JP2000091650A - High temperature thermoelectric transducer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to absorb stress of a thermoelectric transducer due to bending or distortion caused by a difference in temperature by using such material as to make a first electrode movable for a first insulating member. SOLUTION: A second electrode (fixed electrode) 104 connected with thermoelectric transducing semiconductors 101, 102 is fixed to a second insulating member 107 constituted of, for example, an anodized aluminum film with an adhesive, etc., and is disposed on the heating side. In the meantime, a first electrode (movable electrode) 103 also connected with the thermoelectric transducing semiconductors 101, 102 is preferably made by patterning a silver foil attached to a first insulting member 105 constituted of, for example, a silicon resin film and is disposed on the cooling side. It is preferred that the first insulating member 105 disposed on the cooling side should have a thickness and an elasticity good enough to absorb distortion of the thermoelectric transuducing semiconductors 101, 102 caused by thermal stress during heating operation. For the material of the first insulating member 105, ethylene tetrafluoride resin can be used instead of silicon resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a high-temperature thermoelectric conversion element. More specifically, the present invention relates to a high-temperature thermoelectric conversion element capable of converting heat energy discharged from a high-temperature fuel cell, gas engine, or the like into electric energy and outputting the electric energy.

[0002]

2. Description of the Related Art As a conventional thermoelectric conversion element, for example,
One shown in FIG. The thermoelectric conversion element of FIG.
A plurality of p-type thermoelectric conversion semiconductors 401 and n-type thermoelectric conversion semiconductors 402 are alternately and continuously connected via electrodes 403 and 404, and both sides thereof have substrates 405 and 4 having insulating properties.
07, one side of which is in contact with the heating plate 421 and the other side of which is in contact with the cooling plate 420 to be used as a thermoelectric converter. In the thermoelectric conversion element having such a configuration, the heat flowing through the heating plate 421 and the heat absorbed by the cooling plate 420 reach the thermoelectric conversion semiconductors 401 and 402 via the insulating substrates 405 and 407, and a temperature difference occurs. I do. This temperature difference generates an electromotive force between both ends of the thermoelectric conversion semiconductors 401 and 402 by the Seebeck effect. As a result, power is supplied from the electric output wirings 422 and 423.

However, at present, the insulating substrate 40
As the materials of 5, 407, generally, a flat ceramic material or an aluminum material subjected to a surface treatment using a flat alumina material is used. Therefore, since the shape of the substrate is flat, heat propagation is hindered by thermal resistance and the like at the contact surface, the temperature distribution becomes uneven, the temperature difference applied to the thermoelectric conversion semiconductor becomes small, the electric output is small, and the thermoelectric conversion efficiency is low. ,
There was a problem.

As a method for solving this problem, a fitting groove is provided in a contact surface between the heating side substrate 407 and the heating plate 421 and a contact surface between the cooling side substrate 405 and the cooling plate 420 to enlarge the contact area, thereby reducing the heat flow. A method of increasing the temperature distribution to make the temperature distribution uniform is disclosed in Japanese Patent Application Laid-Open No. 10-144968. According to this method, the heat flow at the contact surface between the heating side substrate 407 and the heating plate 421 and the contact surface between the cooling side substrate 405 and the cooling plate 420 can be increased and the temperature distribution can be made uniform, so that the temperature difference applied to the thermoelectric conversion semiconductors 401 and 402 can be increased. Is expected to increase the output.

However, Japanese Patent Application Laid-Open No. H10-144968 discloses
The method disclosed in Japanese Patent Laid-Open Publication No. H06-27138 is good when operated by using a thermoelectric converter having a heat supply temperature of about one hundred and several tens of degrees Celsius, for example, a diesel engine (exhaust heat temperature: 300 to
450 ° C) or gas engine (exhaust heat temperature: 400-60
0 ° C.), solid oxide fuel cell (exhaust heat temperature: 600-8)
When the heat supply operation is performed at an exhaust heat temperature of 300 ° C. or more and 800 ° C. or less as in (00 ° C.), a difference in thermal expansion specific to metal occurs due to a difference in temperature between the heating side substrate 407 and the cooling side substrate 405. However, a new problem has arisen in that thermal stress, which is not a problem at about one hundred and several tens of degrees Celsius, is generated and warpage of the thermoelectric conversion elements 401 and 402 occurs.

When the heat supply temperature is 300 ° C. or higher, the warp distortion is caused by the portions of the thermoelectric conversion elements 401 and 402 where the mechanical strength is weak, that is, the thermoelectric conversion semiconductors 401 and 402.
Body, thermoelectric conversion semiconductors 401 and 402 and electrodes 403,
This causes stress on the connection portions 411 and 412 with the 404. As a result, the thermoelectric conversion semiconductors 401 and 402 are caused by metal fatigue or the like.
Electrodes 403, 4 of the main body and thermoelectric conversion semiconductors 401, 402
There is a problem in that the life of the connection portions 411 and 412 with the 04 is shortened. In particular, thermoelectric conversion semiconductors 401 and 402
Is generally cleaved and has a lower mechanical strength than ordinary metals. Therefore, when the thermoelectric converter is operated at a heat supply temperature of 300 ° C. or more, the method disclosed in
The above-mentioned problem cannot be solved only by the method disclosed in JP-A-144968.

At present, for example, a bismuth-tellurium-based thermoelectric conversion semiconductor is mainly used as a material constituting the thermoelectric conversion semiconductors 401 and 402, and the bismuth-tellurium-based thermoelectric conversion semiconductor has a body temperature of 250 to 300. It has the property of reacting with oxygen in the air and oxidizing when the temperature rises above ℃. Therefore, this oxidation is directly caused by the thermoelectric conversion element 40.
Since the characteristics of 1, 402 are deteriorated and the output is reduced,
It is hoped that this problem will be solved.

Further, substrates 407 and 405 and electrodes 403,
In some cases, a polyimide film (not shown) having a heat resistance of about 400 ° C. is used as an insulating material between the electrodes 404 and 404, but the adhesive (not shown) bonding the electrodes 403 and 404 has a heat resistance of about 200 ° C. , Thermoelectric conversion elements 401, 402
When the supply temperature to the substrate is set to 300 ° C. or higher,
No. 144968 discloses a method for cooling the substrate 40.
5, but not to the heating-side substrate 407.

[0009]

SUMMARY OF THE INVENTION According to the present invention, when supplying a high-temperature heat source at a supply temperature of 300 ° C. or more and 800 ° C. or less, a stable output, high thermoelectric conversion efficiency, and excellent thermoelectric conversion efficiency can be obtained. An object of the present invention is to provide a high-temperature thermoelectric conversion element having both durability and durability.

[0010]

A first high-temperature thermoelectric conversion element according to the present invention comprises a plurality of p-type thermoelectric conversion semiconductors and a plurality of n-type thermoelectric conversion semiconductors which are alternately separated from each other, and the adjacent p-type thermoelectric conversion elements are provided. A first electrode for electrically connecting the conversion semiconductor and the upper surface of the n-type thermoelectric conversion semiconductor;
The plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductors are connected in series by alternately providing second electrodes for electrically connecting the lower surfaces of the type thermoelectric conversion semiconductors, and the first electrode On the side opposite to the side in contact with the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor,
A first insulating member and a cooling-side substrate are provided in contact with each other in order, and the second electrode has a plurality of p-type thermoelectric conversion semiconductors and an n-type thermoelectric conversion semiconductor. A high-temperature thermoelectric conversion device configured to contact and arrange the second insulating member and the heating-side substrate in order, and to obtain an electrical output by contacting the cooling-side substrate with a cooling plate and the heating-side substrate with a heating plate. The element is characterized in that the first insulating member is made of a material that makes the first electrode movable.

[0011] In the above configuration, since the first insulating member is made of a material that allows the first electrode to move, stress caused by warpage or distortion caused by a temperature difference of the thermoelectric conversion element is reduced by the first electrode. It becomes possible to absorb by the elasticity of the material which becomes movable.

As such a material that the first electrode becomes movable, a heat conductive silicon resin or a tetrafluoroethylene resin is preferably used.

A second high-temperature thermoelectric conversion element according to the present invention is provided with a plurality of p-type thermoelectric conversion semiconductors and n-type thermoelectric conversion semiconductors which are alternately separated from each other. By alternately including a first electrode electrically connecting the upper surface of the conversion semiconductor, and a second electrode electrically connecting the lower surface of the adjacent p-type thermoelectric conversion semiconductor and the n-type thermoelectric conversion semiconductor, A side opposite to a side where the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor are connected in series, and the first electrode is in contact with the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor. A first insulating member and a cooling side substrate are provided in contact with each other in order, and the second electrode is provided on the side opposite to the side in contact with the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor. Contact the second insulating member and the heating side substrate in order. Further, in the high-temperature thermoelectric conversion element that obtains an electric output by bringing the cooling-side substrate into contact with the cooling plate and the heating-side substrate into contact with the heating plate, the second insulating member has a temperature of 300 ° C. 800 ℃
It is a material having the following heat resistance.

In the above configuration, 30 second insulating members are used.
By using a material having a heat resistance of 0 ° C. or more and 800 ° C. or less, waste heat of a diesel engine, a gas engine, a solid oxide fuel cell, or the like having a supply temperature in a range of 300 to 800 ° C. is converted to a thermoelectric conversion. It can be used as a heat source for the device.

As such a material having a heat resistance of 300 ° C. or more and 800 ° C. or less, anodized aluminum is preferable.

In the high-temperature thermoelectric conversion element having the above characteristics, the contact surface between the cooling-side substrate and the cooling plate and the contact surface between the heating-side substrate and the heating plate may be formed by a fitting groove structure. By doing so, the area of each contact surface can be increased, so that the heat flow can be increased and the temperature distribution can be made uniform. As a result, the temperature difference applied to the thermoelectric conversion semiconductor increases, so that the output can be increased.

Further, by using a metal foil produced by a vacuum deposition method as the second electrode in the above configuration, when the metal foil is fixed to the second insulating member, the anode constituting the second insulating member is used. The sealing treatment of the aluminum oxide film can be performed at the same time.

Further, in the high-temperature thermoelectric conversion element having the above characteristics, an anodized aluminum film is provided on the side surfaces other than the upper and lower surfaces of the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor, so that oxygen in the air can be reduced. Can prevent oxidation of the thermoelectric conversion semiconductor.

Still further, in the high-temperature thermoelectric conversion element having the above characteristics, a contact surface between the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor and the first electrode; Silver plating is applied to the contact surface between the conversion semiconductor and the n-type thermoelectric conversion semiconductor and the second electrode, thereby reducing heat radiation and convection in each part on the heating side and improving the temperature difference applied to the thermoelectric conversion semiconductor. Can be done.

[0020]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A high-temperature thermoelectric conversion element according to the present invention will be described below in detail with reference to the drawings.

FIG. 1 is a schematic sectional view of a high temperature thermoelectric conversion element according to the present invention. In FIG. 1, 101 is a p-type thermoelectric conversion semiconductor, 102 is an n-type thermoelectric conversion semiconductor, 103
Is a first electrode, 104 is a second electrode, 105 is a first insulating member, 106 is a cooling side substrate, 107 is a second insulating member, 108 is a heating side substrate, and 109 is a cooling side substrate and a cooling plate. Contact surface, 110 contact surface between the heating-side substrate and the heating plate, 1
11 is a contact portion between the thermoelectric conversion semiconductor and the first electrode, 112
Is a contact portion between the thermoelectric conversion semiconductor and the second electrode, 120 is a cooling plate, 121 is a heating plate, and 122 and 123 are electric output wirings.

In the high temperature thermoelectric conversion element shown in FIG. 1, a plurality of p-type thermoelectric conversion semiconductors 101 and n-type thermoelectric conversion
Reference numeral 02 denotes a first electrode 103 provided on the upper surface (cooling side) of an adjacent p-type thermoelectric conversion semiconductor 101 and an n-type thermoelectric conversion semiconductor 102, and a p-type thermoelectric conversion semiconductor 101 adjacent to the p-type thermoelectric conversion semiconductor 101. The plurality of p-type thermoelectric conversion semiconductors 101 and the n-type thermoelectric conversion semiconductors 102 are connected in series by alternately providing second electrodes 104 on the lower surface (heating side) of the n-type thermoelectric conversion semiconductor 102. . At this time, the first electrode 103 is made of a material that can move when heat is applied, and the second electrode 104 is made of a material that maintains a fixed state even when heat is applied.

Further, the high-temperature thermoelectric conversion element shown in FIG. 1 has a first electrode 103 on the side opposite to the side in contact with the plurality of p-type thermoelectric conversion semiconductors 101 and n-type thermoelectric conversion semiconductors 102. One insulating member 105 and a cooling-side substrate 106 are provided in contact with each other in this order, and the side opposite to the side where the second electrode 104 is in contact with the plurality of p-type thermoelectric conversion semiconductors 101 and n-type thermoelectric conversion semiconductors 102. Has a second insulating member 104,
It is configured by arranging the heating side substrates 108 in contact with each other,
Further, an electrical output is obtained by bringing the cooling-side substrate 106 into contact with the cooling plate 120 and the heating-side substrate 108 into contact with the heating plate 121.

At this time, the first electrode 103 is preferably made of a material which can be moved when heat is applied.
As 04, a material that maintains a fixed state even when heat is applied is desirable.

Specifically, a plurality of p-type thermoelectric conversion semiconductors 1
The second electrode (fixed electrode) 104 to which the 01-type and n-type thermoelectric conversion semiconductors 102 are connected is fixed to a second insulating member 107 made of, for example, an anodized aluminum film with an adhesive (not shown) or by vacuum evaporation. Anodized aluminum coating 1
It is fixed together with the sealing process of 07 and provided on the heating side. On the other hand, the first electrode (movable electrode) 103 to which the plurality of p-type thermoelectric conversion semiconductors 101 and n-type thermoelectric conversion semiconductors 102 are connected is a silver foil bonded to a first insulating member 105 made of, for example, a silicon resin film. Patterned ones are preferred and are provided on the cooling side. At this time, it is preferable that the first insulating member 105 provided on the cooling side has a thickness and elasticity that absorb deformation of the thermoelectric conversion semiconductors 101 and 102 due to thermal stress during the heating operation. Here, the silicon resin refers to a material obtained by hardening silicon with an arbitrary resin. Further, as the first insulating member 105, a tetrafluoroethylene resin (such as one called trade name Teflon) may be used instead of the silicon resin.

In the high-temperature thermoelectric conversion element shown in FIG. 1, the contact surface 1 of the cooling-side substrate 106 and the cooling plate 120 is in contact with each other.
09 and the contact surfaces 110 of the heating-side substrate 108 and the heating plate 121 are preferably formed in a fitting groove structure. Such a fitting groove structure can increase the area of each of the contact surfaces 109 and 110, so that the heat flow can be increased and the temperature distribution can be made uniform. As a result, the thermoelectric conversion semiconductor 10
A high-temperature thermoelectric conversion element capable of increasing the output due to a large temperature difference applied to the elements 1 and 102 is obtained.

FIG. 2 is a schematic sectional view showing a state when the high-temperature thermoelectric conversion element shown in FIG. 1 is operated at a high temperature. As shown in FIG.
Since the temperature of the substrate 8 becomes much higher during operation of the apparatus than the substrate 206 having the fitting groove on the cooling side, a thermal expansion phenomenon peculiar to metal occurs, and the dimensions of the substrates 206 and 208 having the fitting groove differ.
In addition, a plurality of p-type thermoelectric conversion semiconductors 201 and n-type thermoelectric conversion semiconductors 202 are also trapezoidally deformed due to a temperature difference between both ends. This deformation is the same for all the thermoelectric conversion semiconductors, but the inclination tends to be smaller at the center of the substrate and larger as approaching the outer periphery of the substrate. The stress due to such thermal expansion is caused by the thermoelectric conversion semiconductor 201 having a cleavage property,
202 body or each thermoelectric conversion semiconductor 201, 202
The connection parts 211 and 212 between the electrodes 203 and 204 are distorted. However, in the high-temperature thermoelectric conversion element according to the present invention, as illustrated in FIG. Can be absorbed by the elasticity of the silicon resin that is the first insulating member 205 provided in the first member.

The thermal expansion of the heating-side substrate 208 in the direction of the thermoelectric conversion semiconductor connecting portion is reduced by the minute smooth surface of the fitting groove portion of the heating-side substrate 221 and the material elasticity, and then the inclination of the thermoelectric conversion semiconductors 201 and 202 is reduced. Appears as. The stress applied to this inclination is caused by the first insulating member 205 on the cooling side.
And the first electrode (movable electrode) 203 on the cooling side is elastically deformed and absorbed. Therefore, the thermoelectric conversion element according to the present invention, even when the difference between the heating temperature and the cooling temperature is in the range of 300 to 800 ° C., the thermoelectric conversion semiconductors 201 and 202 or the thermoelectric conversion semiconductors 201 and 202 and the electrodes 203, The thermal stress applied to the connection portions 211 and 212 with the 204 can be made extremely small as compared with the related art.

FIG. 3 is a schematic perspective view of an n-type or p-type thermoelectric conversion semiconductor constituting the high-temperature thermoelectric conversion element according to the present invention. In FIG. 3, b1 and b2 are electrodes 103, 10
4 and a1 to a4 indicate side surfaces other than the upper and lower surfaces. Conventionally, a thermoelectric conversion semiconductor made of, for example, bismuth-tellurium has a tendency to react with oxygen in air when the body temperature rises to 250 to 300 ° C. or more, and deteriorate. On the other hand, in the thermoelectric conversion semiconductor according to the present invention, in order to prevent this deterioration, the direction from the heating side to the cooling side of the thermoelectric conversion semiconductors 101 and 102, that is, the thermoelectric conversion semiconductor 10
Connection surfaces b1, b2 between electrodes 1, 102 and electrodes 103, 104
By providing an anodized aluminum coating on the side surfaces a1 to a4 other than the above, the atmosphere can be shut off.
1, 102 can be prevented from deteriorating. The anodized aluminum film provided on the side surfaces a1 to a4 of each of the thermoelectric conversion semiconductors 101 and 102 has the advantage of improving the thermal insulation properties of the anodized aluminum film itself in addition to the advantage of shielding from the air, so that the radiation from the surface 108 of the heating-side substrate 108 is improved. There is also a secondary effect of reducing the temperature rise of the thermoelectric conversion semiconductors 101 and 102 due to heat, establishing the temperature difference between the thermoelectric conversion semiconductors 101 and 102, and increasing the output.

Each of the thermoelectric conversion semiconductors 101, 10 with respect to the second electrode (fixed electrode) 104 of the heating-side substrate 108
2 and the connection of each of the thermoelectric conversion semiconductors 101 and 102 to the first electrode (movable electrode) 103 of the cooling-side substrate 106 have different configurations as described below. That is,
The connection of each of the thermoelectric conversion semiconductors 101 and 102 to the second electrode (fixed electrode) 104 of the heating-side substrate 108 is performed at about 500 ° C. after performing silver plating on the connection surface 112 of each of the thermoelectric conversion semiconductors 101 and 102. It was brazed using silver brazing. On the other hand, each thermoelectric conversion semiconductor 101 with respect to the first electrode (movable electrode) 103 of the cooling side substrate 106,
The connection of 102 was performed by applying silver plating or copper plating to the connection surface 111 of each of the thermoelectric conversion semiconductors 101 and 102, and then soldering the solder at about 200 ° C.
With such a configuration, in the operation at a high temperature, the thermal expansion generated on the connection surface 111 between the first electrode (movable electrode) 103 of the cooling-side substrate 108 and each of the thermoelectric conversion semiconductors 101 and 102 can be further reduced. it can.

The high-temperature thermoelectric conversion element shown in FIG. 1 having the above configuration has a supply temperature of 300 to 80 to the thermoelectric conversion element.
It operates stably even when a high-temperature heat source of 0 ° C. is supplied, and its output is ^{2 to} 5 kW / m ² (when the supply temperature is 300 ° C.).
１３13 kW / m ² (at a supply temperature of 800 ° C.), which was confirmed to be sufficiently practical. The thermoelectric conversion efficiency, which is the ratio of the supplied thermal energy to the electrical output, is 2.5 to 9%.
(At a supply temperature of 300 ° C.), 8 to 19% (at a supply temperature of 8
(In the case of 00 ° C.), the efficiency was high, and the volume of the device was sufficiently smaller than that of the conventional device having the same output, so that it was found that the space could be saved. Therefore, it has been clarified that the high-temperature thermoelectric conversion element according to the present invention can directly convert waste heat from a solid oxide fuel cell or a waste incinerator to electric energy.

[0032]

As described above, in the high-temperature thermoelectric conversion element according to the present invention, the supply temperature to the thermoelectric conversion element is 300.
When a high-temperature heat source of up to 800 ° C. is supplied, the connection between each thermoelectric conversion semiconductor and the heating-side substrate is maintained in a fixed state, and the connection between each thermoelectric conversion semiconductor 111 and 112 and the cooling-side substrate is movable. Configuration. Therefore, according to the present invention, the supply temperature to the thermoelectric conversion element is 300 to 8
When a high-temperature heat source of 00 ° C. is supplied, a high-temperature thermoelectric conversion element having stable output, high thermoelectric conversion efficiency, and excellent durability, that is, a supply temperature of 30 ° C.
It is possible to provide a high-temperature thermoelectric conversion element that can use exhaust heat of a diesel engine, a gas engine, a solid oxide fuel cell, or the like having a temperature of 0 to 800 ° C. as a heat supply source to the thermoelectric conversion element.

Further, the high-temperature thermoelectric conversion element according to the present invention can improve the thermoelectric conversion efficiency, so that the device can be made smaller and space-saving as compared with a conventional device having the same output.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a high-temperature thermoelectric conversion element according to the present invention.

FIG. 2 is a schematic sectional view showing a state when the high-temperature thermoelectric conversion element shown in FIG. 1 is operated at a high temperature.

FIG. 3 shows n constituting the high-temperature thermoelectric conversion element according to the present invention.
Alternatively, it is a schematic perspective view of a p-type thermoelectric conversion semiconductor.

FIG. 4 is a schematic sectional view of a conventional high-temperature thermoelectric conversion element.

[Explanation of symbols]

101, 201 p-type thermoelectric conversion semiconductor, 102, 201 n-type thermoelectric conversion semiconductor, 103, 203 first electrode (movable electrode), 104, 204 second electrode (fixed electrode), 105, 205 first insulating member , 106, 206 Cooling-side substrate, 107, 207 Second insulating member, 108, 208 Heating-side substrate, 109, 209 Contact surface between cooling-side substrate and cooling plate, 110, 210 Contact between heating-side substrate and heating plate Surfaces, 111, 211 contact portions between the thermoelectric conversion semiconductor and the first electrode, 112, 212 contact portions between the thermoelectric conversion semiconductor and the second electrode, 120, 220 cooling plate, 121, 221 heating plate, 122, 123, 222, 223 electric output wiring, 401 p-type thermoelectric conversion semiconductor, 402 n-type thermoelectric conversion semiconductor, 403, 404 electrode, 405, 407 insulating substrate, 411 412 connection portion between each of the thermoelectric conversion semiconductor and the electrodes, 420 the cooling plate, 421 heating plate, 422 and 423 electrical output wiring.

Claims (8)

[Claims] 1. A first method for providing a plurality of p-type thermoelectric conversion semiconductors and n-type thermoelectric conversion semiconductors alternately separated from each other, and electrically connecting upper surfaces of adjacent p-type thermoelectric conversion semiconductors and n-type thermoelectric conversion semiconductors. Are alternately provided with a second electrode for electrically connecting the lower surfaces of the adjacent p-type thermoelectric conversion semiconductors and n-type thermoelectric conversion semiconductors, so that the plurality of p-type thermoelectric conversion semiconductors and n-type thermoelectric conversion A semiconductor is connected in series, and a first insulating member and a cooling-side substrate are provided on a side opposite to a side where the first electrode is in contact with the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor. Are provided in order, and a second insulating member and a heating-side substrate are provided on the side opposite to the side where the second electrode is in contact with the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor. The cooling side In a high-temperature thermoelectric conversion element that obtains an electrical output by bringing a plate into contact with a cooling plate and bringing the heating-side substrate into contact with a heating plate, the first insulating member is made of a material that allows the first electrode to move. A high-temperature thermoelectric conversion element characterized by the above-mentioned. 2. The high-temperature thermoelectric conversion element according to claim 1, wherein the material by which the first electrode is movable is silicon resin or tetrafluoroethylene resin. 3. A first method, wherein a plurality of p-type thermoelectric conversion semiconductors and n-type thermoelectric conversion semiconductors are provided alternately and separately, and an upper surface of an adjacent p-type thermoelectric conversion semiconductor and an upper surface of the n-type thermoelectric conversion semiconductor are electrically connected. Are alternately provided with a second electrode for electrically connecting the lower surfaces of the adjacent p-type thermoelectric conversion semiconductors and n-type thermoelectric conversion semiconductors, so that the plurality of p-type thermoelectric conversion semiconductors and n-type thermoelectric conversion A semiconductor is connected in series, and a first insulating member and a cooling-side substrate are provided on a side opposite to a side where the first electrode is in contact with the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor. Are provided in order, and a second insulating member and a heating-side substrate are provided on the side opposite to the side where the second electrode is in contact with the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor. The cooling side In a high-temperature thermoelectric conversion element that obtains an electrical output by bringing a plate into contact with a cooling plate and the heating-side substrate into contact with a heating plate, the second insulating member is made of a material having heat resistance of 300 ° C. or more and 800 ° C. or less. A high-temperature thermoelectric conversion element characterized by the above-mentioned. 4. The high-temperature thermoelectric conversion element according to claim 3, wherein the material having a heat resistance of 300 ° C. or more and 800 ° C. or less is anodized aluminum. 5. A fitting groove structure between a contact surface between the cooling-side substrate and the cooling plate and a contact surface between the heating-side substrate and the heating plate. The high-temperature thermoelectric conversion element according to any one of claims 4 to 4. 6. The high-temperature thermoelectric conversion element according to claim 1, wherein the second electrode is a metal foil produced by a vacuum deposition method. 7. An anodized aluminum film is provided on a side surface other than the upper and lower surfaces of the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor.
The high-temperature thermoelectric conversion element according to item. 8. A contact surface between the plurality of p-type and n-type thermoelectric conversion semiconductors and the first electrode, and
The silver plating is applied to a contact surface between the plurality of p-type thermoelectric conversion semiconductors and the n-type thermoelectric conversion semiconductor and the second electrode. Temperature thermoelectric conversion element.