JP6820564B2 - Thermoelectric module power generation evaluation device - Google Patents

Description

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

Conventionally, exhaust gas from automobiles, factories, incinerators, etc. has been emitted. The emitted exhaust gas is high-quality thermal energy having a temperature of, for example, 500 ° C. or higher. Such heat energy is dilutely dispersed and released, but the total amount is enormous, and it is said that it reaches less than 70% of the primary supply energy.

In recent years, thermoelectric power generation using the Seebeck effect has been attracting attention as a technology for effectively utilizing the heat energy released in a dilute dispersion. For thermoelectric power generation, it is necessary to manufacture a thermoelectric module that increases the voltage by connecting thermoelectric materials that generate voltage due to the temperature difference in series, but most of the thermoelectric modules so far are made of metal. , It was difficult to use it in air at a high temperature of 300 ° C. or higher due to oxidation. However, recently, thermoelectric modules using thermoelectric materials such as oxides and silicides that are durable to oxidation even at high temperatures are being developed.

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

Evaluation equipment manufactured by Kotohira Kogyo Co., Ltd. <http://www.kotohira.biz/lineup/heating_equipment.html> Evaluation equipment manufactured by ULVAC, Inc. <http://www.ulvac-es.co.jp/products/mini-pem/> Evaluation device manufactured by KRI Co., Ltd. <http://www.kri-inc.jp/ts/dept/pdf/dm2-1.pdf#search=%>

The conventional evaluation device that evaluates the output, power generation efficiency, long-term durability, etc. of the thermoelectric module is to put the sample in a vacuum chamber or the like for measurement because of the low durability of the thermoelectric module in the air. , It was not suitable for performance evaluation under practical conditions. Further, in order to develop a highly durable thermoelectric module, an evaluation device capable of accurately measuring the performance of the thermoelectric module in high temperature and air is required.

In view of the above situation, an object of the present invention is to provide a thermoelectric module power generation evaluation device capable of accurately evaluating the performance of a thermoelectric module.

The object of the present invention is a thermoelectric module power generation evaluation device for evaluating the power generation performance of a thermoelectric module, which has a dimension equal to or larger than the dimension of the high temperature surface of the thermoelectric module and is arranged in contact with the high temperature surface. A heating unit having a heating surface, a cooling unit having a dimension equal to or larger 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 an electric power connected to the thermoelectric module. It is achieved by a thermoelectric module power generation evaluation device comprising a take-out line, wherein at least one part of the power take-out line is arranged in close contact with the cooling surface of the cooling part.

Further, in the thermoelectric module power generation evaluation device, it is preferable that the power take-out line is a sheet-shaped wiring having a predetermined width.

Further, 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 can be arranged between the heating unit and the cooling unit, and a weighting unit that pressurizes the thermoelectric module is further provided between the heating unit and the cooling unit.

Further, it is preferable to provide an elastic heat transfer sheet arranged between the cooling surface of the cooling unit and the low temperature surface of the thermoelectric module. It is preferable that the heat transfer sheet further has electrical insulation.

Further, the heating portion includes a heating plate main 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 is formed on the heating surface. It is preferably one side of the heating plate body.

Further, the heating plate main body is preferably made of stainless steel, nickel-based superalloy, or ceramics.

Further, 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 so as to be biased toward the thermoelectric module side with respect to the thickness direction of the heating plate main body. It is preferable that it is.

Further, it is preferable to provide 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 device capable of accurately evaluating the performance of a thermoelectric module.

It is a schematic block side view which shows the thermoelectric module power generation evaluation apparatus which concerns on this invention. Regarding the heating unit included in the thermoelectric module power generation evaluation device shown in FIG. 1, (a) is a plan view thereof, (b) is a side view of (a) seen from the A direction, and (c) is B of (a). It is a side view seen from a direction. FIG. 1A is a plan view of the cooling unit included in the thermoelectric module power generation evaluation device shown in FIG. 1, and FIG. 1B is a side view thereof. FIG. 1 is an enlarged schematic side view of a main part of the thermoelectric module power generation evaluation device shown in FIG. 1, (a) is a side view showing a case where a lead wire is connected to an electrode end on a low temperature side of a module sample, and (b) is a lead wire. Is a side view showing the case where is connected to the electrode end on the high temperature side of the module sample. It is explanatory drawing for demonstrating the thermoelectric module sample large output measured by the thermoelectric module power generation evaluation apparatus shown in FIG. It is explanatory drawing for demonstrating the open circuit voltage and the internal resistance of the thermoelectric module sample measured by the thermoelectric module power generation evaluation apparatus shown in FIG. It is explanatory drawing which is the weighted part provided in the thermoelectric module power generation evaluation apparatus shown in FIG. 1, and is for demonstrating the pneumatic type or the hydraulic type weighted part. It is a modification of the weighted part provided in the thermoelectric module power generation evaluation apparatus shown in FIG. 1, and is explanatory drawing for demonstrating the weighted part of the lever type press type. It is a modification of the weighted part provided in the thermoelectric module power generation evaluation apparatus shown in FIG. 1, and is explanatory drawing for demonstrating the weighted part of the system using a screw and a spring. It is explanatory drawing for demonstrating the modification of the weighted portion shown in FIG. FIG. 5 is an enlarged schematic cross-sectional view of a main part of a modification of the thermoelectric module power generation evaluation device shown in FIG. It is an enlarged schematic side view of the main part about the modification of the thermoelectric module power generation evaluation apparatus shown in FIG. This is an example of a plan view of a thermoelectric module sample whose performance is evaluated by the thermoelectric module power generation evaluation device shown in FIG. (A) is a side view seen from the C direction of FIG. 13, (b) is a side view seen from the D direction of FIG. 13, (c) is a side view seen from the E direction of FIG. 13, (d). Is a side view seen from the F direction of FIG. It is a perspective view regarding the shape example of the thermoelectric element which constitutes the thermoelectric module sample shown in FIG. 13 and FIG. 13 is a schematic side view showing a modified structure example of the thermoelectric module sample shown in FIGS. 13 and 14 in which the number of elements forming a pair of pn thermoelectric element pairs is two for both p-type and n-type. .. 13 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 composed of only one of the p-type element and the n-type element. 13 is an example of a modified structure of the thermoelectric module sample shown in FIGS. 13 and 14, in which FIG. 13A is a plan view thereof, FIG. 13B is a side view of the thermoelectric module sample in FIG. 13A as viewed from the C direction, and FIG. The side view seen from the D direction in (a), (d) is the side view seen from the E direction in (a). 13 is an example of a modified structure of the thermoelectric module sample shown in FIGS. 13 and 14, in which FIG. 13A is a schematic side view showing a case where an electrically insulating substrate is provided on both a high temperature side and a low temperature side, and FIG. , Is a schematic side view showing a case where there is no electrically insulating substrate on both the high temperature side and the 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 where the temperature measurement was performed when the set temperature of the cartridge heater of the heating part which concerns on Example 1 shown in FIG. 20 was set to 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 where the temperature measurement was performed when the set temperature of the cartridge heater of the heating part which concerns on Example 2 shown in FIG. 23 was set to 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 where the temperature measurement was performed when the set 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 to facilitate understanding of the configuration. FIG. 1 is a schematic configuration side view showing a thermoelectric module power generation evaluation device 1 according to an embodiment of the present invention. As shown in FIG. 1, the thermoelectric module power generation evaluation device 1 includes a heating unit 2 and a cooling unit 3 arranged so as to sandwich the thermoelectric module sample 100 in the vertical direction. It also includes a measurement unit and a control calculation unit 5 that evaluate the performance of the thermoelectric module sample 100.

The heating unit 2 is a means for heating the high temperature surface of the thermoelectric module sample 100 sandwiched between the heating unit 2 and the cooling unit 3, and includes a heating plate 21 capable of raising the high temperature surface of the thermoelectric module sample 100 to, for example, about 1000 ° C. ing. As shown in FIG. 2, the heating plate 21 includes a heating plate main body 22 and a plurality of cartridge heaters 23 housed therein. 2 (a) shows a plan view of the heating plate 21, FIG. 2 (b) shows a side view of FIG. 2 (a) as viewed from the A direction, and FIG. 2 (c) shows FIG. The side view of (a) seen from the B direction 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 so as to have a dimension equal to or larger than the dimension of the high temperature surface of the thermoelectric module sample 100. Various shapes of the heating surface can be adopted, but for example, it is preferably configured as a square or rectangle of 50 to 200 mm × 50 to 200 mm. The heating plate 21 may have one or a plurality of holes 24 having a diameter of about 5.5 to 30 mm on one side surface, and may have a thickness that allows the cartridge heater 23 to be inserted into the holes 24. It suffices to have a thickness of about 10 to 20 mm.

The diameter of the cartridge heater 23 housed in the heating plate main body 22 is configured to be 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 and the length is long. The diameter is set to about 30 to 200 mm.

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

The temperature unevenness of the heating surface is within the region where the maximum temperature difference when the thermoelectric module sample 100 is not brought into contact 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 the temperature is 50 ° C. or lower, and 20 ° C. or lower in the region of 50% or less. As a result, when the thermoelectric module sample 100 is heated, the maximum difference in temperature in 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 30 ° C. or lower, and 10 ° C. or lower within a region of 50% or less. In order to realize this, deformation such as warpage and swelling of the heating surface due to thermal expansion at high temperature, and the number of cartridge heaters 23 and the arrangement interval may be appropriately adjusted. In order to suppress the deformation of the heating surface, a material having a coefficient of thermal expansion as low as possible may be used as the material of the high temperature source (heating plate main body 22). In the size of the heating plate main body 22 according to the present invention, deformation of the heated surface can be prevented by using a material having a coefficient of thermal expansion of 15 × 10 ^-6 / k or less at a temperature of 1000 ° C. or less. Further, in order to prevent the temperature non-uniformity, it is preferable that the material has a high thermal conductivity, and if it is 10 w / mk or more, the in-plane temperature non-uniformity can be reduced. Specifically, if the metal material is stainless steel, SUS403, SUS405, SUS430, if it is a nickel-based superalloy, Inconel 600, Incoloy 800, if it is ceramics, silicon carbide, silicon nitride, aluminum nitride, aluminum oxide, etc. Can be used. Considering processing of the hole 24 for the cartridge heater 23 and damage due to rapid heating or cooling, metals such as stainless steel and nickel-based superalloys are preferable to ceramics.

Further, the heating plate 21 is a member for inputting 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 may be such that a temperature difference can be added to the thermoelectric module sample 100 and a measurable amount of power generation can be output, but in general, the heat output per cartridge heater 23 is 50 to 50. The one of about 700W may be used. The distance between the cartridge heaters 23 is preferably equal, and may be about 10 to 30 mm, 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. Considering the high temperature, a K type or R type thermocouple is preferable, and durability up to 1000 ° C. Considering this, the R type thermocouple is the most preferable. Further, in order to measure the temperature unevenness of the heating surface, as shown in FIG. 2A, it is preferable to attach a plurality of temperature sensors 25 inside the heating plate main body 22. At that time, in order to minimize the temperature unevenness, the diameter of the hole 26 for the temperature sensor should be as small as possible, and the length may be set to a length that can measure various points of the heating plate 21. Further, it is preferable that at least one temperature sensor 25 is connected to the temperature controller of the heater of the heating plate 21 and used for temperature adjustment, more preferably, a plurality of such cartridge heaters 23 can be individually controlled. The temperature sensors 25 of the above are arranged, and each of them is connected to the temperature controller.

Further, when 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. Therefore, the heating plate 21 (heating) It is preferable to install the cartridge heater 23 and the temperature sensor 25 in a biased manner 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 to be energized to the cartridge heater 23 is automatically adjusted by the program of the control unit 27, and the temperature, elevating temperature, and holding time are adjusted. It is controlled. Further, the PID control is configured to suppress excessive temperature rise of the heater.

The cooling unit 3 is a means for cooling the low temperature surface of the thermoelectric module sample 100 sandwiched between the cooling unit 3 and the heating unit 2, as shown in the plan view of FIG. 3 (a) and the side view of FIG. 3 (b). It has a form. The cooling unit 3 includes a metal cooling plate 31. Inside the cooling plate 31, a flow path 32 through which cooling water can pass is formed as shown by a dotted line in the plan view of FIG. 3A. 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 these water inlet pipes 33 and water outlet pipes 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 so that water at about 10 to 30 ° C. is circulated. The cooling capacity of the cooling plate 31 is preferably about 0.05 ° C./W or less, and more preferably about 0.03 ° C./W or less in terms of 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 and arranged in 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 obstruct the cooling water flow in the inlet / outlet pipes (inflow pipe 33 and outlet pipe 34). For example, an introduction pipe is provided in the inlet / outlet pipe having an outer diameter of about 5 to 20 mm. , A thermocouple having a diameter of about 1 to 2 mm, a resistance temperature sensor, or the like can be used. Examples include K-type thermocouples and platinum resistance temperature detectors. The water inlet / outlet pipes may be arranged on the same side surface or different side surfaces of the cooling plate 31, and may be arranged on the cooling surface or the opposite surface 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 for cooling the thermoelectric module sample 100, and this cooling surface is a surface capable of contacting the low temperature surface side of the thermoelectric module sample 100 and is smooth. The size of the cooling surface is set to be equal to or larger than the size of the low temperature surface of the thermoelectric module sample 100 to be measured. Further, in order to protect the peripheral members arranged on the cooling plate 31 side from the high temperature due to heat transfer from the heating plate 21, each side of the cooling plate 31 has a longer dimension than each side of the heating surface of the heating plate 21. It is preferable that the structure is such 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.

Further, the thermoelectric module power generation evaluation device 1 includes a power take-out wire (lead wire 4) connected to the thermoelectric module sample 100. The lead wire 4 is a wiring connected to both terminals of the thermoelectric module sample 100 (both ends (both electrode ends) of a pn thermoelectric element group connected in series by electrodes 102). The lead wire 4 becomes hot due to heat dissipation from the heating surface, and heat is generated due to the electric resistance of the lead wire 4 depending on the generated current value. The temperature rise of the lead wire 4 causes fluctuations in the electrical resistance of the lead wire 4 and temperature inhomogeneity in the thermoelectric module due to the inflow of heat, which hinders accurate measurement. Therefore, for example, as shown in FIG. 4A, the cooling plate 31 is configured to be brought into close contact with the surface for cooling. 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 interfere with heat transfer. This enables protection of the lead wire 4 and accurate measurement. Further, since the heat generated by the electric resistance generated in the lead wire 4 can be taken into the cooling water, more accurate power generation efficiency can be measured. The lead wire 4 led from the thermoelectric module sample 100 may be configured to be guided from the low temperature surface side as shown in FIG. 4A, or as shown in FIG. 4B. Although it may be configured to be guided from the high temperature surface side, the lead wire 4 is bent and installed so as to come into contact with the cooling surface over a long distance as much as possible. In particular, when the lead wire 4 is guided from the high temperature surface side, the lead wire 4 is bent while paying attention to contact with the thermoelectric element.

Here, the heating unit 2 and the cooling unit 3 may be arranged in any way, but in consideration of fixing the thermoelectric module and the like, they are arranged vertically as shown in FIGS. 1 and 4. This is preferable because it has a simpler device structure and facilitates measurement. Further, either the heating unit 2 or the cooling unit 3 may be arranged at the upper part, but considering problems such as heating of the cooling surface due to convection of heated air and water leakage, the heating unit 2 is placed at the upper part. It is preferable that the cooling unit 3 is arranged at the bottom and the thermoelectric module sample 100 is sandwiched between the heating unit 2 and the cooling unit 3 from the vertical direction.

The measuring unit is equipped with a plurality of temperature sensors. 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. Further, it is provided with a temperature sensor that measures the temperature of the high temperature surface, the low temperature surface, and the side surface of the thermoelectric module sample 100. The measurement method of the sensor for temperature measurement is not specified, but a thermocouple or a resistance temperature sensor may be used from the viewpoint of measurement accuracy and convenience. Further, in order to realize the measurement in high temperature air, which is a feature of the present invention, a highly durable temperature sensor may be used under operating conditions, and when measuring the high temperature surface of the heating plate 21 or the thermocouple module sample 100, It is preferable to use an R type thermocouple using a platinum-platinum / rhodium alloy, a K type thermocouple using alumel-chromel, or a platinum resistance temperature detector for measuring the cooling plate 31 and water temperature.

Further, the measuring unit includes a heating plate 21, a high-temperature surface and a low-temperature surface of the thermoelectric module sample 100, and a measuring instrument for converting the temperature of an electric signal from a sensor for measuring the temperature of cooling water. Further, the measuring unit is provided with a constant current DC power supply or an electronic load device for applying an external load resistance to the thermoelectric module sample 100, and further is provided with a DC voltmeter capable of measuring the voltage generated by the thermoelectric module sample 100. .. The measurement method may be the DC four-terminal method, and the electric wire for external load resistance through which current flows and the electric wire for voltage measurement 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 measured numerical values such as temperature, voltage, current, and external load resistance, performing calculation processing, and storing them. For example, a general personal computer can be used. In addition, it is preferable to configure the device so that measurement control can be performed by a program such that automatic measurement can be performed at regular time intervals. The control calculation unit 5 is configured to be able to automatically calculate the voltage and the power generation output based on the following equations 1 and 2.

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

Further, 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. There is. In this case, the power generation output value is calculated from the measured current value and voltage value by (Equation 2), 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. It is configured to obtain the maximum output value generated by the thermoelectric module sample 100 by calculation by quadratic function approximation. Further, regarding the voltage (open circuit voltage) and the internal resistance value when no external load resistance is applied to the thermoelectric module sample 100, as shown in FIG. 6, the measured current value and voltage value are plotted on the horizontal axis and the vertical axis, respectively. , The linear approximation is configured to calculate the open circuit voltage, which is the section, and the internal resistance value, which is the absolute value of the slope. 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 match, the maximum output of the thermoelectric module sample 100 may be automatically calculated by the following equation 3. ..

Maximum output (W) = (open circuit voltage) ² / (4 x internal resistance value) (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, and 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) + amount of heat flowing into the 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.

Amount of heat flowing into the cooling water (W) = (water temperature at the outlet (° C) -water temperature at the inlet (° C)) x circulating water volume (cm ³ / min) x temperature-corrected water density (g / cm ³ ) x Specific heat of water (1.0 cal / g ・ ℃) × unit conversion (1.94 × 10 ^-6 W / min) (Equation 5)

Further, as shown in FIG. 1, the thermoelectric module power generation evaluation device 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. Since the degree of contact between the high-temperature and low-temperature 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 load during measurement is precise and constant. It is preferable to keep it at. As a specific configuration of the weighted portion 6 that pressurizes (weights) the thermoelectric module sample 100, a pneumatic or hydraulic type using a compressor as shown in FIG. 7 and a lever principle as shown in FIG. 8 are used. A method of suspending a weight 61 on a lever by a lever-type press to apply a load, a method using a screw and a spring as shown in FIGS. 9 and 10, and the like can be adopted. Further, since the weight value fluctuates due to thermal expansion or the like during measurement, it is preferable to provide a mechanism for constantly measuring the weight with a weight sensor such as a load cell and keeping the weight value constant. Regarding the weighting direction, the weighting may be from both the top and bottom or the left and right, or from either one, but in order to simplify the installation of the thermoelectric module sample 100 and the device structure, the weighting is performed so as to apply the weight in the vertical direction. It is preferable to form the portion 6, and more simply, it is preferable to fix the lower portion and apply a load from the upper portion.

Further, in the thermoelectric module power generation evaluation device 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 dissipation from the heating plate 21. , It is preferable that the thermoelectric module sample 100 is provided with a heat insulating member 7 that covers the periphery of the thermoelectric module sample 100 and also covers the surface of the cooling plate 31 (the cooling surface of the cooling unit 3). When measuring a thin thermoelectric module sample 100, the heating surface and the cooling surface face each other at a short distance, so that the cooling water is heated by the thermal energy that does not pass through the thermoelectric module sample 100, and the measurement accuracy of the power generation efficiency is improved. It may be low. Further, when measuring a thick thermoelectric module, heat is dissipated from the side surface of the thermoelectric material, which may also deteriorate the measurement accuracy of the power generation efficiency. 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 a porous ceramic heat insulating material can be adopted. Further, on the opposite surface of the cooling plate 31 (the surface opposite to the side on which the thermoelectric module sample 100 is arranged; the lower surface of the cooling plate 31 in FIG. 11), a heat insulating material covering the entire surface is arranged. Is preferable. With such a configuration, it is possible to prevent heat dissipation and inflow on the opposite surface of the cooling plate 31, and the amount of heat flowing into the cooling plate 31 is the amount of heat that has passed through the thermoelectric module and the amount of heat from the lead wire 4, which is accurate. It is possible to calculate the power generation efficiency.

Further, as shown in FIG. 1, the thermoelectric module power generation evaluation device 1 according to the present invention includes a safety enclosure 81, an emergency stop button 82, and an alarm indicator light 83. 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, and the heating plate 21, the thermoelectric module sample 100, and the cooling plate 31 are provided from the outside. It is preferably composed of punching metal or a heat-resistant wire net so that it can be observed. A door for replacing the module sample 100 is provided on at least one side surface of the safety enclosure 81, and if this door is opened during measurement, the heater in the heating unit 2 is energized or loaded. It is preferable that the operation of the unit 6 is stopped so that the measurement can be stopped urgently. In addition, at least one temperature sensor is placed in the safety enclosure 81 to control the temperature inside the enclosure, and when the temperature exceeds the set value, the heating unit 2 stops energizing and loading the heater, and measurement is urgent. May be configured to be able to stop

The emergency stop button 82 and the alarm indicator light 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 heating unit 2 can energize the heater and stop the operation of the weighting unit 6 by pressing the button. .. In addition, the alarm indicator lamp 83 operates to notify the measurer when the preset heating conditions, measurement, etc. do not operate according to the program due to some trouble, and during normal operation, the alarm indicator lamp 83 operates. It is configured to light a green lamp, a yellow lamp when measurement is stopped, and a red lamp when an abnormality occurs.

In the thermoelectric module power generation evaluation device 1 according to the present invention, as described above, a heating unit having a dimension equal to or larger than the dimension of the high temperature surface of the thermoelectric module sample 100 and having a heating surface arranged in contact with the high temperature surface. 2 and a cooling unit 3 having a dimension equal to or larger than the dimension 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 take-out wire (lead wire 4) is installed so as to be 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 take-out wire (lead wire 4) connected to the thermoelectric module sample 100 is installed so as to be in close contact with the cooling surface of the cooling plate 31 of the cooling unit 3, it occurs in the lead wire 4. The amount of heat related to the heat generated by the electrical resistance can be taken into the cooling water through the cooling surface, and the amount of heat supplied to the lead wire 4 by heat dissipation from the heating surface of the heating unit 2 is also the cooling water through the cooling surface. It is possible to measure the power generation efficiency more accurately.

The shape and dimensions of the lead wire 4 are not particularly limited, but various shapes such as a plate shape, a strip shape, a round columnar shape, and a stranded wire shape can be adopted. The larger the cross-sectional area of the lead wire 4, the smaller the electric resistance and the loss of the power generation output can be reduced. However, when the cross-sectional area is large, heat from the high temperature side is easily released through the lead wire 4, and the lead wire When 4 is on the high temperature side of the module, heat that is not involved in thermoelectric conversion flows directly from the heat source into the cooling water, which deteriorates the measurement accuracy of the conversion efficiency. In order to prevent this, for example, it is preferable to use a sheet-shaped lead wire 4 having a width of 0.1 cm to 3 cm and a thickness of about 0.005 cm to 0.2 cm, and more preferably a width of 0.5 cm to 1 cm and a thickness of 0.005 cm. It is preferable to use a sheet-shaped lead wire 4 having a size of about 0.1 cm. Such a sheet-shaped lead wire 4 (strip-shaped lead wire 4) having a predetermined width and a thin thickness is adopted, 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, so that the accuracy is extremely high. It is possible to measure 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, the peripheral members arranged on the cooling plate 31 side can be protected from the high temperature due to heat transfer from the heating plate 21, and the amount of heat radiated from the heating plate 21 can be effectively received. This makes it possible to measure power generation efficiency more accurately.

Further, in the thermoelectric module power generation evaluation device 1 according to the present invention, as shown in the enlarged schematic configuration 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. It may be configured to include the elastic heat transfer sheet 9. When such an elastic heat transfer sheet 9 is arranged between the cooling surface and the low temperature surface of the thermoelectric module sample 100, even if a temperature measuring sensor is inserted between the heat transfer sheet 9 and the water cooling surface, the temperature measurement sensor may be inserted. Since no large gap is formed, it is possible to measure the temperature of the element on the low temperature surface more accurately, and it is possible to measure the power generation efficiency of the thermoelectric module sample 100 more accurately. It is preferable that the elastic heat transfer sheet 9 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 elastic heat transfer sheet 9, for example, a sheet material made of silicone-based rubber or acrylic-based rubber can be used.

Here, the thermoelectric module sample 100 whose performance is evaluated by the thermoelectric module power generation evaluation device 1 according to the present invention preferably has a plate-like shape as shown in FIGS. 1, 13, and 14. (In FIG. 14, the dimension in the thickness (height) direction is 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 of 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 configured to be connected in series with each other, such as p-type, n-type, p-type, n-type, etc., via an electrode 102. A part of the electrode 102 is arranged between the low temperature side substrate 101 and a pair of pn type thermoelectric element pairs, 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 components such as the thermoelectric material, the electrode material, and the substrate used in the thermoelectric module sample 100 are not particularly limited as long as they do not melt, evaporate, or pulverize at the measured temperature and maintain their shape. Further, the shapes of the p-type thermoelectric element and the n-type thermoelectric element are not particularly limited, but from the viewpoint of ease of manufacture, as shown in FIG. 15, a square column or a cylindrical shape is preferable. 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 small, the generated current value becomes large, so that the heat generated by the lead wire 4 becomes large and the voltage value becomes large. Therefore, the measurement accuracy may be low. Therefore, in general, it is preferable to use a quadrangular prism having a cross section of about 1 mm to 10 mm or a cylinder having 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 configured to be different, or the cross-sectional dimensions of the p-type thermoelectric element and the n-type thermoelectric element may be different. Good. Further, the height H of the p-type or n-type thermoelectric element is not particularly limited, but the internal resistance, durability, ease of temperature difference, and thermoelectricity that cause a decrease in the accuracy of power generation efficiency of the thermoelectric module sample 100 are not particularly limited. From the viewpoint of preventing heat dissipation from the side surface of the material, it is preferably about 1 to 30 mm, more preferably about 1 to 7 mm. Although the heights H of the p-type and n-type thermoelectric elements may be different, it is preferable that all the 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, there is a case where the number of elements forming a pair of pn thermoelectric element pairs is one for both the p-type and the n-type. For example, it is shown in FIG. As described above, the number of elements forming a pair of pn thermoelectric element pairs may be two for both p-type and n-type, or as shown in FIG. 17, p-type element or n-type. The thermoelectric module sample 100 may be composed of only one of the thermoelectric elements. 16 (a) to 16 (c) and 17 (a) to 17 (c) each correspond to the side views seen from the C direction, the D direction, and the E direction of FIG.

Further, in the configurations of FIGS. 13 and 14, the thermoelectric elements are connected to each other by using the conductive electrodes 102, but the configuration is not particularly limited to such a configuration, and for example, as shown in FIG. 18, p. The type thermoelectric element and the n-type thermoelectric element may be configured to be directly bonded. 18 (a) shows a plan view of the thermoelectric module sample 100, and FIGS. 18 (b) to 18 (d) are side surfaces of FIG. 18 (a) as viewed from the C direction, the D direction, and the E direction. The figure is shown. When forming a bond, solder or conductive paste can be used, but in order to produce a module with high durability in high temperature air, silver or platinum is used rather than solder, which may cause oxidation or melting. It is preferable to use a conductive paste using a precious metal such as gold. The distance between the elements should not be such that the elements come into contact with each other to cause an electric short circuit, but if it is too wide, the number of elements in the thermoelectric module will be small and a high output cannot be obtained. Therefore, the distance between the elements is preferably about 0.1 to 5 mm, more preferably about 0.1 to 1 mm.

Further, in the configurations of FIGS. 13 and 14, the electrically insulating low temperature side substrate 101 is provided on the low temperature surface side of the thermoelectric module sample 100, and the substrate is not provided on the high temperature surface side. The configuration is not particularly limited, and for example, as shown in FIG. 19A, the electrically insulating high temperature side substrate 103 is arranged on the high temperature surface side of the thermoelectric module sample 100 in addition to the low temperature side substrate 101. 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 the side views seen from the D direction in FIG. The thermoelectric module sample 100 is configured so that neither the low temperature side substrate 101 nor the high temperature side substrate 103 is provided, or one of them is 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 the 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 and. In this case, if the thermal conductivity is low, it is difficult to give a temperature difference to the thermoelectric module sample 100. Therefore, it is preferable that the insert has as high thermal conductivity as possible and is thin. For example, a thin ceramic plate such as alumina or silicon nitride can be arranged between the heating surface and the thermoelectric module sample 100, and a commercially available heat can be arranged between the cooling surface and the thermoelectric module sample 100. Conductive grease and polyimide (Kapton®) tape can be arranged.

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

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

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

The configurations of the heating unit 2, the cooling unit 3, the weighting unit 6, and the measuring unit in the thermoelectric module power generation evaluation device according to the first embodiment are as follows.
[Heating part 2]
65 mm x 50 mm square, 25 mm thick Inconel 600 heating plate body 22 is in contact with the thermoelectric module sample 100 at three locations on the side surface, 4.5 mm from the outside of the heating plate body 22, the distance between the outer circumferences is 10 mm. A hole 24 having a diameter of 12 mm was opened so as to be 6 mm from the heating surface side, and a cartridge heater 23 was loaded to form the heating plate 21 (FIG. 20). At this time, the tip of the cartridge heater 23 is arranged so as to reach a depth of 40 mm from the outer edge of the heating plate 21. Two holes 26 having a diameter of 2 mm are formed on the opposite side surface so as to be 20.5 mm from the outside of the heating plate main body 22, the distance between the outer circumferences is 20 mm, and 11 mm from the heating surface side in contact with the thermoelectric module sample 100. Was opened, and an R type thermocouple (temperature sensor 25) was loaded. With this arrangement, the thermocouples are located 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. is adopted. The heat generation amount of the heating plate 21 is two cartridge heaters 23, and the maximum output is 1 kW.

Table 1 shows the temperature distribution of the heating surface when the heating plate 21 is heated at a setting of 900 ° C. in a no-load state without contacting 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. Within the region (the region surrounded by points (1), (7), (15), and (21)) that has the same center as the heating plate 21 and has a length of 80% of each side of the heating plate 21. The maximum temperature difference was 49 ° C. On the other hand, in the region having a length of 50% of each side of the heating plate 21 (the region surrounded by points (22), (23), (24), and (25)), 16 ° C. is the maximum temperature difference. became. The difference between the set temperature and the measured value is caused by exposing the heated surface to the air for measurement.

[Cooling unit 3]
The cooling unit 3 is 80 mm × 80 mm square, 20 mm thick, and is composed of a copper cooling plate 31 having a water pipe (flow path 32) inside and having 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 lower.

[Weighted part 6]
The weighted portion 6 was constructed by a lever press type using the principle of leverage (FIG. 8). The weighted portion 6 is configured such that a weight of up to 5 kg is hung on a lever and a weight is evenly applied to the module sample from the upper part of the heating portion 2. The weight can be set in 1 kg increments. The weight value is confirmed by the load cell even during measurement, and the weight is manually hung on the lever to maintain a constant value. The heating unit 2 and the cooling unit 3 are arranged so that the heating unit 2 is located at the upper part, the cooling unit 3 at the lower part is fixed, and a load is applied from the upper part.

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

Further, as an electronic load device, a constant current DC power source capable of energizing a current of up to 5 A was used, and as a voltmeter, a DC voltmeter capable of measuring up to 10 V was used. For temperature measurement, a digital temperature measuring instrument corresponding to each temperature center was used.

The configurations of the heating unit 2, the cooling unit 3, the weighting unit 6, and the measuring unit in the thermoelectric module power generation evaluation device according to the second embodiment are as follows.

[Heating part 2]
At five locations on the side surface of the Inconel 600 heating plate body 22 of 140 mm x 140 mm square and 25 mm thick, 14 mm from the outside of the heating plate 21, the distance between the outer circumferences is 13 mm, and 6 mm from the heating surface side in contact with the thermoelectric module. A hole 24 having a diameter of 12 mm was formed so as to be such that a cartridge heater 23 was loaded to form a heating plate 21. (Fig. 23). At this time, the tip of the cartridge heater 23 is arranged so as to reach a depth of 135 mm from the outer edge of the heating plate 21. On the opposite side surface, holes 26 having a diameter of 2 mm are 31.5 mm from the outside of the heating plate main body 22, the distance between the outer circumferences is 23 mm, and four holes are formed so as to be 11 mm from the heating surface side in contact with the thermoelectric module sample 100. 26 was opened and an R type thermocouple (temperature sensor 25) was loaded. With this arrangement, each thermocouple is located at equal intervals with the two cartridge heaters 23. The tip of the thermocouple is arranged so as to reach a depth of 70 mm from the outer edge of the heating plate 21. One of the two thermocouples near 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. is adopted. The heat generation amount of the heating plate 21 is 5 cartridge heaters 23, and the maximum output is 2.5 kW.

Table 2 shows the temperature distribution of the heating surface when the heating plate 21 is heated at a setting of 800 ° C. in a no-load state without contacting with the thermoelectric module sample 100. A thermo-viewer is used for the 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. Within the region (the region surrounded by points (1), (7), (15), and (21)) that has the same center as the heating plate 21 and has a length of 80% of each side of the heating plate 21. The maximum temperature difference was 48 ° C. On the other hand, in the region having 50% of the length of each side of the heating plate 21 (the region surrounded by points (22), (23), (24), and (25)), 20 ° C is the maximum temperature difference. became. The difference between the set temperature and the measured value is caused by exposing the heated surface to the air for measurement.

[Cooling unit 3]
The cooling unit 3 is 140 mm × 140 mm square, 20 mm thick, and is composed of a copper cooling plate 31 having a water pipe (flow path 32) inside and having 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 lower.

[Weighted part 6]
The weighted portion 6 was constructed by a lever-type press using the principle of leverage (FIG. 8). The weighting portion 6 is configured such that a weight of up to 10 kg is hung on the lever and the module sample is evenly weighted from the upper part of the heating portion 2. The weight can be set in 1 kg increments. The weight value is confirmed by the load cell even during measurement, and the weight is manually hung on the lever to maintain a constant value. The heating unit 2 and the cooling unit 3 are arranged so that the heating unit 2 is located at the upper part, the cooling unit 3 at the lower part is fixed, and a load is applied from the upper part.

[Measurement unit]
The temperature is measured at 4 points on the heating plate 21, 2 points each on the high temperature surface and the low temperature surface of the thermoelectric module sample 100, and 2 points at the cooling water temperature. A heating plate 21 was used as the temperature sensor, an R type thermocouple was used for the module high temperature surface, and a K type thermocouple was used for the module low temperature surface. A platinum resistance temperature detector is used to measure the cooling water temperature. For the measurement thermocouple of the heating plate 21, the thermocouple is inserted into a hole provided on the side surface of the heating plate 21. For the thermocouple for measuring the high temperature surface of the module sample, when the substrate of the module sample is on the high temperature surface, an R type thermocouple is adhered to the surface on the element side using silver paste. When there is no substrate for the module sample, an alumina plate having a thickness of 0.8 mm is inserted between the module sample and the heating plate 21, and an R type thermocouple is bonded to the element side using silver paste.

Further, as an electronic load device, a constant current DC power source capable of energizing a current of up to 10 A was used, and as a voltmeter, a DC voltmeter capable of measuring up to 10 V was used. For temperature measurement, a digital temperature measuring instrument corresponding to each temperature center was used.

The configurations of the heating unit 2, the cooling unit 3, the weighting unit 6, and the measuring unit in the thermoelectric module power generation evaluation device according to the third embodiment are as follows.

[Heating part 2]
Six places on the side surface of the Inconel 600 heating plate body 22 of 160 mm x 150 mm square and 30 mm thick, 11.5 mm from the outside of the heating plate 21, the distance between the outer circumferences is 15 mm, and the heating surface in contact with the thermoelectric module sample 100. A hole 24 having a diameter of 12 mm was opened so as to be 7 mm from the side, and a cartridge heater 23 was loaded to form a heating plate 21 (FIG. 26). At this time, the tip of the cartridge heater 23 is arranged so as to reach a depth of 155 mm from the outer edge of the heating plate 21. Holes 26 having a diameter of 2 mm are formed on the opposite side surface by 25 mm from the outside of the heating plate main body 22, the distance between the outer circumferences is 27.5 mm, and 5 holes are formed so as to be 12 mm from the heating surface side in contact with the thermoelectric module sample 100. Was opened, and an R type thermocouple (temperature sensor 25) was loaded. With this arrangement, each thermocouple is located 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. is adopted. The heat generation amount of the heating plate 21 is 5 cartridge heaters 23, and the maximum output is 3 kW.

Table 3 shows the temperature distribution of the heating surface when the heating plate 21 is heated at a setting of 600 ° C. in a no-load state without contacting with the thermoelectric module sample 100. A thermo-viewer is used for the measurement, and the measurement points displayed in Table 3 are shown in FIG. 27. There was a tendency for the temperature to be higher when the measurement point was closer to the cartridge heater 23. Within the region (the region surrounded by points (1), (7), (15), and (21)) that has the same center as the heating plate 21 and has a length of 80% of each side of the heating plate 21. The maximum temperature difference was 19 ° C. On the other hand, 19 ° C is the maximum temperature difference even within the region having 50% of the length of each side of the heating plate 21 (the region surrounded by points (22), (23), (24), and (25)). became. The difference between the set temperature and the measured value is caused by exposing the heated surface to the air for measurement.

[Cooling unit 3]
The cooling unit 3 is 300 mm × 300 mm square, 50 mm thick, and is composed of a copper cooling plate 31 having a water pipe (flow path 32) inside and having 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 lower.

[Weighted part 6]
The weighted portion 6 was configured by a pneumatic compressor type (FIG. 7). The weighted portion 6 can evenly load the module sample from the upper part of the heating portion 2 up to a maximum of 200 kg. The weight can be set in 1 kg increments. The weight value is confirmed by the load cell even during measurement, and it is configured so that the weight can be adjusted automatically. The heating unit 2 and the cooling unit 3 are arranged so that the heating unit 2 is located at the upper part, the cooling unit 3 at the lower part is fixed, and a load is applied from the upper part.

[Measurement unit]
The temperature is measured at 5 points on the heating plate 21, 5 points each on the high temperature surface and the low temperature surface of the thermoelectric module, and 15 points at 2 points based on the cooling water temperature. A heating plate 21 was used as the temperature sensor, an R type thermocouple was used for the module high temperature surface, and a K type thermocouple was used for the module low temperature surface. A platinum resistance temperature detector is used to measure the cooling water temperature. For the measurement thermocouple of the heating plate 21, the thermocouple is inserted into a hole provided on the side surface of the heating plate 21. For the thermocouple for measuring the high temperature surface of the module, if the module substrate is on the high temperature surface, an R type thermocouple is adhered to the surface on the element side using silver paste. If there is no module substrate, an alumina plate with a thickness of 0.8 mm is inserted between the module and the heating plate 21, and an R-type thermocouple is bonded to the element side using silver paste.

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

Next, Test Examples 1 to 33 performed by the thermoelectric module power generation evaluation device according to Examples 1 to 3 will be described. Test Examples 1 to 7 were carried out by the thermoelectric module power generation evaluation device according to Example 1. Further, Test Examples 8 to 30 were carried out by the thermoelectric module power generation evaluation device according to Example 2, and Test Examples 31 to 33 were carried out by the thermoelectric module power generation evaluation device 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 prepared based on the following [Reference 1] to [Reference 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)

The thermoelectric module samples according to Test Examples 18 to 25, 28 to 30, and 32 are thermoelectric modules using silicide-based materials prepared 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 electronics-based thermoelectric modules at high temperatures in air, Journal of Electronic Materials, Vol. 44, Issue 8, pp 2946-2952 (2015)

<Test Examples 1-5>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 1 has elements 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 elements are 3.5 mm × 3.5 mm. It has a length of 5 mm and is joined to a silver electrode using a silver paste. The number of pairs of elements is eight, and the number of pairs of elements is one for both p and n types. There is no substrate, and 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 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. Further, when a heat radiation 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating member 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module sample 100 are stacked to cover the periphery of the thermoelectric module sample 100 and cover the entire cooling plate 31 to cover the heating plate. The heating due to the heat radiation from 21 was prevented. The heating plate temperature was set in the range of 200 to 900 ° C. in every 100 ° C., and a 3 kg weight was suspended from the handle lever and weighted. The cooling water temperature set to 20 ° C. was circulated through the cooling plate 31 at a water volume of 5 liters / minute. After the temperature of the heating plate 21 reached the set value, the external load resistance was scanned, the current value and the voltage value were measured, and the maximum output of the thermoelectric module sample 100 was calculated by the above equation 3 using these values. .. Further, 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. Table 4 shows the details of the thermoelectric module sample 100 whose performance was evaluated in Test Example 1, and Table 5 shows the results regarding the power generation output (W) and power generation efficiency (%) for each temperature of the heating plate 21. The points indicated by "-" in Table 5 indicate that the power generation output (W) and power generation efficiency (%) for each temperature of the heating plate 21 have not been measured.

Further, in Test Examples 2 to 5, the performance of the thermoelectric module sample 100 different from that of Test Example 1 was evaluated under the same conditions as in Test Example 1. The details of the thermoelectric module sample 100 whose performance was evaluated in Test Examples 2 to 5 are 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 has elements 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 elements are 3.5 mm × 3.5 mm. It has a length of 5 mm and is joined to a silver electrode using a silver paste. The logarithm of the elements is 14 pairs, and the number of pairs of elements is 2 for both the p and n types. Alumina having a thickness of 32 mm × 34 mm and a thickness of 0.8 mm is used as a substrate on the high temperature surface 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 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. Further, when a heat radiation 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating members 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and the entire cooling plate 31 to be covered from the heating plate 21. Prevented heating due to heat dissipation. A 3 kg weight was hung on the handle lever and weighted by the heating plate 21 at the top. While circulating the cooling water temperature set at 20 ° C to the cooling plate 31 at a water volume 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, the heating of the heating plate 21 was stopped and left for 3 hours. As a result, the temperature of the heating plate became 100 ° C. or lower. After that, 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 cycle test of the module.

<Test Example 7>
The thermoelectric module sample 100 whose performance is evaluated in Test Example 7 has elements 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 elements are 3.5 mm × 3.5 mm. It has a length of 3.5 mm and is bonded to a silver electrode using a silver paste. The logarithm of the elements is 10 pairs, and the number of pairs of elements is 2 for p-type and 1 for n-type. Alumina having a thickness of 32 mm × 36 mm and a thickness of 0.8 mm is used as a substrate on the high temperature surface side. The dimensions of the thermoelectric module sample 100 excluding the substrate are 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 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a heat radiation gel sheet (elastic heat transfer sheet 9; trade name: Lambda gel) with a thickness of 0.5 mm 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating member 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module sample 100 are stacked to cover the periphery of the thermoelectric module sample 100 and cover the entire cooling plate 31 to cover the heating plate. The heating due to the heat radiation from 21 was prevented. A 3 kg weight was hung on the handle lever and weighted by the heating plate 21 at the top. While circulating the cooling water temperature set to 20 ° C. on the cooling plate 31 at a water volume of 5 liters / minute, the heating plate temperature was raised from room temperature to 1000 ° C. in 3 hours, and the external load resistance was scanned to measure the maximum output. .. After the measurement, the heating of the heating plate 21 was stopped and left for 4 hours. As a result, the temperature of the heating plate became 100 ° C. or lower. Then, heating was started again, the temperature was raised 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 measurement was performed every time up to the 20th time, and after 3 to 5 temperature cycles.

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

<Test Examples 8 to 25>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 8 has elements 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 elements are 3.5 mm × 3.5 mm. It has a length of 5 mm and is joined to a silver electrode using a silver paste. The logarithm of the elements is 34 pairs, and the number of pairs of elements is two for both the p and n types. Alumina of 45 mm x 60 mm and 0.8 mm thickness is used as the substrate on the high temperature surface side. The length of 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 surface side of the module. For electrical insulation, a 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a heat radiation gel sheet (elastic heat transfer sheet 9; trade name: Lambda gel) with a thickness of 0.5 mm 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating members 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and the entire cooling plate 31 to be covered from the heating plate 21. Prevented heating due to heat dissipation. The heating plate temperature was set in the range of 200 to 900 ° C. in every 100 ° C., and a weight of 5 kg was suspended from the handle lever and weighted. The cooling water temperature set to 20 ° C. was circulated through the cooling plate 31 at a water volume of 5 liters / minute. After the temperature of the heating plate 21 reached the set value, the maximum output of the thermoelectric module was measured by scanning the external load resistance. Furthermore, the power generation efficiency was also measured using this maximum output.

Further, in Test Examples 9 to 25, the performance evaluation of the thermoelectric module sample 100 different from that in Test Example 8 was performed under the same conditions as in Test Example 8. In some test examples, the upper and lower limits of the set temperature of the heating plate 21 were set to be different from those of the 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 (%) for each temperature of the heating plate 21. In addition, the part indicated by "-" in Table 9 indicates that the power generation output (W) and the power generation efficiency (%) for each temperature of the heating plate 21 have not been measured.

<Test Examples 26 and 27>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 26 has elements 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 elements are 3.5 mm × 3.5 mm. It has a length of 5 mm and is joined to a silver electrode using a silver paste. The logarithm of the elements is 34 pairs, and the number of pairs of elements is two for both the p and n types. Alumina having a thickness of 32 mm × 34 mm and a thickness of 0.8 mm is used as a substrate on the high temperature surface 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 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a heat radiation gel sheet (elastic heat transfer sheet 9; trade name: Lambda gel) with a thickness of 0.5 mm 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating members 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and the entire cooling plate 31 to be covered from the heating plate 21. Prevented heating due to heat dissipation. A 5 kg weight was hung on the handle lever and weighted by the heating plate 21 at the top. While circulating the cooling water temperature set at 20 ° C to the cooling plate 31 at a water volume 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, the heating of the heating plate 21 was stopped and left for 3 hours. As a result, the temperature of the heating plate became 100 ° C. or lower. After that, 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 cycle test of the module.

In Test Example 27, a sample having the same configuration as the thermoelectric module sample 100 according to Test Example 26 was separately prepared, and the sample was subjected to the same conditions as in Test Example 26. Table 10 shows the 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 exactly the same composition and shape, there is a difference in the deterioration phenomenon. This is because the cause of deterioration is different, and it was found that in Test Example 26, 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 has elements of p-type MnSi _1.7 and n-type Mn ₃ Si ₄ Al ₂ , and the cross-sectional dimensions of the elements are 3.5 mm × 3.5 mm and the length is 7.5 mm. It is joined to the silver electrode using silver paste. The logarithm of the elements is 7, and the number of pairs of elements is 2 for both the p and n types. Alumina having a thickness of 30 mm × 20 mm and a thickness of 0.8 mm is used as a substrate on the high temperature surface 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 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a heat radiation gel sheet (elastic heat transfer sheet 9; trade name: Lambda gel) with a thickness of 0.5 mm 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating members 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and the entire cooling plate 31 to be covered from the heating plate 21. Prevented heating due to heat dissipation. A 3 kg weight was hung on the handle lever and weighted by the heating plate 21 at the top. While circulating the cooling water temperature set at 20 ° C to the cooling plate 31 at a water volume of 5 liters / minute, the heating plate temperature is raised from room temperature to 500 ° C in 2 hours, and the external load resistance is scanned for maximum output and power generation efficiency. I measured it. Even after the measurement, the maximum output and power generation efficiency were measured every 24 hours for 43 days while maintaining the heating plate temperature at 500 ° C. Table 12 shows the details of the thermoelectric module of Test Example 28, and Table 13 shows the results of the long-term continuous heating test of Test Example 28.

<Test Example 29>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 29 has elements of p-type MnSi _1.7 and n-type Mn _2.7 Cr _0.3 Si ₄ Al ₂ , and the cross-sectional dimensions of the elements are 3.5 mm × 3.5 mm and the length is 7. It is 5.5 mm and is joined to the silver electrode using a silver paste. The logarithm of the elements is 7, and the number of pairs of elements is 2 for both the p and n types. Alumina having a thickness of 30 mm × 20 mm and a thickness of 0.8 mm is used as a substrate on the high temperature surface 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 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a heat radiation gel sheet (elastic heat transfer sheet 9; trade name: Lambda gel) with a thickness of 0.5 mm 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating members 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and the entire cooling plate 31 to be covered from the heating plate 21. Prevented heating due to heat dissipation. A 3 kg weight was hung on the handle lever and weighted by the heating plate 21 at the top. While circulating the cooling water temperature set at 20 ° C to the cooling plate 31 at a water volume of 5 liters / minute, the heating plate temperature is raised from room temperature to 500 ° C in 2 hours, and the generated current of 1 A is constant by the constant current DC power supply. The external load resistance was controlled so as to be maintained at, and the voltage generated by the thermoelectric module sample 100 was measured by the DC four-terminal method. The power generation output was calculated from this voltage value and current value. Even after the measurement, the power generation output when 1 A was generated was measured every 50 hours for 750 hours while maintaining 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 long-term constant current continuous test results of Test Example 29.

<Test Example 30>
The thermoelectric module sample 100 whose performance was evaluated in Test Example 30 has elements of p-type MnSi _1.7 and n-type Mn _2.7 Cr _0.3 Si ₄ Al ₂ , and the cross-sectional dimensions of the elements are 3.5 mm × 3.5 mm and the length is 7. It is 5.5 mm and is joined to the silver electrode using a silver paste. The logarithm of the elements is 7, and the number of pairs of elements is 2 for both the p and n types. Alumina having a thickness of 30 mm × 20 mm and a thickness of 0.8 mm is used as a substrate on the high temperature surface 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 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a heat radiation gel sheet (elastic heat transfer sheet 9; trade name: Lambda gel) with a thickness of 0.5 mm 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating members 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and the entire cooling plate 31 to be covered from the heating plate 21. Prevented heating due to heat dissipation. A 3 kg weight was hung on the handle lever and weighted by the heating plate 21 at the top. While circulating the cooling water temperature set at 20 ° C to the cooling plate 31 at a water volume of 5 liters / minute, the heating plate temperature is raised from room temperature to 500 ° C in 2 hours, and the generated voltage of 1 V is constant by the constant current DC power supply. The external load resistance was controlled so that the temperature was maintained at, 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. Even after the measurement, the power generation output when 1 V was generated was measured every 50 hours for 900 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 long-term constant voltage continuous test results of Test Example 30.

<Test Example 31>
In the thermoelectric module sample 100 whose performance was evaluated in Test Example 31, the elements of the thermoelectric module were 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 elements were 3.5 mm × 3. It is 5.5 mm long and 5 mm long and is bonded to a silver electrode using a silver paste. The logarithm of the elements is 64 pairs, and the number of pairs of elements is two for both the p and n types. Alumina having a size of 64.5 mm × 64.5 mm and a thickness of 0.8 mm is used as a substrate on the high temperature surface 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 surface side of the module. For electrical insulation, a 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a heat radiation gel sheet (elastic heat transfer sheet 9; trade name: Lambda gel) with a thickness of 0.5 mm 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating members 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and the entire cooling plate 31 to be covered from the heating plate 21. Prevented heating due to heat dissipation. The heating plate temperature was set in the range of 200 to 900 ° C. in every 100 ° C., and a load of 20 kg was applied from above with a pneumatic compressor. The cooling water temperature set to 20 ° C. is circulated to the cooling plate 31 at a water volume of 8 liters / minute. After the temperature of the heating plate 21 reached the set value, the maximum output of the thermoelectric module was measured by scanning the external load resistance. 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 has elements of p-type MnSi _1.7 and n-type Mn _2.7 Cr _0.3 Si ₄ Al ₂ , and the cross-sectional dimensions of the elements are 3.5 mm × 3.5 mm and the length is 7. It is 5.5 mm and is joined to the silver electrode using a silver paste. The logarithm of the elements is 14 pairs, and the number of pairs of elements is 2 for both the p and n types. Alumina having a thickness of 30 mm × 35 mm and a thickness of 0.8 mm is used as a substrate on the high temperature surface 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 located on the high temperature surface side of the module. For electrical insulation, a 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a heat radiation gel sheet (elastic heat transfer sheet 9; trade name: Lambda gel) with a thickness of 0.5 mm 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating members 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and the entire cooling plate 31 to be covered from the heating plate 21. Prevented heating due to heat dissipation. The temperature of the hot plate was set in the range of 100 to 600 ° C. in every 100 ° C., and a pneumatic compressor was applied from the top of a 10 kg load. The cooling water temperature set to 20 ° C. is circulated to the cooling plate 31 at a water volume of 8 liters / minute. After the temperature of the heating plate 21 reached the set value, the maximum output of the thermoelectric module was measured by scanning the external load resistance. Furthermore, the power generation efficiency was also measured using this maximum output.

Table 18 shows the 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 has elements of p-type Ca _2.7 Bi _0.3 Co ₄ O ₉ and n-type Ca Mn _0.98 Mo _0.02 O ₃ , and the cross-sectional dimensions of the elements are 3.5 mm × 3.5 mm. It has a length of 7 mm and is joined to a silver electrode using a silver paste. The logarithm of the elements is 64 pairs, and the number of pairs of elements is two for both the p and n types. Alumina having a size of 64.5 mm × 64.5 mm and a thickness of 0.8 mm is used as a substrate on the high temperature surface 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 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 0.07 mm thick polyimide (Kapton (registered trademark)) tape was wound around the lead wire 4, and further adhered to the cooling plate 31 with a polyimide (Kapton (registered trademark)) tape. In addition, a heat radiation gel sheet (elastic heat transfer sheet 9; trade name: Lambda gel) with a thickness of 0.5 mm 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 transfer gel sheet. Further, several glass wool heat insulating materials (heat insulating members 7) hollowed out with the same dimensions as the high temperature surface of the thermoelectric module are stacked to cover the periphery of the thermoelectric module sample 100 and the entire cooling plate 31 to be covered from the heating plate 21. Prevented heating due to heat dissipation. It was applied from the top with a weight of 10 kg using a pneumatic compressor. While circulating the cooling water temperature set at 20 ° C to the cooling plate 31 at a water volume of 8 liters / minute, the heating plate temperature is raised from room temperature to 500 ° C in 2 hours, and the generated current of 1 A is constant by the constant current DC power supply. The external load resistance was controlled so that the temperature was maintained at, 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. Even after the measurement, the power generation output when 1 A was generated was measured every 50 hours for 750 hours while maintaining the heating plate temperature at 500 ° C. Table 20 shows the details of the thermoelectric module sample 100 of Test Example 33. Table 21 shows the results of a long-term constant current continuous test of Test Example 33.

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

1 Thermoelectric module power generation evaluation device 2 Heating unit 21 Heating plate 22 Heating plate body 23 Cartridge heater 25 Temperature sensor 3 Cooling unit 32 Flow path 31 Cooling plate 33 Water inlet pipe 34 Outflow pipe 37 Cooling water circulation device 38, 39 Temperature sensor 4 Lead wire 5 Control calculation unit 6 Weighted unit 7 Insulation member 9 Heat transfer sheet 100 Thermoelectric module sample

Claims (10)

A thermoelectric module power generation evaluation device that evaluates the power generation performance of a thermoelectric module.
A heating unit having a dimension equal to or larger than the dimension of the high temperature surface of the thermoelectric module and having a heating surface arranged in contact with the high temperature surface.
A cooling unit having a dimension equal to or larger 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.
It is equipped with a power outlet line connected to the thermoelectric module.
A thermoelectric module power generation evaluation device, characterized in that at least one part of the power take-out line is arranged in close contact with the cooling surface of the cooling part. The thermoelectric module power generation evaluation device according to claim 1, wherein the power take-out line is a sheet-shaped wiring having a predetermined width. The thermoelectric module power generation evaluation device according to claim 1 or 2, wherein the cooling surface of the cooling unit has an area larger than that of 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 device 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 device according to any one of claims 1 to 4, further comprising an elastic heat transfer sheet arranged between the cooling surface of the cooling unit and the low temperature surface of the thermoelectric module. The thermoelectric module power generation evaluation device according to claim 5, wherein the heat transfer sheet further has electrical insulation. The heating unit includes a heating plate body made of an oxidation-resistant material having a coefficient of thermal expansion of 15 × ^10-6 / K or less and a thermal conductivity of 10 W / mK or more, and the heating surface is heated. The thermoelectric module power generation evaluation device according to any one of claims 1 to 6, wherein the plate body has one surface. The thermoelectric module power generation evaluation device according to claim 7, wherein the heating plate main body is made of stainless steel, a nickel-based 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 so as to be biased toward the thermoelectric module side with respect to the thickness direction of the heating plate main body. The thermoelectric module power generation evaluation device according to claim 7 or 8, wherein the thermoelectric module power generation evaluation device is characterized. The thermoelectric module power generation evaluation device according to any one of claims 1 to 9, further comprising a heat insulating member that covers the periphery of the thermoelectric module and covers the cooling surface of the cooling unit.

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