WO2017164104A1

WO2017164104A1 - Thermoelectric module power generation evaluation device

Info

Publication number: WO2017164104A1
Application number: PCT/JP2017/010875
Authority: WO
Inventors: 舟橋　良次
Original assignee: 国立研究開発法人産業技術総合研究所
Priority date: 2016-03-23
Filing date: 2017-03-17
Publication date: 2017-09-28
Also published as: CN108886086B; CN108886086A; JPWO2017164104A1; JP6820564B2

Abstract

Provided is a thermoelectric module power generation evaluation device with which it is possible to accurately evaluate the performance of a thermoelectric module. The thermoelectric module power generation evaluation device for evaluating the power generation performance of the thermoelectric module is characterized in comprising: a heating unit having dimensions that are at least the dimensions of a high-temperature surface of the thermoelectric module, and having a heating surface arranged in contact with the high-temperature surface; a cooling unit having dimensions that are at least the dimensions of a low-temperature surface of the thermoelectric module, and having a cooling surface arranged in contact with the low-temperature surface of the thermoelectric module; and a power extraction line connected to the thermoelectric module, at least some of the power extraction line is arranged adhered on the cooling surface of the cooling unit.

Description

Thermoelectric module power generation evaluation device

The present invention relates to a thermoelectric module power generation evaluation apparatus.

Conventionally, exhaust gas from automobiles, factories, incinerators, etc. has been released. The discharged exhaust gas is high-quality heat energy having a temperature of, for example, 500 ° C. or higher. Although such thermal energy is released in a dilute manner, the total amount is enormous and is said to reach 70% of the primary supply energy.

In recent years, thermoelectric power generation using the Seebeck effect has attracted attention as a technique for effectively using the heat energy released in a dilute manner. Thermoelectric power generation requires the production of thermoelectric modules that increase the voltage by connecting thermoelectric materials that generate voltage due to temperature differences, but most of the conventional thermoelectric modules are metallic materials. It was difficult to use by oxidation at a high temperature of 300 ° C. or higher in the air. However, recently, thermoelectric modules using thermoelectric materials having oxidation durability even at high temperatures such as oxides and silicides (silicides) are being developed.

Here, for the evaluation of the output of the thermoelectric module, power generation efficiency, long-term durability, etc., non-patented equipment equipped with a heating unit and cooling unit for creating a temperature difference in the thermoelectric module, a measuring instrument for evaluating power generation performance, a personal computer, etc. It is performed by an evaluation apparatus as shown in Documents 1 to 3.

Conventional evaluation devices that evaluate the output, power generation efficiency, long-term durability, etc. of thermoelectric modules measure samples by placing them in a vacuum chamber, etc. due to the low durability of thermoelectric modules in air. Therefore, it was not suitable for performance evaluation under practical conditions. Further, in order to develop a highly durable thermoelectric module, there is a need for an evaluation device that can accurately measure the performance of the thermoelectric module in high temperature and air.

In view of the above situation, an object of the present invention is to provide a thermoelectric module power generation evaluation apparatus that can accurately evaluate the performance of a thermoelectric module.

The object of the present invention is a thermoelectric module power generation evaluation apparatus for evaluating the power generation performance of a thermoelectric module, and has a dimension equal to or larger than the dimension of the high temperature surface of the thermoelectric module and is disposed in contact with the high temperature surface. A heating unit having a heating surface, a cooling unit having a dimension equal to or greater than the dimension of the low-temperature surface of the thermoelectric module and having a cooling surface arranged in contact with the low-temperature surface, and electric power connected to the thermoelectric module The thermoelectric module power generation evaluation apparatus is characterized in that at least one part of the power extraction line is disposed in close contact with the cooling surface of the cooling unit.

Moreover, in the thermoelectric module power generation evaluation apparatus, it is preferable that the power extraction line is a sheet-like wiring having a predetermined width.

Moreover, it is preferable that the cooling surface of the cooling unit has a larger area than the heating surface of the heating unit.

Further, it is preferable that the thermoelectric module is disposed between the heating unit and the cooling unit, and further includes a weighting unit that pressurizes the thermoelectric module between the heating unit and the cooling unit.

Moreover, it is preferable that an elastic heat transfer sheet is provided between the cooling surface of the cooling unit and the low temperature surface of the thermoelectric module. This heat transfer sheet preferably further has electrical insulation.

Further, the heating unit includes a heating plate body made of an oxidation resistant material having a thermal expansion coefficient of 15 × 10 ⁻⁶ / K or less and a thermal conductivity of 10 W / mK or more, It is preferable that it is one side of the said heating plate main body.

The heating plate body is preferably made of stainless steel, nickel-base superalloy, or ceramics.

In addition, a cartridge heater and a temperature sensor disposed inside the heating plate main body are provided, and the cartridge heater and the temperature sensor are disposed so as to be biased toward the thermoelectric module with respect to the thickness direction of the heating plate main body. It is preferable that

Moreover, it is preferable to include a heat insulating member that covers the periphery of the thermoelectric module and covers the cooling surface of the cooling unit.

According to the present invention, it is possible to provide a thermoelectric module power generation evaluation apparatus that can accurately evaluate the performance of a thermoelectric module.

It is a schematic structure side view showing a thermoelectric module power generation evaluation apparatus according to the present invention. 1A is a plan view of the heating unit included in the thermoelectric module power generation evaluation apparatus shown in FIG. 1, FIG. 1B is a side view as viewed from the A direction of FIG. 1A, and FIG. It is the side view seen from the direction. 1A is a plan view and FIG. 2B is a side view of a cooling unit included in the thermoelectric module power generation evaluation apparatus shown in FIG. 1. It is a principal part expansion schematic side view of the thermoelectric module power generation evaluation apparatus shown in FIG. 1, (a) is a side view which shows the case where a lead wire is connected to the electrode end of the low temperature side of a module sample, (b) is a lead wire. It is a side view which shows the case where is connected to the electrode end of the module sample at the high temperature side. It is explanatory drawing for demonstrating the thermoelectric module sample large output measured by the thermoelectric module electric power generation evaluation apparatus shown in FIG. It is explanatory drawing for demonstrating the open voltage and internal resistance of the thermoelectric module sample measured by the thermoelectric module electric power generation evaluation apparatus shown in FIG. It is a weighting part with which the thermoelectric module power generation evaluation apparatus shown in FIG. 1 is provided, Comprising: It is explanatory drawing for demonstrating a pneumatic type or a hydraulic type weighting part. It is a modification of the weighting part with which the thermoelectric module power generation evaluation apparatus shown in FIG. 1 is provided, Comprising: It is explanatory drawing for demonstrating the weighting part of a lever type press system. It is a modification of the weighting part with which the thermoelectric module power generation evaluation apparatus shown in FIG. 1 is provided, Comprising: It is explanatory drawing for demonstrating the weighting part of the system using a screw and a spring. It is explanatory drawing for demonstrating the modification of the weighting part shown in FIG. It is a principal part expansion schematic sectional drawing regarding the modification of the thermoelectric module power generation evaluation apparatus shown in FIG. It is a principal part expansion schematic side view regarding the modification of the thermoelectric module power generation evaluation apparatus shown in FIG. FIG. 2 is an example of a plan view of a thermoelectric module sample whose performance is evaluated by the thermoelectric module power generation evaluation apparatus shown in FIG. 1. (A) is the side view seen from the C direction of FIG. 13, (b) is the side view seen from the D direction of FIG. 13, (c) is the side view seen from the E direction of FIG. 13, (d). [FIG. 14] It is the side view seen from the F direction of FIG. It is a perspective view regarding the example of a shape of the thermoelectric element which comprises the thermoelectric module sample shown in FIG.13 and FIG.14. FIG. 15 is a schematic side view showing a modified structure example of the thermoelectric module sample shown in FIGS. 13 and 14, wherein the number of elements constituting a pair of pn thermoelectric element pairs is both p-type and n-type. . FIG. 15 is a schematic side view showing a modified structure example of the thermoelectric module sample shown in FIGS. 13 and 14, in which the thermoelectric module sample is configured by only one of the p-type element and the n-type element. FIG. 13 and FIG. 14 show a modified structure example of the thermoelectric module sample, in which (a) is a plan view thereof, (b) is a side view seen from the C direction in (a), and (c) is The side view seen from D direction in (a), (d) is the side view seen from E direction in (a). FIG. 13 is a modified structure example of the thermoelectric module sample shown in FIG. 13 and FIG. 14, (a) is a schematic side view showing a case where there are electrically insulating substrates on both the high temperature side and the low temperature side, and (b) is It is a schematic side view which shows the case where there is no electrically insulating board | substrate in both a high temperature side and a low temperature side. It is explanatory drawing of the heating part used in Example 1 of the thermoelectric module power generation evaluation apparatus which concerns on this invention. It is explanatory drawing which shows the point which performed temperature measurement, when the preset temperature of the cartridge heater of the heating part which concerns on Example 1 shown in FIG. 20 is 900 degreeC. It is explanatory drawing of the cooling part used in Example 1 of the thermoelectric module power generation evaluation apparatus which concerns on this invention. It is explanatory drawing of the heating part used in Example 2 of the thermoelectric module power generation evaluation apparatus which concerns on this invention. It is explanatory drawing which shows the point which performed temperature measurement, when the preset temperature of the cartridge heater of the heating part which concerns on Example 2 shown in FIG. 23 is 800 degreeC. It is explanatory drawing of the cooling part used in Example 2 of the thermoelectric module power generation evaluation apparatus which concerns on this invention. It is explanatory drawing of the heating part used in Example 3 of the thermoelectric module power generation evaluation apparatus which concerns on this invention. It is explanatory drawing which shows the point which performed temperature measurement, when the preset temperature of the cartridge heater of the heating part which concerns on Example 3 shown in FIG. 26 is 600 degreeC. It is explanatory drawing of the cooling part used in Example 3 of the thermoelectric module power generation evaluation apparatus which concerns on this invention.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. Each figure is partially enlarged or reduced in order to facilitate understanding of the configuration. FIG. 1 is a schematic configuration side view showing a thermoelectric module power generation evaluation apparatus 1 according to an embodiment of the present invention. As shown in FIG. 1, the thermoelectric module power generation evaluation apparatus 1 includes a heating unit 2 and a cooling unit 3 that are arranged so as to sandwich a thermoelectric module sample 100 in the vertical direction. Moreover, the measurement part and control calculating part 5 which perform the performance evaluation of the thermoelectric module sample 100 are provided.

The heating unit 2 is a means for heating the high temperature surface of the thermoelectric module sample 100 sandwiched between the cooling unit 3 and includes a heating plate 21 that can raise the high temperature surface of the thermoelectric module sample 100 to about 1000 ° C., for example. ing. As shown in FIG. 2, the heating plate 21 includes a heating plate main body 22 and a plurality of cartridge heaters 23 accommodated therein. 2A shows a plan view of the heating plate 21, FIG. 2B shows a side view seen from the direction A of FIG. 2A, and FIG. 2C shows FIG. The side view seen from the B direction of (a) is shown. The lower surface side of the heating plate main body 22 functions as a heating surface for heating the thermoelectric module sample 100, and this heating surface is a surface that can come into contact with the high temperature surface side of the thermoelectric module sample 100 and is formed smoothly. The dimension of the heating surface of the heating plate 21 is set to have a dimension equal to or larger than the dimension of the high temperature surface of the thermoelectric module sample 100. Various shapes can be adopted as the shape of the heating surface. For example, it is preferable to configure the heating surface as a square or rectangle of 50 to 200 mm × 50 to 200 mm. The heating plate 21 has only to have a thickness that allows one or a plurality of holes 24 having a diameter of about 5.5 to 30 mm to be formed on one side surface, and the cartridge heater 23 can be inserted into the holes 24. In particular, it may have a thickness of about 10 to 20 mm.

The cartridge heater 23 accommodated in the heating plate main body 22 is configured such that the diameter thereof is in close contact with the inner peripheral surface of the hole 24 formed in the heating plate main body 22. For example, the diameter is about 5 to 30 mm. Is set to about 30 to 200 mm.

In the evaluation apparatus of the present application, in order to enable heating in high-temperature air, the material of the heating plate 21 needs to be excellent in heat resistance and oxidation resistance. Furthermore, good thermal contact between the heating surface and the thermoelectric module sample 100 is important in terms of reproducibility of power generation performance and stability in a long-term test, and it is preferable to ensure temperature uniformity within the heating surface. That is, it is preferable that the material of the heating plate 21 has a low thermal expansion coefficient and a high thermal conductivity at high temperatures. Furthermore, the thermal conductivity does not change greatly due to oxidation, and damage such as deformation or cracking due to heat or oxidation. It is preferable that the material is an oxidation-resistant material that is less likely to generate oxidization. As such a material, for example, stainless steel, nickel-base superalloy, or ceramics can be used.

The temperature unevenness of the heating surface is within a region where the maximum temperature difference when no load is applied without contacting the thermoelectric module sample 100 is the same as the center of the heating plate 21 and has a length of 80% of each side of the heating plate 21. It is preferable that it becomes 20 degrees C or less in the area | region of 50 degrees C or less and 50% or less similarly. As a result, when the thermoelectric module sample 100 is heated, the maximum difference in temperature within the high temperature surface of the module is the same as that of the heating plate 21 and within a region having a length of 80% of each side of the heating plate 21. It can be made 30 ° C. or lower, and can be made 10 ° C. or lower in a region of 50% or less. In order to realize this, it is only necessary to appropriately adjust the deformation of the heating surface due to thermal expansion at a high temperature, such as warping and swelling, and the number and arrangement interval of the cartridge heaters 23. In order to suppress the deformation of the heating surface, a material having a thermal expansion coefficient as low as possible may be used as the material of the high temperature source (heating plate body 22). With the size of the heating plate body 22 according to the present invention, if a material having a coefficient of thermal expansion of 15 × 10 ⁻⁶ / k or less at a temperature of 1000 ° C. or less is used, deformation of the heating surface can be prevented. Furthermore, in order to prevent temperature non-uniformity, it is preferable that the thermal conductivity of the material is high, and if it is 10 w / mk or more, in-plane temperature non-uniformity can be reduced. Specifically, if the metal material is stainless steel, SUS403, SUS405, SUS430, nickel-base superalloy, Inconel 600, Incoloy 800, ceramics, silicon carbide, silicon nitride, aluminum nitride, aluminum oxide, etc. Can be used. In view of processing the hole 24 for the cartridge heater 23, damage due to rapid heating and cooling, etc., metals such as stainless steel and nickel-base superalloy are preferable to ceramics.

The heating plate 21 is a member that inputs thermal energy to the thermoelectric module sample 100, and its heat output is also important. The heat output from the heating plate 21 is determined by the output and the number of cartridge heaters 23. The heat output of the heating plate 21 is not limited as long as a temperature difference is provided to the thermoelectric module sample 100 and a measurable power generation amount can be output. Generally, the heat output per cartridge heater 23 is 50 to 50. A thing of about 700W may be used. The intervals between the cartridge heaters 23 are preferably equal, and may be about 10 to 30 mm, although depending on the heater output and the material of the heating plate 21.

The temperature of the heating plate 21 may be measured by using a temperature sensor such as a thermocouple or a resistance temperature sensor. In consideration of the high temperature, a K type or R type thermocouple is preferable, and durability up to 1000 ° C. In consideration, R type thermocouple is most preferable. Further, in order to measure temperature unevenness on the heating surface, a plurality of temperature sensors 25 may be attached inside the heating plate main body 22 as shown in FIG. At that time, in order to minimize the temperature unevenness, the diameter of the hole 26 for the temperature sensor should be as thin as possible, and the length thereof should be set to a length that can measure various portions of the heating plate 21. In addition, it is preferable to connect at least one temperature sensor 25 to the temperature controller of the heater of the heating plate 21 and use it for temperature adjustment. More preferably, a plurality of temperature sensors 25 can be controlled individually. Temperature sensors 25 are arranged, and each is connected to a temperature controller.

In addition, since both the cartridge heater 23 and the temperature sensor 25 are closer to the thermoelectric module sample 100, the high temperature surface of the thermoelectric module sample 100 can be heated to a high temperature, and accurate temperature measurement can be performed. It is preferable that the cartridge heater 23 and the temperature sensor 25 are biased and installed on the thermoelectric module sample 100 side with respect to the thickness direction of the plate body 22).

Further, the cartridge heater 23 in the heating unit 2 is connected to the heater control unit 27, and the power supplied to the cartridge heater 23 is automatically adjusted by the program of the control unit 27, and the temperature, the temperature rising / lowering speed, and the holding time are adjusted. It is controlled. Further, the heater temperature is prevented from being excessively increased by PID control.

The cooling unit 3 is a means for cooling the low temperature surface of the thermoelectric module sample 100 sandwiched between the heating unit 2 and as shown in the plan view of FIG. 3A and the side view of FIG. It has a form. The cooling unit 3 includes a metal cooling plate 31. Inside the cooling plate 31, there is formed a flow path 32 through which cooling water can pass, as indicated by a dotted line in the plan view of FIG. A water inlet pipe 33 is connected to the inlet side end of the flow path 32, and a water outlet pipe 34 is connected to the outlet side end of the flow path 32. A cooling water circulation device 37 such as a chiller is connected to the water inlet pipe 33 and the water outlet pipe 34 via

pipes

35 and 36, and in the cooling plate 31, for example, at a flow rate of about 5 to 20 liters / minute. It is configured to circulate water at about 10-30 ° C. The cooling capacity of the cooling plate 31 is preferably about 0.05 ° C./W or less, more preferably about 0.03 ° C./W or less in terms of the thermal resistance value. The flow rate of the circulating cooling water is controlled and measured by a flow meter such as a flow meter. Further,

temperature sensors

38 and 39 are inserted into the water inlet pipe 33 and the water outlet pipe 34 of the cooling plate 31. The

temperature sensors

38 and 39 are not particularly limited as long as they do not interfere with the cooling water flow in the water inlet / outlet pipes (the water inlet pipe 33 and the water outlet pipe 34). For example, an introduction pipe is provided in the water inlet / outlet pipe having an outer shape of about 5 to 20 mm. A thermocouple having a diameter of about 1 to 2 mm, a resistance temperature sensor, etc. can be used. Examples include a K-type thermocouple or a platinum resistance thermometer. The inlet / outlet pipes may be arranged on the same side surface or different side surfaces of the cooling plate 31, and may be on the cooling surface or on the opposite side as long as it does not interfere with the arrangement with the thermoelectric module, the heating plate 21, or the like.

Further, the upper surface of the cooling plate 31 shown in FIG. 3 functions as a cooling surface that cools the thermoelectric module sample 100, and this cooling surface is a surface that can come into contact with the low temperature surface side of the thermoelectric module sample 100. The dimension of the cooling surface configured as described above is set to have a dimension equal to or larger than the dimension of the low temperature surface of the thermoelectric module sample 100 to be measured. Moreover, in order to protect the peripheral member arrange | positioned at the cooling plate 31 side from the high temperature by the heat transfer from the heating plate 21, each side of the cooling plate 31 becomes a dimension longer than each side of the heating surface of the heating plate 21. It is preferable to configure the cooling plate 31 so that the area of the cooling plate 31 is larger than the area of the heating plate 21. The thickness of the cooling plate 31 is not particularly limited, but can be set to about 10 to 80 mm.

In addition, the thermoelectric module power generation evaluation apparatus 1 includes a power extraction line (lead wire 4) connected to the thermoelectric module sample 100. The lead wires 4 are wirings respectively connected to both terminals of the thermoelectric module sample 100 (both ends (both electrode ends) of a pn thermoelectric element group configured in series by electrodes 102). The lead wire 4 becomes high temperature due to heat radiation from the heating surface, and heat generation due to the electric resistance of the lead wire 4 occurs depending on the current value generated. The rise in temperature of the lead wire 4 causes fluctuations in the electrical resistance of the lead wire 4 and temperature non-uniformity in the thermoelectric module due to heat inflow, which hinders accurate measurement. Therefore, for example, as shown in FIG. 4A, the cooling plate 31 is configured to be in close contact with the surface and cooled. At this time, it is preferable to electrically insulate the surface of the lead wire 4 with a thin film such as a polyimide (Kapton (registered trademark)) tape so as not to prevent heat transfer. This enables protection of the lead wire 4 and accurate measurement. Furthermore, since heat generated by the electrical resistance generated in the lead wire 4 can also be taken into the cooling water, more accurate power generation efficiency can be measured. The lead wire 4 guided from the thermoelectric module sample 100 may be configured to be guided from the low temperature surface side as shown in FIG. 4 (a), or as shown in FIG. 4 (b). The lead wire 4 may be bent so as to be in contact with the cooling surface over a long distance as much as possible. In particular, when the lead wire 4 is led from the high temperature surface side, the lead wire 4 is bent with attention to contact with the thermoelectric element.

Here, the heating unit 2 and the cooling unit 3 described above may be arranged in any manner, but if the fixing of the thermoelectric module is taken into consideration, they are arranged up and down as shown in FIG. 1 and FIG. This is preferable because it provides a simpler device structure and facilitates measurement. In addition, either the heating unit 2 or the cooling unit 3 may be arranged at the upper part. However, in consideration of problems such as heating of the cooling surface by convection of heated air and water leakage, the heating part 2 is arranged at the upper part. It is preferable that the cooling unit 3 is arranged at the lower part and the thermoelectric module sample 100 is sandwiched between the heating unit 2 and the cooling unit 3 from above and below.

The measuring unit is equipped with multiple temperature sensors. More specifically, the temperature sensor 25 (thermocouple, resistance temperature sensor, etc.) used for measuring the temperature of the heating plate 21 and the

temperature sensors

38, 39 used for measuring the water temperature at the inlet / outlet of the cooling plate 31. It has. Moreover, the thermoelectric module sample 100 is provided with a temperature sensor that measures the temperature of the high temperature surface, the low temperature surface, and the side surface. Although the measurement method of the sensor for temperature measurement is not specified, a thermocouple or a resistance temperature sensor may be used from the viewpoint of measurement accuracy and convenience. In order to realize measurement in high-temperature air, which is a feature of the present invention, a temperature sensor having high durability under operating conditions may be used. When measuring the hot surface of the heating plate 21 or the thermoelectric module sample 100, An R-type thermocouple using platinum-platinum / rhodium alloy, a K-type thermocouple using alumel-chromel and a platinum resistance thermometer are preferably used for measuring the cooling plate 31 and water temperature.

Further, the measuring unit includes a measuring device for converting the temperature of the electric signal from the heating plate 21, the high and low temperature surfaces of the thermoelectric module sample 100, and the temperature measurement sensor for the cooling water. Further, the measurement unit includes a constant current DC power source or an electronic load device for applying an external load resistance to the thermoelectric module sample 100, and further includes a DC voltmeter that can measure the voltage generated by the thermoelectric module sample 100. . The measuring method may be performed by the DC four-terminal method, and an electric wire for external load resistance and a voltage measuring wire through which current flows are connected to the end of the lead wire 4 connected to the thermoelectric module sample 100.

The control calculation unit 5 is a means having a function of taking in numerical values such as measured temperature, voltage, current, and external load resistance, and performing calculation processing and storage. For example, a general personal computer can be used. Further, it is preferable that the measurement can be controlled by a program such that automatic measurement is possible at regular time intervals. The control calculation unit 5 is configured so that the voltage and the power generation output can be automatically calculated based on the following

formulas

1 and 2.

Voltage (V) = Current (A) x Resistance (Ω) (Equation 1)
Power generation output (W) = Current (A) x Voltage (V) (Formula 2)

In addition, the control calculation unit 5 is configured to continuously scan the external load resistance, measure the power generation output at different external load resistance values, and calculate the maximum value of the power generation output of the thermoelectric module sample 100. Yes. In this case, the power generation output value is calculated from the measured current value and voltage value by (Equation 2), and the current value is plotted on the horizontal axis and the power generation output value is plotted on the vertical axis, as shown in FIG. The maximum output value generated by the thermoelectric module sample 100 is obtained by calculation using a quadratic function approximation. Further, regarding the voltage (open voltage) and the internal resistance value when the external load resistance is not applied to the thermoelectric module sample 100, the measured current value and voltage value are plotted on the horizontal axis and the vertical axis, respectively, as shown in FIG. The open circuit voltage that is an intercept and the internal resistance value that is the absolute value of the slope are calculated by the linear approximation. The maximum output value (maximum value of power generation output) can be calculated in principle from the open-circuit voltage value and the internal resistance value. That is, since the maximum output of the thermoelectric module sample 100 is obtained when the external load resistance value and the internal load value of the module coincide with each other, the maximum output of the thermoelectric module sample 100 may be automatically calculated by the following equation 3. .

Maximum output (W) = (open voltage) ² / (4 x internal resistance) (Equation 3)

Further, the control calculation unit 5 is configured to be able to calculate the power generation efficiency of the thermoelectric module sample 100. The power generation efficiency is configured to be automatically calculated by the following equation 4.

Power generation efficiency (%) = Power generation output (W) / (Power generation output (W) + Heat flow into cooling water (W)) x 100 (Equation 4)
Here, the amount of heat (W) flowing into the cooling water is calculated by the following equation (5).

Heat flow into cooling water (W) = (water temperature at outlet (° C.) − Water temperature at inlet (° C.)) × circulated water volume (cm ³ / min) × temperature-corrected water density (g / cm ³ ) × Specific heat of water (1.0 cal / g · ° C) × unit conversion (1.94 × 10 ^-6 W / min) (Formula 5)

Moreover, the thermoelectric module power generation evaluation apparatus 1 according to the present invention includes a weighting unit 6 that pressurizes the thermoelectric module sample 100 between the heating unit 2 and the cooling unit 3 as shown in FIG. Since the degree of contact between the hot and cold surfaces of the thermoelectric module sample 100 and the heating plate 21 and the cooling plate 31 is very important in terms of heat input / output and temperature control, the weight during measurement is precise and constant. Is preferably maintained. As a specific configuration of the weighting unit 6 that pressurizes (weights) the thermoelectric module sample 100, a pneumatic or hydraulic type using a compressor as shown in FIG. 7 or an insulator principle as shown in FIG. 8 is used. It is possible to adopt a method in which the weight 61 is suspended from the lever by a lever-type press and a weight is used, or a method using screws and springs as shown in FIGS. Further, since the weight value fluctuates due to thermal expansion during measurement, it is preferable to provide a mechanism that always measures the weight by a weight sensor such as a load cell and keeps the weight value constant. With regard to the weighting direction, weighting from either the top or bottom or from the left or right may be used. However, in order to simplify the installation of the thermoelectric module sample 100 and the device structure, weighting is performed so that the weight is applied in the top-bottom direction. It is preferable to configure the portion 6, and more simply, it is preferable to fix the lower portion and apply a weight from the upper portion.

Further, in the thermoelectric module power generation evaluation apparatus 1 according to the present invention, as shown in FIG. 11, in order to prevent heat from directly flowing into the cooling plate 31 outside the thermoelectric module sample 100 due to heat radiation from the heating plate 21. It is preferable that the thermoelectric module sample 100 is configured to include the heat insulating member 7 that covers the periphery of the thermoelectric module sample 100 and covers the surface of the cooling plate 31 (the cooling surface of the cooling unit 3). When the thin thermoelectric module sample 100 is measured, the heating surface and the cooling surface face each other at a short distance, whereby the cooling water is heated even by thermal energy that does not pass through the thermoelectric module sample 100, and the measurement accuracy of power generation efficiency is improved. May be lowered. In addition, when measuring a thick thermoelectric module, heat dissipation from the side surface of the thermoelectric material occurs, and the measurement accuracy of the power generation efficiency may also deteriorate. The heat insulating member 7 that covers the periphery of the thermoelectric module sample 100 and covers the surface of the cooling plate 31 can effectively suppress such a decrease in measurement accuracy. As the heat insulating member 7, for example, glass wool or porous ceramic heat insulating material can be employed. Further, a heat insulating material covering the entire surface of the cooling plate 31 is disposed on the opposite surface (the surface opposite to the side on which the thermoelectric module sample 100 is disposed; the lower surface of the cooling plate 31 in FIG. 11). Is preferred. With such a configuration, heat dissipation and inflow on the opposite surface of the cooling plate 31 can be prevented, and the amount of heat flowing into the cooling plate 31 becomes the amount of heat that has passed through the thermoelectric module and the lead wire 4, and is accurate. It is possible to calculate the power generation efficiency.

The thermoelectric module power generation evaluation apparatus 1 according to the present invention includes a safety area 81, an emergency stop button 82, and an alarm indicator lamp 83 as shown in FIG. The safety enclosure 81 is provided to prevent contact with the high-temperature heating plate 21 and impact on the thermoelectric module sample 100 during measurement. The safety plate 81, the thermoelectric module sample 100, and the cooling plate 31 are externally attached. It is preferable to use a punching metal or a heat-resistant wire mesh so that it can be observed. Note that a door for replacing the module sample 100 is provided on at least one side surface of the safety enclosure 81. If this door is opened during measurement, the heater 2 is energized or weighted. It is preferable that the operation of the unit 6 is stopped and the measurement can be stopped in an emergency. In addition, at least one temperature sensor is placed in the safety enclosure 81, and the temperature inside the enclosure is controlled. When the temperature exceeds the set value, energization and weighting to the heater in the heating unit 2 is stopped and measurement is made urgently. It may be configured to be able to stop

The emergency stop button 82 and the warning indicator lamp 83 are connected to the control calculation unit 5 and operate in conjunction with the control calculation unit 5. The emergency stop button 82 is used when the measurement is immediately stopped due to some trouble, and is set so that the energization to the heater and the operation of the weighting unit 6 can be stopped by pressing the button. . The warning indicator lamp 83 is operated to notify the measurer when the preset heating condition or measurement does not operate according to the program due to some trouble. A green lamp, a yellow lamp when measurement is stopped, and a red lamp are lit when an abnormality occurs.

In the thermoelectric module power generation evaluation apparatus 1 according to the present invention, as described above, the heating unit having a heating surface having a dimension equal to or larger than the dimension of the high temperature surface of the thermoelectric module sample 100 and disposed in contact with the high temperature surface. 2 and a cooling unit 3 having a cooling surface 3 having a size equal to or larger than the size of the low-temperature surface of the thermoelectric module sample 100 and having a cooling surface arranged in contact with the low-temperature surface, and further connected to the thermoelectric module sample 100 Since at least a part of the power lead-out line (lead wire 4) is installed in close contact with the cooling surface of the cooling unit 3, the power generation efficiency can be evaluated with high accuracy. In particular, since at least a part of the power lead wire (lead wire 4) connected to the thermoelectric module sample 100 is installed in close contact with the cooling surface of the cooling plate 31 of the cooling unit 3, the lead wire 4 is generated. The amount of heat related to the heat generated by the electrical resistance can be taken into the cooling water via the cooling surface, and the amount of heat supplied to the lead wire 4 by the heat radiation from the heating surface of the heating unit 2 is also cooled via the cooling surface. More accurate power generation efficiency and the like can be measured.

Further, the shape and dimensions of the lead wire 4 are not particularly limited, but various shapes such as a plate shape, a belt shape, a round column shape, and a stranded wire shape can be employed. The larger the cross-sectional area of the lead wire 4, the smaller the electric resistance and the power generation output loss can be reduced. However, if the cross-sectional area is large, heat from the high temperature side is easily released via the lead wire 4. When 4 is on the high temperature side of the module, heat that is not involved in thermoelectric conversion flows directly into the cooling water from the heat source, which degrades the conversion efficiency measurement accuracy. In order to prevent this, for example, it is preferable to employ a sheet-like lead wire 4 having a width of about 0.1 cm to 3 cm and a thickness of about 0.005 cm to 0.2 cm, more preferably a width of 0.5 cm to 1 cm and a thickness of 0.005 cm. It is preferable to employ a sheet-like lead wire 4 of about 0.1 cm. Such a thin sheet-like lead wire 4 (band-like lead wire 4) having a predetermined width is employed, and at least a part of the lead wire 4 having the shape is brought into close contact with the cooling surface of the cooling plate 31. By installing in this way, the contact area between the lead wire 4 and the cooling surface is increased, and the amount of heat accumulated in the lead wire 4 can be effectively moved to the cooling water side via the cooling surface. It becomes possible to measure the power generation efficiency and the like.

Further, it is preferable that the area of the cooling surface of the cooling plate 31 is larger than the area of the heating surface of the heating plate 21. According to such a configuration, it is possible to protect the peripheral members arranged on the cooling plate 31 side from the high temperature due to the heat transfer from the heating plate 21 and to effectively receive the amount of heat radiated from the heating plate 21. It is possible to measure the power generation efficiency and the like more accurately.

Further, in the thermoelectric module power generation evaluation apparatus 1 according to the present invention, as shown in the enlarged side view of the main part of FIG. 12, it is arranged between the cooling surface of the cooling unit 3 and the low temperature surface of the thermoelectric module sample 100. You may comprise so that the heat-transfer sheet | seat 9 which has elasticity may be provided. When such a heat transfer sheet 9 having elasticity is disposed between the cooling surface and the low temperature surface of the thermoelectric module sample 100, even if a temperature sensor is inserted between the heat transfer sheet 9 and the water cooling surface, Since there is no large gap, the temperature of the element on the low temperature surface can be measured with higher accuracy, and the power generation efficiency and the like of the thermoelectric module sample 100 can be measured with higher accuracy. The elastic heat transfer sheet 9 preferably further has electrical insulation. When the heat transfer sheet 9 has electrical insulation, the thermoelectric module sample 100 can be configured by omitting the low temperature side substrate 101 in the thermoelectric module sample 100, and the configuration of the module sample can be simplified. Is possible. Here, as the heat transfer sheet 9 having elasticity, for example, a sheet material made of silicone rubber or acrylic rubber can be used.

Here, the thermoelectric module sample 100 whose performance is evaluated by the thermoelectric module power generation evaluation apparatus 1 according to the present invention preferably has a plate shape as shown in FIGS. 1, 13, and 14. (In FIG. 14, the dimension in the thickness (height) direction is particularly enlarged and displayed). 13 is a plan view of the thermoelectric module sample 100, and FIGS. 14A to 14D are side views seen from the C direction, the D direction, the E direction, and the F direction in FIG. Is shown. As shown in FIGS. 13 and 14, the thermoelectric module sample 100 includes an electrically insulating low-temperature side substrate 101, a plurality of p-type thermoelectric elements, and a plurality of n-type thermoelectric elements. Each p-type thermoelectric element and each n-type thermoelectric element are connected to each other in series, such as p-type, n-type, p-type, n-type,... A part of the electrode 102 is disposed between the low temperature side substrate 101 and the pair of pn-type thermoelectric elements, and the other part of the electrode 102 is a pair of pn-type thermoelectric elements. It is arranged on the upper surface side of the element pair.

Further, the thermoelectric material, the electrode material, the substrate, and other constituent members used for the thermoelectric module sample 100 are not particularly limited as long as they maintain the shape without being melted, evaporated, crushed or the like at the measurement temperature. Further, the shape of the p-type thermoelectric element and the n-type thermoelectric element is not particularly limited, but is preferably a quadrangular prism or a cylinder as shown in FIG. Further, the cross-sectional dimension of the thermoelectric element is not particularly limited, but when the cross-sectional area is large and the number of thermoelectric elements is reduced, the generated current value is increased, so that the heat generation in the lead wire 4 is increased and the voltage value is increased. Therefore, the measurement accuracy may be lowered. Therefore, in general, it is preferable to use a quadrangular column with one side of the cross section of about 1 mm to 10 mm or a cylinder with a diameter of about 1 mm to 10 mm. Further, the cross-sectional shape of the p-type thermoelectric element and the cross-sectional shape of the n-type thermoelectric element may be different, or the cross-sectional dimensions of the p-type thermoelectric element and the n-type thermoelectric element may be different. Good. Also, the height H of the p-type or n-type thermoelectric element is not particularly limited, but the thermoelectric module 100 causes a decrease in internal resistance, durability, ease of temperature difference, and accuracy of power generation efficiency. From the viewpoint of preventing heat dissipation from the side of the material, it is preferably about 1 to 30 mm, more preferably about 1 to 7 mm. Although the height H of the p-type and n-type thermoelectric elements may be different, it is preferable that all elements have the same length in consideration of good thermal contact with the heating plate 21 and the cooling plate 31. .

Further, the number of thermoelectric elements constituting the thermoelectric module sample 100 and the number of elements constituting one pn pair are not limited. For example, in the configurations shown in FIGS. 13 to 14, the case where the number of elements constituting a pair of pn thermoelectric element pairs is one for both the p-type and the n-type is shown, for example, as shown in FIG. As shown in FIG. 17, the number of elements constituting a pair of pn thermoelectric element pairs may be two for both p-type and n-type, or as shown in FIG. The thermoelectric module sample 100 may be configured with only one of the thermoelectric elements. Each of FIGS. 16A to 16C and FIGS. 17A to 17C corresponds to side views viewed from the C direction, the D direction, and the E direction in FIG.

13 and 14, the thermoelectric elements are connected to each other using the conductive electrode 102. However, the present invention is not particularly limited to such a configuration. For example, as shown in FIG. A type thermoelectric element and an n-type thermoelectric element may be directly joined. FIG. 18A shows a plan view of the thermoelectric module sample 100, and FIGS. 18B to 18D are side views of the thermoelectric module sample 100 as viewed from the C direction, the D direction, and the E direction in FIG. The figure is shown. When forming a bond, solder or conductive paste can be used, but in order to produce a highly durable module in high-temperature air, silver or platinum, rather than solder that may oxidize or melt, It is preferable to use a conductive paste using a noble metal such as gold. The distance between the elements may be as long as the elements do not come into contact with each other to cause an electrical short, but if it is too wide, the number of elements in the thermoelectric module is reduced, and a high output cannot be obtained. Therefore, the interval between the elements is preferably about 0.1 to 5 mm, more preferably about 0.1 to 1 mm.

Further, in the configuration of FIGS. 13 and 14, the thermoelectric module sample 100 is configured such that the electrically insulating low temperature side substrate 101 is provided on the low temperature surface side and the substrate is not provided on the high temperature surface side. For example, as shown in FIG. 19A, in addition to the low temperature side substrate 101, an electrically insulating high temperature side substrate 103 is disposed on the high temperature surface side of the thermoelectric module sample 100. It may be configured. Further, as shown in FIG. 19B, the thermoelectric module sample 100 may be configured by omitting the low temperature side substrate 101. Here, FIGS. 19A and 19B correspond to side views as viewed from the direction D in FIG. This is a case where the thermoelectric module sample 100 is configured so that both or one of the low temperature side substrate 101 and the high temperature side substrate 103 is not provided, and a part of the electrode 102 is exposed. When the heating surface of the heating plate 21 and the cooling surface of the cooling plate 31 of the cooling unit 3 have electrical conductivity, the heating surface and cooling surface and the thermoelectric module sample 100 are used to prevent a short circuit between the thermoelectric elements. An electrically insulating substance may be sandwiched between the two. In this case, if the thermal conductivity is low, it becomes difficult to give a temperature difference to the thermoelectric module sample 100. Therefore, it is preferable that the insert has as high a thermal conductivity as possible and a thin thickness. For example, a thin ceramic plate such as alumina or silicon nitride can be disposed between the heating surface and the thermoelectric module sample 100, and a commercially available heat plate can be disposed between the cooling surface and the thermoelectric module sample 100. Conductive grease or polyimide (Kapton (registered trademark)) tape can be provided.

Further, as a form of the thermoelectric module sample 100, it is possible to adopt a cascade module in which a plurality of thermoelectric module samples 100 shown in FIG. 14 or the like are stacked. In this case, the sum of the thicknesses of all thermoelectric modules is 50 mm or less. Is preferably about 5 to 20 mm. Moreover, the outer edge of the high temperature surface of the thermoelectric module sample 100 is 80% or less of the length of one side of the heating plate 21 to be described later, regardless of the presence of the substrate (low temperature side substrate 101, high temperature side substrate 103). More preferably, it is preferably set to 50% or less. By setting in this way, most of the heat quantity of the heating plate 21 can be input to the thermoelectric module sample 100, so that the power generation output is also increased, and a power generation output close to the limit value that the thermoelectric module sample 100 can generate can be obtained. Moreover, even when there is no substrate, the influence of reduction of the thermal contact area due to deformation of the high temperature surface and the low temperature surface can be reduced.

The inventor of the present invention created a plurality of examples according to the thermoelectric module power generation evaluation apparatus 1 and conducted performance evaluation tests on various thermoelectric module samples 100, which will be described below.

First, the thermoelectric module power generation evaluation apparatus 1 according to Examples 1 to 3 created by the inventors will be described.

The configurations of the heating unit 2, the cooling unit 3, the weighting unit 6, and the measurement unit in the thermoelectric module power generation evaluation apparatus according to the first embodiment are as follows.
[Heating unit 2]
65 mm × 50 mm square, 25 mm thick Inconel 600 made hot plate main body 22 has three sides on the side surface of 4.5 mm from the outer side of the hot plate main body 22, a distance between the outer circumferences of 10 mm, and is further in contact with the thermoelectric module sample 100. A hole 24 having a diameter of 12 mm was formed so as to be 6 mm from the heating surface side, and a cartridge heater 23 was loaded to constitute the heating plate 21 (FIG. 20). At this time, the cartridge heater 23 is arranged so that the tip of the cartridge heater 23 reaches a depth of 40 mm from the outer edge of the heating plate 21. On the opposite side surface, there are two holes 26 having a diameter of 2 mm so that the distance between the outer periphery of the heating plate body 22 is 20.5 mm, the distance between the outer circumferences is 20 mm, and the heating surface side in contact with the thermoelectric module sample 100 is 11 mm. And an R type thermocouple (temperature sensor 25) was loaded. With this arrangement, the thermocouple is positioned at equal intervals with the two cartridge heaters 23. The tip of the thermocouple is arranged so as to reach a depth of 25 mm from the outer edge of the heating plate 21. One of the two thermocouples was connected to the heater temperature controller and used to control the heater temperature. As the cartridge heater 23, one that can be used up to a normal temperature of 800 ° C. and a maximum temperature of 1000 ° C. was adopted. The heating amount of the heating plate 21 is two cartridge heaters 23 and the output is a maximum of 1 kW.

Table 1 shows the temperature distribution on the heating surface when the heating plate 21 is heated at a setting of 900 ° C. in a no-load state without being brought into contact with the thermoelectric module sample 100. A thermo viewer is used for the measurement, and the measurement points displayed in Table 1 are shown in FIG. There was a tendency for the temperature to be higher when the measurement point was closer to the cartridge heater 23. In the same area as the heating plate 21 and having a length of 80% of each side of the heating plate 21 (area surrounded by points (1), (7), (15), (21)) The maximum temperature difference was 49 ° C. On the other hand, in a region having a length of 50% of each side of the heating plate 21 (region surrounded by the points (22), (23), (24), (25)), 16 ° C. is the maximum temperature difference. became. Note that the difference between the set temperature and the actually measured value occurs because the measurement was performed with the heating surface exposed in the air.

[Cooling unit 3]
The cooling unit 3 was constituted by a copper cooling plate 31 having an 80 mm × 80 mm square and a thickness of 20 mm and having a water pipe (flow path 32) therein and a thermal resistance of 0.03 ° C./W or less (FIG. 22). The chiller has a maximum cooling capacity of 1.4 kW and a maximum flow rate of 14 liters. The set temperature is 30 ° C. or less.

[Weighting unit 6]
The load portion 6 was configured by a lever press type using the lever principle (FIG. 8). The weighting unit 6 is configured to suspend a weight of 5 kg at the maximum to the lever and to apply an even weight to the module sample from the upper part of the heating unit 2. The weight can be set in increments of 1 kg. The weight is confirmed by the load cell during measurement, and the weight is manually suspended on the lever to maintain a constant value. The arrangement of the heating unit 2 and the cooling unit 3 is configured such that the heating unit 2 is in the upper part, the cooling unit 3 in the lower part is fixed, and a load is applied from the upper part.

[Measurement section]
The temperature is measured at two locations on the heating plate 21, one location on each of the high and low temperature surfaces of the thermoelectric module sample 100, and two locations on the cooling water temperature. As the temperature sensor, an R type thermocouple was used for the heating plate 21, the module high temperature surface, and a K type thermocouple was used for the module low temperature surface. A platinum resistance thermometer is used to measure the cooling water temperature. The thermocouple for measurement of the heating plate 21 is inserted into a hole provided on the side surface of the heating plate 21. When there is a module sample substrate on the high temperature surface of the thermocouple for measuring the high temperature surface of the module sample, an R type thermocouple is bonded to the element side surface using silver paste. When there was no module sample substrate, an alumina plate having a thickness of 0.8 mm was inserted between the heating plate 21 and an R type thermocouple was bonded to the element side using silver paste.

Also, as the electronic load device, a constant current DC power supply capable of supplying a maximum current of 5 A was used, and a DC voltmeter capable of measuring up to 10 V was used as a voltmeter. For temperature measurement, a digital temperature measuring device corresponding to each temperature center was used.

The configurations of the heating unit 2, the cooling unit 3, the weighting unit 6, and the measurement unit in the thermoelectric module power generation evaluation apparatus according to Example 2 are as follows.

[Heating unit 2]
14 mm from the outside of the

heating plate

21, 13 mm from the outer periphery of the

heating plate

21, and 6 mm from the heating surface side in contact with the thermoelectric module. A heating plate 21 was constructed by opening a hole 24 having a diameter of 12 mm and mounting a cartridge heater 23. (FIG. 23). At this time, the cartridge heater 23 is arranged so that the tip of the cartridge heater 23 reaches a depth of 135 mm from the outer edge of the heating plate 21. On the opposite side surface, there are four holes 26 with a diameter of 2 mm so that the distance between the outer periphery of the heating plate body 22 is 31.5 mm, the distance between the outer circumferences is 23 mm, and the heating surface side in contact with the thermoelectric module sample 100 is 11 mm. 26 was opened and an R type thermocouple (temperature sensor 25) was loaded. With this arrangement, each thermocouple is positioned at equal intervals with the two cartridge heaters 23. The tip of the thermocouple is disposed so as to reach a depth of 70 mm from the outer edge of the heating plate 21. One of the two thermocouples close to the center is connected to the heater temperature controller and used to control the heater temperature. As the cartridge heater 23, one that can be used up to a normal temperature of 800 ° C. and a maximum temperature of 1000 ° C. was adopted. The heating amount of the heating plate 21 is five cartridge heaters 23, and the output is 2.5 kW at maximum.

Table 2 shows the temperature distribution on the heating surface when the heating plate 21 is heated at a setting of 800 ° C. in a no-load state without being brought into contact with the thermoelectric module sample 100. A thermo viewer is used for measurement, and the measurement points displayed in Table 2 are shown in FIG. There was a tendency for the temperature to be higher when the measurement point was closer to the cartridge heater 23. In the same area as the heating plate 21 and having a length of 80% of each side of the heating plate 21 (area surrounded by points (1), (7), (15), (21)) The maximum temperature difference was 48 ° C. On the other hand, in the region having a length of 50% of each side of the heating plate 21 (region surrounded by the points (22), (23), (24), (25)), 20 ° C. is the maximum temperature difference. became. Note that the difference between the set temperature and the actually measured value occurs because the measurement was performed with the heating surface exposed in the air.

[Cooling unit 3]
The cooling unit 3 was constituted by a copper cooling plate 31 having a 140 mm × 140 mm square and a thickness of 20 mm and having a water pipe (flow path 32) therein and a thermal resistance of 0.005 ° C./W or less (FIG. 25). The chiller has a maximum cooling capacity of 1.4 kW and a maximum flow rate of 14 liters. The set temperature is 30 ° C. or less.

[Weighting unit 6]
The load portion 6 was configured by a lever press using the lever principle (FIG. 8). The weighting unit 6 is configured to suspend a weight of 10 kg at the maximum to the lever and to apply an even weight to the module sample from the upper part of the heating unit 2. The weight can be set in increments of 1 kg. The weight is confirmed by the load cell during measurement, and the weight is manually suspended on the lever to maintain a constant value. The arrangement of the heating unit 2 and the cooling unit 3 is configured such that the heating unit 2 is in the upper part, the cooling unit 3 in the lower part is fixed, and a load is applied from the upper part.

[Measurement section]
The temperature is measured at four locations on the heating plate 21, two locations on the high and low temperature surfaces of the thermoelectric module sample 100, and two locations on the cooling water temperature. The temperature sensor used was a heating plate 21, an R type thermocouple for the module high temperature surface, and a K type thermocouple for the module low temperature surface. A platinum resistance thermometer is used to measure the cooling water temperature. The thermocouple for measurement of the heating plate 21 is inserted into a hole provided on the side surface of the heating plate 21. When there is a module sample substrate on the high temperature surface of the thermocouple for measuring the high temperature surface of the module sample, an R type thermocouple is bonded to the element side surface using silver paste. When there is no module sample substrate, an alumina plate having a thickness of 0.8 mm is inserted between the heating plate 21 and an R type thermocouple is bonded to the element side using silver paste.

Also, as the electronic load device, a constant current DC power supply capable of supplying a maximum current of 10 A was used, and a DC voltmeter capable of measuring up to 10 V was used as a voltmeter. For temperature measurement, a digital temperature measuring device corresponding to each temperature center was used.

The configuration of the heating unit 2, the cooling unit 3, the weighting unit 6, and the measurement unit in the thermoelectric module power generation evaluation apparatus according to Example 3 is as follows.

[Heating unit 2]
Heating surface in contact with the thermoelectric module sample 100 at six locations on the side surface of the heating plate body 22 made of Inconel 600 having a size of 160 mm × 150 mm square and a thickness of 30 mm, 11.5 mm from the outside of the

heating plate

21, 15 mm between the outer circumferences. A heating plate 21 was constructed by opening a hole 24 with a diameter of 12 mm so as to be 7 mm from the side and loading a cartridge heater 23 (FIG. 26). At this time, the cartridge heater 23 is arranged so that the tip of the cartridge heater 23 reaches a depth of 155 mm from the outer edge of the heating plate 21. On the opposite side surface, there are five holes 26 having a diameter of 2 mm so that the distance between the outer periphery of the heating plate body 22 is 25 mm, the distance between the outer circumferences is 27.5 mm, and the heating surface side in contact with the thermoelectric module sample 100 is 12 mm. And an R type thermocouple (temperature sensor 25) was loaded. With this arrangement, each thermocouple is positioned at equal intervals with the two cartridge heaters 23. The tip of the thermocouple is arranged so as to reach a depth of 80 mm from the outer edge of the heating plate 21. Of the five, the central thermocouple is connected to the heater temperature controller and used to control the heater temperature. As the cartridge heater 23, one that can be used up to a normal temperature of 800 ° C. and a maximum temperature of 1000 ° C. was adopted. The heating amount of the heating plate 21 is five cartridge heaters 23 and the output is 3 kW at maximum.

Table 3 shows the temperature distribution on the heating surface when the heating plate 21 is heated at a setting of 600 ° C. in a no-load state without being brought into contact with the thermoelectric module sample 100. The measurement points displayed in Table 3 are shown in FIG. 27 using a thermo viewer. There was a tendency for the temperature to be higher when the measurement point was closer to the cartridge heater 23. In the same area as the heating plate 21 and having a length of 80% of each side of the heating plate 21 (area surrounded by points (1), (7), (15), (21)) The maximum temperature difference was 19 ° C. On the other hand, 19 ° C. is the maximum temperature difference even in an area having a length of 50% of each side of the heating plate 21 (area surrounded by points (22), (23), (24), (25)). became. Note that the difference between the set temperature and the actually measured value occurs because the measurement was performed with the heating surface exposed in the air.

[Cooling unit 3]
The cooling unit 3 was composed of a copper cooling plate 31 having a 300 mm × 300 mm square and a thickness of 50 mm and having a water pipe (flow path 32) therein and a thermal resistance of 0.0015 ° C./W or less (FIG. 28). The chiller has a maximum cooling capacity of 3 kW and a maximum flow rate of 27 liters. The set temperature is 30 ° C. or less.

[Weighting unit 6]
The weighting unit 6 was configured by a pneumatic compressor type (FIG. 7). The weighting unit 6 can evenly apply a load to the module sample from the upper part of the heating unit 2 up to 200 kg. The weight can be set in increments of 1 kg. The weight value is confirmed by the load cell even during measurement, and can be automatically adjusted to the set weight. The arrangement of the heating unit 2 and the cooling unit 3 is configured such that the heating unit 2 is in the upper part, the cooling unit 3 in the lower part is fixed, and a load is applied from the upper part.

[Measurement section]
The temperature is measured at five locations on the heating plate 21, at five locations on the high and low temperature surfaces of the thermoelectric module, and at two locations on the cooling water temperature. The temperature sensor used was a heating plate 21, an R type thermocouple for the module high temperature surface, and a K type thermocouple for the module low temperature surface. A platinum resistance thermometer is used to measure the cooling water temperature. The thermocouple for measurement of the heating plate 21 is inserted into a hole provided on the side surface of the heating plate 21. When there is a module substrate on the high temperature surface of the thermocouple for measuring the high temperature surface of the module, an R type thermocouple is bonded to the surface on the element side using silver paste. When there is no module substrate, an alumina plate having a thickness of 0.8 mm is inserted between the heating plate 21 and an R type thermocouple is bonded to the element side using silver paste.

Also, as the electronic load device, a constant current DC power source capable of supplying a maximum current of 10 A was used, and a DC voltmeter capable of measuring up to 20 V was used as a voltmeter. For temperature measurement, a digital temperature measuring device corresponding to each temperature center was used.

Next, Test Examples 1 to 33 performed by the thermoelectric module power generation evaluation apparatus according to Examples 1 to 3 will be described. Test Examples 1 to 7 were performed using the thermoelectric module power generation evaluation apparatus according to Example 1. In addition, Test Examples 8 to 30 were performed by the thermoelectric module power generation evaluation apparatus according to Example 2, and Test Examples 31 to 33 were performed by the thermoelectric module power generation evaluation apparatus according to Example 3.

The thermoelectric module samples according to Test Examples 1 to 17, 26, 27, 31, and 33 are thermoelectric modules using oxide-based materials manufactured based on the following [Document 1] to [Document 3].
[Reference 1] R. Funahashi, and S. Urata, K. Mizuno, T. Kouuchi, and M. Mikami, Ca2.7Bi0.3Co4O9 / La0.9Bi0.1NiO3 thermoelectrics devices with high output power density, Applied Physics Letters, Vol 85 No. 6, pp.1036-1038 (2004)
[Reference 2] R. Funahashi, M. Mikami, T. Mihara, S. Urata, and N. Ando, A portable thermoelectric-power-generating module of Composed of oxide devices, Journal of Applied Physics, Vol. 99 No. 6 , pp. 066117-066119 (2006)
[Reference 3] S. Urata, R. Funahashi, T. Mihara, A. Kosuga, S. Sodeoka, T. Tanaka, Power generation of a p-type Ca3Co4O9 / n-type CaMnO3 module, International Journal of Applied Ceramic Technology, Vol. 4, No. 6, pp. 535-540 (2007)

Further, the thermoelectric module samples according to Test Examples 18 to 25, 28 to 30, and 32 are thermoelectric modules using a silicide-based material manufactured based on the following

documents

4 and 5.
[Reference 4] R. Funahashi, Y. Matsumura, H. Tanaka, T. Takeuchi, W. Norimatsu, E. Combe, RO Suzuki, Y. Wang, C. Wan, S. Katsuyama, M. Kusunoki, and K. Koumoto, Thermoelectric Properties of n-type Mn3-xCrxSi4Al2 in Air, Journal of Applied Physics, 112, 073713 (2012)
[Reference 5] R. Funahashi, Y. Matsumura, T. Barbier, T. Takeuchi, RO Suzuki, S. Katsuyama, A. Yamamoto, H. Takazawa, E. Combe, Durability of silicide-based thermoelectric modules at high temperatures in air, Journal of Electronic Materials, Vol. 44, Issue 8, pp 2946-2952 (2015)

<Test Examples 1 to 5>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 1 was composed of p-type Ca _2.7 Bi _0.3 Co ₄ O ₉ and n-type Ca _0.9 Yb _0.1 MnO ₃ , and the cross-sectional dimensions of the element were 3.5 mm × 3.5 mm. It is 5 mm long and is joined to the silver electrode using a silver paste. There are 8 pairs of elements, and there are one pair of p-type and n-type elements. There is no substrate, the length of the side of the high temperature surface of the thermoelectric module sample 100 is 15.5 mm × 15.5, and the thickness is 5.2 mm. The lead wire 4 is a silver sheet having a width of 3.5 mm, a thickness of 0.1 mm, and a length of 30 mm, and is connected to the electrode end on the low temperature surface side of the module sample. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, when a heat-dissipating gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) having a thickness of 0.5 mm is inserted between the low-temperature surface of the thermoelectric module sample 100 and the cooling plate 31, heat conduction and electrical insulation are ensured. At the same time, a K-type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed to the same size as the high temperature surface of the thermoelectric module sample 100 are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, Heating by heat dissipation from 21 was prevented. The heating plate temperature was set in the range of 200 to 900 ° C. every 100 ° C., and a weight of 3 kg was hung on the handle lever and loaded. The cooling water temperature set at 20 ° C. was circulated through the cooling plate 31 at a water amount of 5 liters / minute. After the temperature of the heating plate 21 reaches the set value, the external load resistance is scanned, the current value and the voltage value are measured, and the maximum output of the thermoelectric module sample 100 is calculated by the above equation 3 using the numerical values. . Furthermore, the power generation efficiency was calculated using Equation 4 from this maximum output and the amount of heat flowing into the cooling water calculated by Equation 5. The details of the thermoelectric module sample 100 whose performance was evaluated in Test Example 1 are shown in Table 4, and the results concerning the power generation output (W) and the power generation efficiency (%) with respect to each temperature of the heating plate 21 are shown in Table 5. In Table 5, the part indicated by “-” indicates that the power generation output (W) and power generation efficiency (%) for each temperature of the heating plate 21 are not measured.

In Test Examples 2 to 5, performance evaluation for the thermoelectric module sample 100 different from Test Example 1 was performed under the same conditions as in Test Example 1. Details regarding the thermoelectric module sample 100 whose performance was evaluated in Test Examples 2 to 5 are also shown in Table 4 above, and the results regarding the power generation output (W) and power generation efficiency (%) for each temperature of the heating plate 21 are shown in Table 5 above. Also shown.

<Test Example 6>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 6 was composed of p-type Ca _2.7 Bi _0.3 Co ₄ O ₉ and n-type Ca _0.9 Yb _0.1 MnO ₃ , and the cross-sectional dimensions of the element were 3.5 mm × 3.5 mm, It is 5 mm long and is joined to the silver electrode using a silver paste. There are 14 pairs of elements, and there are two pairs of p-type and n-type elements. Alumina having a size of 32 mm × 34 mm and a thickness of 0.8 mm is used as the substrate on the high temperature side. The length of the side of the low-temperature surface without the substrate is 27.5 mm × 31.5 mm, and the thickness of the thermoelectric module is 7 mm. The lead wire 4 is a silver sheet having a width of 5 mm, a thickness of 0.1 mm, and a length of 7.5 mm, and is connected to the electrode end on the high temperature surface side of the module sample. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, when a heat-dissipating gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) having a thickness of 0.5 mm is inserted between the low-temperature surface of the thermoelectric module sample 100 and the cooling plate 31, heat conduction and electrical insulation are ensured. At the same time, a K-type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed with the same dimensions as the hot surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, and from the heating plate 21. Heating due to heat dissipation was prevented. A weight of 3 kg was hung on the handle lever, and the weight was applied by the heating plate 21 at the top. While circulating the cooling water temperature set to 20 ° C. to the cooling plate 31 at a rate of 5 liters / minute, the heating plate temperature was raised from room temperature to 900 ° C. in 3 hours, and the external load resistance was scanned to measure the maximum output. . After the measurement, heating of the heating plate 21 was stopped and left for 3 hours. Thereby, the heating plate temperature became 100 ° C. or less. Thereafter, heating was started again, the temperature was raised to 900 ° C. in 3 hours, and the maximum output of the thermoelectric module was measured. This test was repeated a total of 6 times to perform a module cycle test.

<Test Example 7>
The thermoelectric module sample 100 whose performance is evaluated in Test Example 7 includes p-type Ca _2.7 Bi _0.3 Co ₄ O ₉ and n-type Ca _0.9 Yb _0.1 MnO ₃ , and the cross-sectional dimensions of the element are 3.5 mm × 3.5 mm. The length is 3.5 mm and the silver electrode is used to join the silver electrode. The number of pairs of elements is 10, and the number of pairs of elements is two for p-type and one for n-type. Alumina having a size of 32 mm × 36 mm and a thickness of 0.8 mm is used as the substrate on the high temperature side. The dimension of the thermoelectric module sample 100 excluding the substrate is 30 mm × 30 mm. The lead wire 4 is a silver sheet having a width of 5 mm, a thickness of 0.1 mm, and a length of 7.5 mm, and is connected to the electrode end on the high temperature surface side of the module. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a 0.5 mm thick heat dissipation gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) is inserted between the low temperature surface of the thermoelectric module and the cooling plate 31 to ensure heat conduction and electrical insulation, A K type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed to the same size as the high temperature surface of the thermoelectric module sample 100 are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, Heating by heat dissipation from 21 was prevented. A weight of 3 kg was hung on the handle lever, and the weight was applied by the heating plate 21 at the top. While circulating the cooling water temperature set at 20 ° C. to the cooling plate 31 with a water amount of 5 liters / minute, the heating plate temperature was increased from room temperature to 1000 ° C. in 3 hours, the external load resistance was scanned, and the maximum output was measured. . After the measurement, heating of the heating plate 21 was stopped and left for 4 hours. Thereby, the heating plate temperature became 100 ° C. or less. Thereafter, heating was started again, the temperature was increased to 1000 ° C. in 3 hours, and the maximum output of the thermoelectric module sample 100 was measured. This temperature cycle was repeated 53 times in total, and the measurement was performed every time until the 20th time and after 3 to 5 temperature cycles.

Table 6 shows the details of the thermoelectric module samples 100 of Test Examples 6 and 7, and Table 7 shows the results of the cycle test. In addition, the cycle test was not performed about the part shown by "-" in Table 7.

<Test Examples 8 to 25>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 8 was composed of p-type Ca _2.7 Bi _0.3 Co ₄ O ₉ and n-type Ca _0.9 Yb _0.1 MnO ₃ , and the cross-sectional dimensions of the element were 3.5 mm × 3.5 mm, It is 5 mm long and is joined to the silver electrode using a silver paste. There are 34 pairs of elements, and there are two pairs of p-type and n-type elements. Alumina of 45 mm x 60 mm and 0.8 mm thickness is used as the substrate on the high temperature side. The side of the low-temperature surface without the substrate is 15.5 mm × 15.5 mm, and the thickness of the thermoelectric module is 6 mm. The lead wire 4 is a silver sheet having a width of 3.5 mm, a thickness of 0.1 mm, and a length of 30 mm, and is connected to the electrode end on the low temperature side of the module. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a 0.5 mm thick heat dissipation gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) is inserted between the low temperature surface of the thermoelectric module and the cooling plate 31 to ensure heat conduction and electrical insulation, A K type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed with the same dimensions as the hot surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, and from the heating plate 21. Heating due to heat dissipation was prevented. The heating plate temperature was set in the range of 200 to 900 ° C. every 100 ° C., and a weight of 5 kg was suspended from the handle lever. The cooling water temperature set at 20 ° C. was circulated through the cooling plate 31 at a water amount of 5 liters / minute. After the temperature of the heating plate 21 reached the set value, the external load resistance was scanned to measure the maximum output of the thermoelectric module. Furthermore, the power generation efficiency was also measured using this maximum output.

Also, in Test Examples 9 to 25, performance evaluation for the thermoelectric module sample 100 different from Test Example 8 was performed under the same conditions as in Test Example 8. In some test examples, the test was performed such that the upper and lower limits of the set temperature of the heating plate 21 were different from those in Test Example 8. Table 8 shows details of the thermoelectric module sample 100 whose performance was evaluated in Test Examples 8 to 25. Table 9 shows the results regarding the power generation output (W) and the power generation efficiency (%) with respect to each temperature of the heating plate 21. In Table 9, the part indicated by “-” indicates that the power generation output (W) and the power generation efficiency (%) for each temperature of the heating plate 21 are not measured.

<Test Examples 26 and 27>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 26 was composed of p-type Ca _2.7 Bi _0.3 Co ₄ O ₉ and n-type Ca _0.9 Yb _0.1 MnO ₃ , and the cross-sectional dimensions of the element were 3.5 mm × 3.5 mm. It is 5 mm long and is joined to the silver electrode using a silver paste. There are 34 pairs of elements, and there are two pairs of p-type and n-type elements. Alumina having a size of 32 mm × 34 mm and a thickness of 0.8 mm is used as the substrate on the high temperature side. The length of the side of the low-temperature surface without the substrate is 43.5 mm × 47.5 mm, and the thickness of the thermoelectric module is 6 mm. The lead wire 4 is a silver sheet having a width of 5 mm, a thickness of 0.1 mm, and a length of 7.5 mm, and is connected to the electrode end on the high temperature surface side of the module. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a 0.5 mm thick heat dissipation gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) is inserted between the low temperature surface of the thermoelectric module and the cooling plate 31 to ensure heat conduction and electrical insulation, A K type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed with the same dimensions as the hot surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, and from the heating plate 21. Heating due to heat dissipation was prevented. A weight of 5 kg was hung on the handle lever, and a weight was applied by the heating plate 21 at the top. While circulating the cooling water temperature set to 20 ° C. to the cooling plate 31 at a rate of 5 liters / minute, the heating plate temperature was raised from room temperature to 900 ° C. in 3 hours, and the external load resistance was scanned to measure the maximum output. . After the measurement, heating of the heating plate 21 was stopped and left for 3 hours. Thereby, the heating plate temperature became 100 ° C. or less. Thereafter, heating was started again, the temperature was raised to 900 ° C. in 3 hours, and the maximum output of the thermoelectric module was measured. This test was repeated a total of 5 times to perform a module cycle test.

Test Example 27 was prepared separately with the same configuration as the thermoelectric module sample 100 according to Test Example 26, and the sample was performed under the same conditions as in Test Example 26. Table 10 shows details of the thermoelectric modules of Test Examples 26 and 27. Table 11 shows the results of these cycle tests. Although these two thermoelectric modules have the same composition and the same shape, there is a difference in deterioration phenomenon. This is because the causes of deterioration are different. In Test Example 26, it was found that the electrode portion was peeled off, and in Test Example 27, the n-type element was cracked.

<Test Example 28>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 28 was composed of p-type MnSi _1.7 and n-type Mn ₃ Si ₄ Al ₂ , and the cross-sectional dimensions of the element were 3.5 mm × 3.5 mm and the length was 7.5 mm. Then, the silver paste is used to join the silver electrode. There are 7 pairs of elements, and there are two pairs of p-type and n-type elements. Alumina with a thickness of 30 mm × 20 mm and a thickness of 0.8 mm is used as the substrate on the high temperature side. The length of the side of the low temperature surface without the substrate is 27.5 mm × 15.5 mm, and the thickness of the thermoelectric module is 8.5 mm. The lead wire 4 is a silver sheet having a width of 5 mm, a thickness of 0.1 mm, and a length of 7.5 mm, and is connected to the electrode end on the high temperature surface side of the module. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a 0.5 mm thick heat dissipation gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) is inserted between the low temperature surface of the thermoelectric module and the cooling plate 31 to ensure heat conduction and electrical insulation, A K type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed with the same dimensions as the hot surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, and from the heating plate 21. Heating due to heat dissipation was prevented. A weight of 3 kg was hung on the handle lever, and the weight was applied by the heating plate 21 at the top. While circulating the cooling water temperature set to 20 ° C through the cooling plate 31 at a rate of 5 liters / minute, the heating plate temperature is increased from room temperature to 500 ° C in 2 hours, and the external load resistance is scanned to maximize the output and power generation efficiency. Measured. After the measurement, the maximum output and power generation efficiency were measured over 43 days every 24 hours while maintaining the heating plate temperature at 500 ° C. Table 12 shows details of the thermoelectric module of Test Example 28, and Table 13 shows long-term continuous heating test results of Test Example 28.

<Test Example 29>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 29 was composed of p-type MnSi _1.7 and n-type Mn _2.7 Cr _0.3 Si ₄ Al ₂ , the cross-sectional dimensions of the element were 3.5 mm × 3.5 mm, and the length was 7 .5 mm, using silver paste and bonded to the silver electrode. There are 7 pairs of elements, and there are two pairs of p-type and n-type elements. Alumina with a thickness of 30 mm × 20 mm and a thickness of 0.8 mm is used as the substrate on the high temperature side. The length of the side of the low temperature surface without the substrate is 27.5 mm × 15.5 mm, and the thickness of the thermoelectric module is 8.5 mm. The lead wire 4 is a silver sheet having a width of 5 mm, a thickness of 0.1 mm, and a length of 7.5 mm, and is connected to the electrode end on the high temperature surface side of the module. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a 0.5 mm thick heat dissipation gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) is inserted between the low temperature surface of the thermoelectric module and the cooling plate 31 to ensure heat conduction and electrical insulation, A K type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed with the same dimensions as the hot surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, and from the heating plate 21. Heating due to heat dissipation was prevented. A weight of 3 kg was hung on the handle lever and applied with a heating plate 21 at the top. While circulating the cooling water temperature set at 20 ° C to the cooling plate 31 at a rate of 5 liters / minute, the heating plate temperature is raised from room temperature to 500 ° C in 2 hours, and the generated current of 1A is constant by the constant current DC power supply. The external load resistance was controlled so as to be maintained at a voltage, and the voltage generated by the thermoelectric module sample 100 was measured by a DC four-terminal method. The power generation output was calculated from this voltage value and current value. After the measurement, the power generation output at the time of 1 A generation was measured over 750 hours every 50 hours while keeping the heating plate temperature at 500 ° C. Table 14 shows the details of the thermoelectric module of Test Example 29, and Table 15 shows the results of the long-term constant current continuous test of Test Example 29.

<Test Example 30>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 30 was composed of p-type MnSi _1.7 and n-type Mn _2.7 Cr _0.3 Si ₄ Al ₂ , the cross-sectional dimensions of the element were 3.5 mm × 3.5 mm, and the length was 7 .5 mm, using silver paste and bonded to the silver electrode. There are 7 pairs of elements, and there are two pairs of p-type and n-type elements. Alumina with a thickness of 30 mm × 20 mm and a thickness of 0.8 mm is used as the substrate on the high temperature side. The length of the side of the low temperature surface without the substrate is 27.5 mm × 15.5 mm, and the thickness of the thermoelectric module is 8.5 mm. The lead wire 4 is a silver sheet having a width of 5 mm, a thickness of 0.1 mm, and a length of 7.5 mm, and is connected to the electrode end on the high temperature surface side of the module. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a 0.5 mm thick heat dissipation gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) is inserted between the low temperature surface of the thermoelectric module and the cooling plate 31 to ensure heat conduction and electrical insulation, A K type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed with the same dimensions as the hot surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, and from the heating plate 21. Heating due to heat dissipation was prevented. A weight of 3 kg was hung on the handle lever and applied with a heating plate 21 at the top. While circulating the cooling water temperature set to 20 ° C to the cooling plate 31 at a rate of 5 liters / minute, the heating plate temperature is raised from room temperature to 500 ° C in 2 hours, and the generated voltage of 1V is constant by the constant current DC power supply. The external load resistance was controlled so that the temperature was maintained at the current, and the current generated by the thermoelectric module was measured by the DC four-terminal method. The power generation output was calculated from this voltage value and current value. After the measurement, the power generation output when 1 V was generated was measured over 900 hours every 50 hours while keeping the heating plate temperature at 500 ° C. Table 16 shows the details of the thermoelectric module sample 100 of Test Example 30, and Table 17 shows the results of the long-term constant voltage continuous test of Test Example 30.

<Test Example 31>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 31 is that the elements of the thermoelectric module are p-type Ca _2.7 Bi _0.3 Co ₄ O ₉ and n-type Ca _0.9 Yb _0.1 MnO ₃ , and the cross-sectional dimension of the element is 3.5 mm × 3 .5 mm, 5 mm in length, and joined to the silver electrode using a silver paste. There are 64 pairs of elements, and there are two pairs of p-type and n-type elements. Alumina having a thickness of 64.5 mm × 64.5 mm and a thickness of 0.8 mm is used as the substrate on the high temperature side. The length of the side of the low temperature surface without the substrate is 63.5 mm × 63.5 mm, and the thickness of the thermoelectric module is 6 mm. The lead wire 4 is a silver sheet having a width of 5 mm, a thickness of 0.1 mm, and a length of 7.5 mm, and is connected to the electrode end on the low temperature side of the module. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a 0.5 mm thick heat dissipation gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) is inserted between the low temperature surface of the thermoelectric module and the cooling plate 31 to ensure heat conduction and electrical insulation, A K type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed with the same dimensions as the hot surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, and from the heating plate 21. Heating due to heat dissipation was prevented. The heating plate temperature was set in the range of 200 to 900 ° C. every 100 ° C., and a weight of 20 kg was applied from the top with a pneumatic compressor. The cooling water temperature set at 20 ° C. is circulated through the cooling plate 31 at a water amount of 8 liters / minute. After the temperature of the heating plate 21 reached the set value, the external load resistance was scanned to measure the maximum output of the thermoelectric module. Furthermore, the power generation efficiency was also measured using this maximum output.

<Test Example 32>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 32 was composed of p-type MnSi _1.7 and n-type Mn _2.7 Cr _0.3 Si ₄ Al ₂ , the cross-sectional dimensions of the element were 3.5 mm × 3.5 mm, and the length was 7 .5 mm, using silver paste and bonded to the silver electrode. There are 14 pairs of elements, and there are two pairs of p-type and n-type elements. Alumina with a thickness of 30 mm × 35 mm and a thickness of 0.8 mm is used as the substrate on the high temperature side. The length of the side of the low-temperature surface without the substrate is 27.5 mm × 31.5 mm, and the thickness of the thermoelectric module is 8.5 mm. The lead wire 4 is a silver sheet having a width of 5 mm, a thickness of 0.1 mm, and a length of 7.5 mm, and is on the high temperature surface side of the module. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a 0.5 mm thick heat dissipation gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) is inserted between the low temperature surface of the thermoelectric module and the cooling plate 31 to ensure heat conduction and electrical insulation, A K type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed with the same dimensions as the hot surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, and from the heating plate 21. Heating due to heat dissipation was prevented. The heating plate temperature was set in the range of 100 to 600 ° C. every 100 ° C., and was applied from the top of the weight of 10 kg with a pneumatic compressor. The cooling water temperature set at 20 ° C. is circulated through the cooling plate 31 at a water amount of 8 liters / minute. After the temperature of the heating plate 21 reached the set value, the external load resistance was scanned to measure the maximum output of the thermoelectric module. Furthermore, the power generation efficiency was also measured using this maximum output.

Table 18 shows details of the thermoelectric module samples 100 of Test Examples 31 and 32. Table 19 shows the measurement results.

<Test Example 33>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 33 was composed of p-type Ca _2.7 Bi _0.3 Co ₄ O ₉ and n-type CaMn _0.98 Mo _0.02 O ₃ , and the cross-sectional dimensions of the element were 3.5 mm × 3.5 mm. It has a length of 7 mm and is joined to a silver electrode using a silver paste. There are 64 pairs of elements, and there are two pairs of p-type and n-type elements. Alumina having a thickness of 64.5 mm × 64.5 mm and a thickness of 0.8 mm is used as the substrate on the high temperature side. The side of the low-temperature surface without the substrate is 63.5 mm × 63.5 mm, and the thickness of the thermoelectric module is 8 mm. The lead wire 4 is a silver sheet having a width of 5 mm, a thickness of 0.1 mm, and a length of 7.5 mm, and is connected to the electrode end on the high temperature surface side of the module. For electrical insulation, a polyimide (Kapton (registered trademark)) tape having a thickness of 0.07 mm was wound around the lead wire 4, and was further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a 0.5 mm thick heat dissipation gel sheet (elastic heat transfer sheet 9; trade name: lambda gel) is inserted between the low temperature surface of the thermoelectric module and the cooling plate 31 to ensure heat conduction and electrical insulation, A K type thermocouple for low-temperature surface measurement was inserted between the cooling plate 31 and the heat radiation gel sheet. Furthermore, several sheets of glass wool heat insulating material (heat insulating member 7) hollowed with the same dimensions as the hot surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and to cover the entire cooling plate 31, and from the heating plate 21. Heating due to heat dissipation was prevented. It was applied from the top of the weight of 10kg with a pneumatic compressor. While circulating the cooling water temperature set to 20 ° C to the cooling plate 31 at a rate of 8 liters / minute, the heating plate temperature is increased from room temperature to 500 ° C in 2 hours, and the generated current of 1A is constant by the constant current DC power supply. The external load resistance was controlled so that the voltage was maintained, and the voltage generated by the thermoelectric module was measured by the DC four-terminal method. The power generation output was calculated from this voltage value and current value. After the measurement, the power generation output at the time of 1 A generation was measured over 750 hours every 50 hours while keeping the heating plate temperature at 500 ° C. Table 20 shows details of the thermoelectric module sample 100 of Test Example 33. Table 21 shows the results of the long-term constant current continuous test of Test Example 33.

As described above, according to the thermoelectric module power generation evaluation apparatus according to the present invention, the performance evaluation of various evaluation items such as the output of the thermoelectric module, the power generation efficiency, the cycle characteristics, and the long-term durability under practical conditions such as high temperature and in air. Can be confirmed.

DESCRIPTION OF SYMBOLS 1 Thermoelectric module power generation evaluation apparatus 2 Heating part 21 Heating plate 22 Heating plate main body 23 Cartridge heater 25 Temperature sensor 3 Cooling part 32 Flow path 31 Cooling plate 33 Inlet pipe 34 Outlet pipe 37 Cooling

water circulation device

38, 39 Temperature sensor 4 Lead wire 5 Control calculation unit 6 Weighting unit 7 Heat insulation member 9 Heat transfer sheet 100 Thermoelectric module sample

Claims

A thermoelectric module power generation evaluation device for evaluating the power generation performance of a thermoelectric module,
A heating unit having a dimension equal to or greater than the dimension of the high temperature surface of the thermoelectric module, and having a heating surface disposed in contact with the high temperature surface;
A cooling unit having a dimension equal to or greater than the dimension of the low-temperature surface of the thermoelectric module and having a cooling surface disposed in contact with the low-temperature surface;
A power extraction line connected to the thermoelectric module;
The thermoelectric module power generation evaluation apparatus, wherein at least a part of the power lead-out line is disposed in close contact with the cooling surface of the cooling unit.
The thermoelectric module power generation evaluation apparatus according to claim 1, wherein the power lead-out line is a sheet-like wiring having a predetermined width.
The thermoelectric module power generation evaluation apparatus according to claim 1 or 2, wherein the cooling surface of the cooling unit has a larger area than the heating surface of the heating unit.
The thermoelectric module can be arranged between the heating unit and the cooling unit,
The thermoelectric module power generation evaluation apparatus according to any one of claims 1 to 3, further comprising a weighting unit that pressurizes the thermoelectric module between the heating unit and the cooling unit.
The thermoelectric module power generation evaluation apparatus according to any one of claims 1 to 4, further comprising an elastic heat transfer sheet disposed between a cooling surface of the cooling unit and a low temperature surface of the thermoelectric module.
The thermoelectric module power generation evaluation apparatus according to claim 5, wherein the heat transfer sheet further includes electrical insulation.
The heating unit includes a heating plate body made of an oxidation-resistant material having a thermal expansion coefficient of 15 × 10 −6 / K or less and a thermal conductivity of 10 W / mK or more, and the heating surface includes the heating surface The thermoelectric module power generation evaluation apparatus according to any one of claims 1 to 6, wherein the thermoelectric module power generation evaluation apparatus is one side of a plate body.
The thermoelectric module power generation evaluation apparatus according to claim 7, wherein the heating plate main body is made of stainless steel, nickel-base superalloy, or ceramics.
A cartridge heater and a temperature sensor arranged inside the heating plate main body are provided, and the cartridge heater and the temperature sensor are installed biased toward the thermoelectric module with respect to the thickness direction of the heating plate main body. The thermoelectric module power generation evaluation apparatus according to claim 7 or 8, wherein
10. The thermoelectric module power generation evaluation apparatus according to claim 1, further comprising a heat insulating member that covers the periphery of the thermoelectric module and covers the cooling surface of the cooling unit.