 mm thick. A plurality of nickel porous metals were obtained through the same process. Bi _0.5 Sb _1.5 Te ₃ composed of these nickel porous bodies and the theoretical density processed into the same shape was alternately laminated to obtain a plate-like thermoelectric power generation device of 30 × 30 × 2 mm. Bonding of the porous metal and the thermoelectric material was performed by applying Bi-Sn solder paste to the bonding surface and heating at 150 ° C.

  A nickel porous metal having several different theoretical density ratios (20%, 30%, 50%) was produced by changing the amount of nickel to be charged when making the porous body. Thermoelectric power generation devices obtained by the same method as in Example 1-1 using porous metals at the respective densities are referred to as Examples 1-2, 1-3, and 1-4, respectively.

Next, the production method of Comparative Example 1-5 will be described in detail. Comparative Example 1-5 was manufactured using nickel having a substantially theoretical density and Bi _0.5 Sb _1.5 Te _{3 serving} as a thermoelectric material. Nickel and Bi _0.5 Sb _1.5 Te ₃ were respectively molded and joined in the same size and method as in Example 1-1.

  In this embodiment, two copper wires are connected to both ends of the thermoelectric power device obtained by the above procedure using indium, and two copper heat sinks coated with aluminum nitride having a thickness of 1 μm are used. -1 was sandwiched and fixed with Apiezon grease to produce a power generation unit as shown in FIG. A copper pipe is embedded inside the copper heat sink. The heat sink can be cooled by flowing cold water through the pipe, and the heat sink can be heated by flowing hot water through the pipe. In Comparative Example 1-2, a similar power generation device was created. A temperature difference was given to the thermoelectric power generation device by flowing 15 ° C. cold water through one of the copper heat sinks and 80 ° C. hot water through the other. Table 1 shows the power generation at that time. In Comparative Example 1-5, the power generation amount was 0.04 W / g, whereas in each Example, a maximum of about three times as much power as that of Comparative Example 1-5 was extracted in the same configuration. I was able to do it. Also, in this example, it was revealed that the amount of power generation greatly depends on the porosity of the metal and has an optimal porosity. It was found that this result is clearly different from the result in (Non-patent Document 1), that is, the result that the power generation amount increases as the material becomes more porous.

(Example 2)
In this example, the dependency of the power generation performance on the lamination angle of the thermoelectric material and the porous metal will be described.

Using the same method as in Example 1, nickel porous metals having a theoretical density ratio of 10, 20, 30, and 50% were produced. In order to confirm the dependence of the power generation performance on the angle, nickel porous metals having respective theoretical density ratios were cut and molded using a wire saw so that the angles θ shown in FIG. 3 were 20 °, 30 °, and 45 °. . The size of the molded body was 20 mm wide, 2 mm high, and 2 mm thick. Through a similar process, a plurality of nickel porous bodies having respective angles and theoretical density ratios were produced. Next, thermoelectric material Bi _0.5 Sb _1.5 Te ₃ to be alternately laminated was formed into a similar size, and a plate-like thermoelectric power generation device of 30 × 30 × 2 mm was obtained. Bonding of the porous metal and the thermoelectric material was performed by applying Bi-Sn solder paste to the bonding surface and heating at 150 ° C. Thermoelectric power generation devices using nickel porous metals having respective theoretical density ratios of 10, 20, 30, and 50% are referred to as Examples 2-1, 2-2, 2-3, and 2-4.

Next, a method for producing Comparative Example 2-4 will be described in detail. Comparative Example 2-5 was manufactured using nickel having a substantially theoretical density and Bi _0.5 Sb _1.5 Te _{3 serving} as a thermoelectric material. Similarly to Example 2, nickel and Bi _0.5 Sb _1.5 Te ₃ were cut and molded so that the angle θ shown in FIG. 3 was 20 °, 30 °, and 45 °. In addition, the same method was used for bonding.

  The power generation performance was evaluated in the same manner as in Example 1. Using two copper heat sinks coated with aluminum nitride, the thermoelectric power generation devices of the present example and the comparative example were sandwiched and fixed with Apiezon grease to produce a power generation unit. A temperature difference was given to the thermoelectric power generation device by flowing 15 ° C. cold water through one of the copper heat sinks and 80 ° C. hot water through the other. Table 2 shows the power generation at that time. The results showed that the power generation amount of the example was larger than that of the comparative example at all angles.

(Example 3)
In this example, the dependency of the power generation performance on the ratio of the thickness of the thermoelectric material to the porous metal will be described.

A nickel porous metal having a theoretical density ratio of 10, 20, 30, and 50% was produced using the same method as in Example 1, and the dependency of the power generation performance on the ratio of the thickness of the porous metal to the thermoelectric material was confirmed. The nickel porous metal of each theoretical density ratio is cut and molded using a wire saw so that the angle θ shown in FIG. 3 is 30 °, the size of the molded body is 30 mm in width, 2 mm in height, and different thicknesses 1, 2 3 mm. A plurality of porous nickel bodies having respective thicknesses and theoretical density ratios are produced through the same process, and the same size 30 mm, height 2 mm, thickness (t) in the thermoelectric material Bi _0.5 Sb _1.5 Te ₃ to be alternately laminated. Was formed to be 1, 2, 3 mm. Thickness ratios t _BiSbTe / t _Ni were combined such that the thicknesses were 3, 1, and 0.33, and the respective thermoformed devices of 30 × 30 × 5 mm were obtained by bonding. Bonding of the porous metal and the thermoelectric material was performed in the same manner as in the above example. The thermoelectric power generation devices at the respective theoretical density ratios are referred to as Examples 3-1, 3-2, 3-3, and 3-4.

Next, a method for producing Comparative Example 3-5 will be described in detail. Comparative Example 3-5 was prepared using nickel and Bi _0.5 Sb _1.5 Te ₃ having a substantially theoretical density. In the same manner as in Example 3, a molded body made of nickel and Bi _0.5 Sb _1.5 Te ₃ was combined so that the thickness ratio t _BiSbTe / t _Ni would be _{3, 1} , 0.33, respectively. A flat thermoelectric device was obtained. In addition, the same method was used for bonding. Table 3 shows the power generation at that time. In all thickness ratios, the power generation amount of the example was larger than that of the comparative example.

Example 4
In this embodiment, a thermoelectric power generation device of the present invention configured in a pipe shape will be described.

In constructing a pipe-type thermoelectric power generation device, the present inventors produced a cup-shaped porous metal and a thermoelectric material shown in FIG. Porous nickel was used as the porous metal, and Bi _0.5 Sb _1.5 Te ₃ was used as the thermoelectric material. The cup-shaped porous metal was obtained by the method and conditions described in detail in Example 1 for foaming from the slurry. The cup-shaped molding was performed using a cup-shaped mold. Cup-shaped Bi _0.5 Sb _1.5 Te ₃ was produced by a casting method. The shape and size of the produced cup were almost the same among different materials, and the inner diameter was 10 mm, the outer diameter was 14 mm, and the height was 5.4 mm. 24 cups were prepared through the same process. Further, the lamination surface when the cup-shaped components were laminated was set to an angle of 30 ° with respect to the lamination direction. Bonding of the porous metal and the thermoelectric material was performed by applying Bi-Sn solder paste to the bonding surface and heating at 150 ° C. From the above process, a pipe-type thermoelectric generator having an inner diameter of 10 mm, an outer diameter of 14 mm, a length of 100 mm, and an inclination angle of 30 ° was produced. The above pipe type thermoelectric generator is referred to as Example 4-1. Furthermore, the amount of nickel to be charged when creating the porous body was changed to produce nickel porous metal having several different theoretical density ratios (20%, 30%, 50%). The thermoelectric power generation devices obtained by the same method as in Example 4-1 using the porous metal at each density are referred to as Examples 4-2, 4-3, and 4-4, respectively.

As a comparative example, a method for producing Comparative Example 4-5 will be described in detail below. Comparative Example 4-5 was fabricated using nickel having a substantially theoretical density and Bi _0.5 Sb _1.5 Te _{3 serving} as a thermoelectric material. Cup-shaped nickel and Bi _0.5 Sb _1.5 Te ₃ were prepared using a casting method, and the respective joints were performed in the same manner as in the above examples.

  After applying a caulking agent to the inner and outer surfaces of the pipe of the pipe-type thermoelectric power generation device obtained by the above-described procedure and performing a water stop treatment, two copper wires were connected to both ends of the pipe using indium. Next, a silicone tube is connected to both ends of the pipe-type thermoelectric power generation device, 80 ° C hot water is circulated inside the pipe, and the entire pipe-type thermoelectric power generation device is submerged in a water tank maintained at a water temperature of 20 ° C. The power generation performance of the comparative example was measured. Table 4 shows the power generation at that time. In Comparative Example 4-5, the power generation amount was 0.017 W / g, whereas in each Example, the power generation amount increased in comparison with Comparative Example 1-5 in the same configuration, and the maximum 4 .7 times more power could be taken out.

(Example 5)
In this example, the dependence of the power generation performance on the lamination angle of the thermoelectric material and the porous metal in the thermoelectric power generation device of the present invention configured in a pipe shape will be described.

Using the same method as in Example 1, nickel porous metals having different theoretical density ratios were produced. In order to confirm the dependence of the power generation performance on the angle, the molds used for gelling the slurry so that the angle θ shown in FIG. 6 is 20 °, 30 °, and 45 ° for the nickel porous metal having the respective theoretical density ratios. The frame angle was adjusted. Through the same process, 24 nickel porous bodies with respective angles and theoretical density ratios were produced. Next, the thermoelectric material Bi _0.5 Sb _1.5 Te ₃ to be alternately laminated is prepared by a casting method so as to have the same size and angle, and joined in the same manner as in Example 4, and at each lamination angle, an inner diameter of 10 mm, an outer diameter of 14 mm, A pipe-type thermoelectric power generation device having a length of 100 mm was prepared. The thermoelectric power generation devices at the respective theoretical density ratios are referred to as Examples 5-1, 5-2, 5-3, and 5-4.

Next, a method for producing Comparative Example 5-4 will be described in detail. It was fabricated using nickel having a substantially theoretical density and Bi _0.5 Sb _1.5 Te _{3 serving} as a thermoelectric material. Similarly to Example 2, nickel and Bi _0.5 Sb _1.5 Te ₃ were molded by a casting method so that the angle θ shown in FIG. 6 was 20 °, 30 °, and 45 °. In addition, the same method was used for bonding.

  In the pipe-type thermoelectric power generation device obtained by the above-described procedure, the power generation performance was measured for each example and comparative example under the same configuration and conditions as in Example 4. Table 5 shows the power generation at that time. The power generation amount larger than that of the comparative example was obtained in each example at all angles.

(Example 6)
In this example, the dependence of the power generation performance on the ratio of the thickness of the thermoelectric material to the porous metal in the thermoelectric power generation device of the present invention configured in a pipe shape will be described. The theoretical density is calculated using the same method as in Example 4 and Example 5. A cup-shaped nickel porous metal having a ratio of 10, 20, 30, and 50% was prepared, and the dependency of the power generation performance on the ratio of the thickness of the porous metal to the thermoelectric material was confirmed. Nickel porous metals having respective theoretical density ratios were cut and molded using a wire saw so that the angle θ shown in FIG. 6 was 30 °. The size of the molded body was 10 mm in inner diameter and 14 mm in outer diameter, and the cup-shaped thickness was adjusted so that the heights were 4.4, 5.4, and 6.4 mm, respectively. A plurality of porous nickel bodies having respective thicknesses and theoretical density ratios are produced through the same process, and the same size 30 mm, height 2 mm, thickness (t) in the thermoelectric material Bi _0.5 Sb _1.5 Te ₃ to be alternately laminated. Was formed to be 1, 2, 3 mm. Thickness ratios t _BiSbTe / t _Ni were combined so that the thicknesses were 3, 1, and 0.33, and a pipe-type thermoelectric power generation device having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 100 mm was produced. Bonding of the porous metal and the thermoelectric material was performed in the same manner as in the above example. The thermoelectric power generation devices at the respective theoretical density ratios are referred to as Examples 6-1, 6-2, 6-3, and 6-4.

Next, a method for producing Comparative Example 6-5 will be described in detail. Comparative Example 6-5 was fabricated using nickel and Bi _0.5 Sb _1.5 Te ₃ having a substantially theoretical density. In the same manner as in Example 6, a molded body made of nickel and Bi _0.5 Sb _1.5 Te ₃ was combined so that the thickness ratio t _BiSbTe / t _Ni would be _{3, 1} , 0.33, respectively, and 30 × 30 × 2 mm by joining. A flat thermoelectric device was obtained. In addition, the same method was used for bonding. Table 6 shows the power generation at that time. In all thickness ratios, the power generation amount of the example was larger than that of the comparative example.

The thermoelectric power generation device according to the present invention is useful for an in-vehicle thermoelectric power generation device or the like because the power generation amount per device weight is greatly improved.

The invention derived from the above disclosure is as follows.

1. A method for generating electricity using a thermoelectric device comprising the following steps:

(A) preparing the thermoelectric power generation device comprising:
First electrode (15),
A plate-like laminate in which a second electrode (16), and a plurality of porous metal layers (11) and a plurality of thermoelectric material layers (12) are alternately laminated, wherein in cross-sectional view, the plate-like laminate is A thermoelectric material layer (sandwiched between the first electrode (15) and the second electrode (16) and adjacent to the one porous metal layer (11) and the one porous metal layer (11) ( 12) is inclined with respect to the direction in which the first electrode (15) and the second electrode (16) face each other, and

(B) A step of generating a voltage difference between the first electrode (15) and the second electrode (16) by applying a temperature difference between the upper surface and the lower surface of the plate-shaped laminate.

DESCRIPTION OF SYMBOLS 11 Porous metal 12 Thermoelectric material 15 1st electrode 16 2nd electrode 21 Lower heat bath 22 Upper heat bath 23 Lamination direction 30 Molding body 31 Width 32 Thickness 33 Angle 34 Height 41 Pipe-shaped laminated body 42 Through-hole 50 Stop Water layer 51 Inner fluid 52 Outer fluid 53 Axial direction of through hole 61 Inner diameter 62 Outer diameter 63 Angle 64 Height

Claims (3)

A first electrode;
A second electrode facing the first electrode;
A laminated body sandwiched between the first electrode and the second electrode and electrically connected to both the first electrode and the second electrode;
The laminate is formed by alternately laminating a porous metal and a thermoelectric material, and a laminate surface of the metal and the thermoelectric material is inclined with respect to a lamination direction of the laminate.
Thermoelectric power generation device.   The thermoelectric power generation device according to claim 1, wherein the laminated body has a flat plate shape.   The thermoelectric power generation device according to claim 1, wherein the laminated body has a cylindrical shape.

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