WO2005117154A1 - Module thermoélectrique à couche mince de type intégré haute densité et système de production d’énergie hybride - Google Patents

Module thermoélectrique à couche mince de type intégré haute densité et système de production d’énergie hybride Download PDF

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WO2005117154A1
WO2005117154A1 PCT/JP2005/009864 JP2005009864W WO2005117154A1 WO 2005117154 A1 WO2005117154 A1 WO 2005117154A1 JP 2005009864 W JP2005009864 W JP 2005009864W WO 2005117154 A1 WO2005117154 A1 WO 2005117154A1
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layer
thermoelectric
thin
semiconductor element
thermoelectric semiconductor
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Japanese (ja)
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WO2005117154B1 (fr
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Kazukiyo Yamada
Kiyoshi Ineizumi
Naohisa Taguchi
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device

Definitions

  • thermoelectric module High-density integrated thin-layer thermoelectric module and hybrid power generation system
  • the present invention relates to a thin-layer thermoelectric module that uses thermoelectric effects in a range from a relatively low temperature (normal temperature range) to a high temperature close to about 800 ° C, and a thin-film thermoelectric module using such a module. ) Regarding power generation system.
  • the thermoelectric effect is a general term for the Seebeck effect, the Pelch effect, or the Thomson effect of thermoelectric semiconductors. Therefore, the present invention belongs to the technical field of thermoelectric semiconductors or power generation devices or cooling Z heating devices using the same.
  • thermoelectric device has, as a basic type, a “ ⁇ structure” including a P-type thermoelectric semiconductor element, an N-type thermoelectric semiconductor element, and an electrode for joining them.
  • a thermoelectric semiconductor module having a “ ⁇ structure” generates a thermoelectric power by the Seebeck effect when a temperature difference ( ⁇ ) is taken between the electrodes at both ends of the thermoelectric semiconductor module, and generates a Peltier effect when a current flows through the thermoelectric semiconductor element. The electrons move, creating an endothermic side and a radiating side.
  • the " ⁇ structure” is a type II thermoelectric semiconductor element, a type II thermoelectric semiconductor element, and a plurality of electrodes connected alternately in multiple pairs and electrically in series. And are formed in parallel.
  • thermal energy (temperature difference ⁇ ⁇ ) is supplied to the low-temperature side and the high-temperature side, a power generation device is obtained by the Seebeck effect as shown in Fig. 13 (a). If power is supplied to an electrically serial circuit, the circuit becomes a cooling device or a heating device by the Peltier effect as shown in FIG. 13 (b).
  • thermoelectric element In the Seebeck effect model of a thermoelectric element, when a temperature difference is given between two points in the element, many carriers diffuse to the low-temperature side, and a directional electric field is generated from the high-temperature side to the low-temperature side as shown in FIG. As the carrier moves, the balance is maintained and a potential difference is created across the element.
  • a load is connected between the thermoelectric semiconductors, a current flows to the load, and a potential difference is generated between both ends of the load.
  • thermoelectric semiconductor element the heat that enters the high-temperature side connection point escapes through the lead wire, and by connecting the lead wire to the low-temperature side, the thermal start-up power of the ⁇ -type thermoelectric semiconductor element can be reduced by the multiple carriers of the ⁇ -type thermoelectric semiconductor element.
  • ⁇ -type and ⁇ -type thermoelectric semiconductors have a ⁇ -type structure With such a configuration, it is possible to connect them electrically in series and thermally in parallel.
  • thermoelectric device a rigid structure.
  • thermoelectric semiconductor elements 127 pairs are arranged as a ⁇ structure unit between 4 cm square plates.
  • thermoelectric device is an ingot or a sintered thermoelectric element module in which chips sliced into a predetermined size are aligned on predetermined electrodes, and integrated through a soldering process.
  • the rigid structure of the thermoelectric module was inferior in mass productivity, and its life was varied due to thermal strain, which caused problems in reliability, and the performance improvement was sluggish.
  • thermoelectric element has to be improved only by increasing the ⁇ value, which is a characteristic factor of a thermoelectric material that becomes less powerful.
  • ⁇ value is proportional to electrical conductivity and inversely proportional to thermal conductivity.
  • a material having a high electric conductivity has a property having a high heat conductivity. This makes it difficult to set the ⁇ value to the desired value, and no significant improvement has been seen to date.
  • Patent Document 1 relates to a thermoelectric material having a high ⁇ value.
  • Patent Document 2 relates to a highly integrated thermoelectric array power generation module.
  • Patent Document 3 is a technology for applying a hot water tank and a Peltier II heating element unit to a solar cell.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2001-223392
  • Patent Document 2 JP-A-2002-171775
  • Patent Document 3 JP-A-10-295953
  • An object of the present invention is to provide an integrated thin-layer thermoelectric module that can be used from a relatively low temperature range to a high temperature range close to 1000 ° C.
  • durability which is currently a difficult problem, and the life of strain rupture due to thermal expansion
  • Another object is to solve the problem of variation. More specifically, to improve the efficiency of the thermoelectric effect while energizing the characteristics of the thermoelectric semiconductor, first, the total power generation should be improved by integration, and second, the thin-layer thermoelectric semiconductor It is necessary to increase the current density by increasing the contact area with the electrodes, and thirdly, to provide a structure that prevents heat dissipation and loss of heat flow.
  • thermoelectric module In order to maximize the power generation efficiency of the element size (length and width) of the ⁇ structure, it is conceivable to set the internal resistance of the module low. If the internal resistance of the module is set to a low value, it seems that the amount of power generation appears to increase, but at the same time, losses due to Joule heat and heat conduction must be considered. Joule heat is generated when an electric current is applied to a substance having electrical resistance, and heat conduction is generated through a thermoelectric element when there is a temperature gradient in the thermoelectric element. Seebeck effect, Peltier effect and Thomson effect are reversible phenomena Force Joule heat and heat conduction are irreversible phenomena. The heat balance of a thin-layer thermoelectric module is a combined effect of reversible and irreversible phenomena, and the irreversible phenomena are likely to be factors that reduce the Seebeck effect and Peltier effect.
  • thermoelectric semiconductors In a circuit in which ⁇ -type and ⁇ -type thermoelectric semiconductors are joined as a pair, the electric resistance is low and the thermal conductivity is high.
  • ⁇ ⁇ When forming a ⁇ structure through a dissimilar metal (copper electrode), On the other hand, the direction of movement of a large number of carriers generated in the ⁇ -type and ⁇ -type thermoelectric semiconductors, which are equal to the junction of the thermoelectric semiconductor element, is the same. This means that when the ⁇ structure is formed to be electrically in series and thermally in parallel, the transfer of heat related to Joule heat and heat conduction is minimized, and there is no loss due to heat dissipation. Means This is a necessary condition for increasing the amount of power generation in a large number of integrated vehicles.
  • the main problem of the present invention is to improve the total power generation by integrating a large number of thin-layer thermoelectric semiconductor units based on the ⁇ structure, and to solve the problem of thermal distortion and its variation. It is to provide a means to minimize.
  • a second main problem of the present invention is to propose specific means for increasing the contact area between a thermoelectric semiconductor element and an electrode. Therefore, it is an object of the present invention to provide an improved electrode configuration and a thermoelectric semiconductor device configuration, and a contact relationship with the electrode.
  • a third object of the present invention is to provide a shape and structure of a ⁇ -structure with less loss due to heat dissipation and heat flow. It is to propose a structure. Means for solving the problem
  • thermoelectric element having a ⁇ structure which is the main problem, as a thin-layer base that is not a conventional rigid structure (a “thin layer” includes a so-called thin film or thick film).
  • a thin layer includes a so-called thin film or thick film.
  • It achieves the flexibility, mass production and low cost that are characteristic of thin layers. That is, a large number of ⁇ -type and ⁇ -type thermoelectric semiconductor element pairs and electrodes for joining them are formed in one or more rows as a thin layer pattern on a flexible heat insulating and electrically insulating sheet. The sheet is folded in a zigzag or spirally wound to form a large number of ⁇ -structures in a three-dimensional structure, forming a high-density integrated thin-layer thermoelectric module.
  • the form of the electrode is widened from the end face of the thermoelectric semiconductor element to the side face of the element.
  • the electrode area is substantially increased, and a free carrier corresponding to the electrode area is formed by the Seebeck effect, thereby generating a thermoelectromotive force.
  • the substantial contact area between the thermoelectric semiconductor element and the electrode can be further increased.
  • the high-density integrated thin-layer thermoelectric module of the present invention has a structure having a dot hole at an arbitrary position of the thermoelectric semiconductor element, so that the contact area between the thermoelectric semiconductor element unit and the electrode is positively increased. In addition, it is desirable that the resistance of the thermoelectric semiconductor element unit can be adjusted.
  • thermoelectric module In a high-density integrated thin-layer thermoelectric module, a gap is created between adjacent thermoelectric element units even if the thermoelectric element units are to be brought into close contact with each other.
  • the air gap formed between the adjacent thermoelectric element units is positively used as a layer of a thermal insulator, and such an air layer is interposed. This provided thermal insulation between the internal units and solved the problem of heat dissipation and heat flow.
  • the layer of the thermal insulator includes vacuum, air, and other materials having low thermal conductivity.
  • thermoelectric semiconductor element is made non-planar at the joint surface between the thermoelectric semiconductor element and the thin-layer electrode.
  • the contact area can be substantially increased and the current density can be increased.
  • the resistance value of the thermoelectric semiconductor element can be arbitrarily adjusted by changing a non-planar shape such as a dot hole or a slit in a manufacturing process.
  • thermoelectric semiconductor element has a constricted structure.
  • thermoelectric module of the present invention a part or all of the surroundings can be sealed with a sheet-like film to also serve as moisture proof and dust proof.
  • thermoelectric module pattern By forming a thermoelectric module pattern on a flexible sheet and then forming a three-dimensional structure, it is possible to perform various three-dimensional processing based on a thermoelectric semiconductor element module having both flexibility and adaptability. Thus, a thin-layer thermoelectric module in which thermoelectric semiconductor elements are integrated at a high density can be configured.
  • thermoelectric module of the present invention which is integrated by the spiral structure and the zigzag structure, is because a large number of thermoelectric semiconductor units are efficiently assembled and integrated, and the efficiency per unit area is improved. And a small device provides high Seebeck effect and Peltier effect.
  • thermoelectric module of the present invention An even greater effect of the high-density integrated thin-layer thermoelectric module of the present invention is that the material of the base sheet is flexible, and a thermoelectric semiconductor or a thin-layer electrode is formed on the spiral structure. As a result of accumulating due to the zigzag and zigzag structures, it is possible to provide flexibility even in a three-dimensional structure. Therefore, the problems of durability and strain destruction due to thermal expansion that the rigid structure has were solved.
  • thermoelectric semiconductor element and the electrode are formed into thin layers to achieve a flexible structure
  • the size, shape, and number of the module are appropriately selected. It can be well adapted for use in various devices. Use Even if the device has various shapes and shapes such as irregularities, a large number and various sizes of modules can be prepared and arranged in combination so as to match the device to be used.
  • the high-density integrated thin-layer thermoelectric element utilizes patterning technology in its manufacture, and achieves low cost by mass production.
  • FIG. 1 Embodiment 1 in which a spiral is three-dimensionally processed (a) A single-sided electrode pattern (b) A thermoelectric semiconductor element and a single-sided electrode pattern
  • thermoelectric semiconductor elements are joined by a double-sided electrode.
  • (d) is a schematic diagram in which a spiral is drawn.
  • (e) is a diagram in which a spiral is processed.
  • Example 2 Example of the present invention in which three-dimensional processing is performed in a single-row zigzag pattern (a) is a single-sided electrode pattern (b) is a thermoelectric semiconductor element and a single-sided electrode pattern
  • thermoelectric semiconductor elements are joined by double-sided electrodes.
  • (d) is a cross-sectional view.
  • FIG. 3 Embodiment 3 Embodiment of the present invention in which three-dimensional processing is performed into a plurality of rows of zigzags.
  • FIG. 3c Example 3 in which a zigzag sheet pattern, its cross section, and a zigzag processed portion are enlarged.
  • FIG. 4 (Example 4) A cross-sectional view parallel to the thickness of the thin layer of the thin-layer thermoelectric semiconductor element of the embodiment in which the contact area between the thin-layer thermoelectric semiconductor element and the thin-layer electrode is increased.
  • thermoelectric semiconductor element is sandwiched or surrounded by electrodes (b), (c): An example in which the surface of the thermoelectric semiconductor element is non-planar; (d): An example in which the thermoelectric semiconductor element is provided with a dot hole structure ( e) Example in which a slit is provided in the thermoelectric semiconductor element
  • FIG. 5 shows a method of mass-producing an embodiment for performing spiral processing.
  • FIG. 6 (Embodiment 6) Methods (a) and (b) of mass-producing an embodiment of zigzag processing are shown.
  • FIG. 7 An embodiment in which the resistance value of a thermoelectric semiconductor element is adjusted to thermally shut off the high-temperature side and the low-temperature side.
  • Example (b) is an example in which the thermoelectric semiconductor element has a constricted shape.
  • thermoelectric semiconductor element is formed into a constricted shape in the embodiment shown in FIG.
  • thermoelectric semiconductor element is formed into a constricted shape by applying to the embodiments 2 and 3 in which the zigzag three-dimensional processing is performed in FIGS.
  • FIG. 10 (Embodiment 10) An embodiment of the present invention in which a solar cell power generation device and a thin layer thermoelectric module are combined (a) is a schematic diagram of a solar cell power generation device (b) is a schematic diagram of a thin layer thermoelectric module (c) Is an embodiment of the present invention in which a solar cell power generation device and a thin-layer thermoelectric module are combined.
  • FIG. 11 A schematic rear view (a) and a cross-sectional view (b) of a combined power generation system of the present invention in which a solar cell power generation device and a thin-layer thermoelectric module are combined.
  • FIG. 12 shows an embodiment of the present invention in which thin-layer thermoelectric modules having different temperature ranges are combined in multiple stages (a) and a schematic diagram of temperature characteristics of a thermoelectric semiconductor element (b)
  • thermoelectric device (b) Principle diagram of heating / cooling device with ⁇ structure (a) Principle diagram of power generation by ⁇ structure
  • FIG. 14 is an explanatory view of electron transfer in a thermoelectric semiconductor element of an existing thermoelectric device
  • thermoelectric semiconductor device 1 Type I or type II thermoelectric semiconductor device
  • a thin layer of a P-type thermoelectric semiconductor element and a thin layer of an N-type thermoelectric semiconductor element are alternately arranged in a longitudinal direction on a flexible vertically elongated thin sheet having thermal insulation and electrical insulation.
  • a thin-layer electrode for joining thermoelectric semiconductor elements from P-type to N-type is provided on the edge, and a thin-layer electrode for joining thermoelectric semiconductor elements from N-type to P-type is provided on the opposite edge of the sheet.
  • a ⁇ -structured thermoelectric unit is formed on a sheet, and the sheet is rolled into a snoral (swirl) to form a columnar or prismatic solid.
  • High-density integrated thin-layer thermoelectric module characterized by a high-temperature side.
  • a thin layer of a ⁇ ⁇ -type thermoelectric semiconductor element, a ⁇ -type thin layer of a thermoelectric semiconductor element, and an electrode for joining each thermoelectric semiconductor element are vertically arranged on a thin sheet that is thermally and electrically insulative and flexible.
  • Each thin layer is arranged in one or more rows, and a large number of ⁇ -structured thermoelectric units are cascaded in a three-dimensional manner by bending the approximate center of the electrode in a zigzag (bellows, wavy) along a horizontal line.
  • a high-density integrated thin-layer thermoelectric module characterized in that two surfaces formed and assembled with three-dimensional lateral bending lines are a low-temperature side and a high-temperature side, respectively.
  • the electrode sandwiches or surrounds the thermoelectric semiconductor element from the end face to the side face of the thermoelectric semiconductor element, and / or has a non-contact surface with the electrode of the thermoelectric semiconductor element.
  • the spiral or zigzag-type high-density integrated thin-layer thermoelectric module wherein the current density is increased by making the contact area between the electrode and the thermoelectric semiconductor element wider by making it flat.
  • the thin layer of each thermoelectric semiconductor element has a constricted shape, a slit, a Z or a dot hole at an intermediate portion between the low-temperature side and the high-temperature side, and a part or all of the surroundings is heat-insulated as necessary.
  • the above-described high-density integrated thin-layer thermoelectric module which is sealed with an electrically insulating and moisture-proof material (including air or vacuum) to reduce heat transmission loss.
  • FIG. 1 shows Example 1 of the present invention in which a high-density integrated thin-layer thermoelectric module is spirally three-dimensionally processed.
  • 1 is a P-type and N-type thermoelectric semiconductor element
  • 2 is a thin-layer electrode
  • 3 is a thermally insulating and electrically insulating flexible film sheet, which is vertically long in this example.
  • Numeral 4 denotes a plate-shaped heat radiation section or heat reception section 4, which may be provided with a thin electric insulating layer.
  • the thin-layer electrode 2 forms a pattern on the film sheet 3 by printing, vapor deposition, or the like.
  • a thin layer of a P-type thermoelectric semiconductor element and a thin layer of an N-type thermoelectric semiconductor element 2 is placed on a vertically elongated thin sheet 3 that is thermally and electrically insulative. It is formed by printing or vapor deposition as a pattern that is alternately continuous.
  • the electrodes 2 are also patterned on the left and right edges of the sheet by printing, vapor deposition, etc., as shown in bold type in FIG.
  • the electrode pattern on one edge of the sheet joins the thermoelectric semiconductor elements 2 from the P-type to the N-type, and the electrode pattern on the opposite edge of the sheet joins the thermoelectric semiconductor elements 2 from the N-type to the P-type.
  • Fig. 1 (c) a large number of ⁇ -structure thermoelectric units are continuously formed on the plane of the vertically long sheet 3.
  • Fig. 1 (d) is a schematic diagram in which (c) is spirally wound, and (e) is a side view of (d), which is smaller than the above figures.
  • Fig. 1 (f) shows the sheet rolled into a round spiral and curled into a cylindrical shape. It may be a solid prism (square, hexagon, etc.) joined by cylinders.
  • This three-dimensional structure is a high-density integrated thin-layer thermoelectric module, and the upper and lower surfaces of the figure where the electrodes are gathered are the low-temperature side and the high-temperature side, respectively.
  • the low-temperature side and high-temperature side of the high-density integrated thin-layer thermoelectric module are sandwiched between a pair of heat transfer plates 4 (radiator, heat receiver), and the heat transfer plates 4 are sandwiched as shown in FIG. And install it on the equipment to be used and operate it as a power generator, cooling or heating device.
  • the module transmits and receives thermal energy via the plate unit 4. With such a pattern, a thermoelectric element having hundreds to thousands of pairs can be obtained.
  • a power generator Is electrically connected to the device that uses the power that is stored in the battery from the electrode that also draws both ends.
  • thermoelectric semiconductor element 2 used in Example 1 is BiTePb (low temperature to 200 ° C.) / Iron silicide (300 to 700 ° C.).
  • the sheet 3 serving as a base has electrical insulation, heat insulation, and moisture resistance, and includes polyimide resin, aramide resin, fluorine resin, and sheet ceramic.
  • the electrode is preferably made of a material having high conductivity such as copper. The same material can be used in the following examples.
  • FIG. 2 shows Example 2 of the present invention, in which a high-density integrated thin-layer thermoelectric module is formed by processing a vertically long sheet 3 in a zigzag (bellows, wavy) three-dimensionally. Is the same as in Example 1, but the film sheet 3 is preferably provided with a number of parts 6 and 7 which can be folded in the horizontal direction as required.
  • Example 2 as shown in FIG. 2 (b), a P-type thermoelectric semiconductor element, an electrode, an N-type thermoelectric semiconductor element, The thin layers are arranged in a line as in. Further, the electrodes are joined from the P-type thermoelectric semiconductor element on both sides to the N-type thermoelectric semiconductor element or from the N-type thermoelectric semiconductor element to the P-type thermoelectric semiconductor element.
  • thermoelectric units are formed as a three-dimensional structure by bending the center of the electrode in a zigzag manner along the dashed lines 6 and 7 in the horizontal direction.
  • bend at the arrow the figure is exaggerated in thickness, but the electrodes are thin layers.
  • the bent portions 6 and 7 of the alternate long and short dash line gather on the upper surface and the opposite lower surface, respectively, to become the low-temperature side and the high-temperature side, respectively.
  • the heat transfer plate 4 is mounted as needed and mounted on the equipment to be used.
  • thermoelectric semiconductor a force vj and a hole are drilled at equal intervals between the electrodes on the film sheet, and the electrodes are deposited from the front and back of the sheet to form a thermoelectric semiconductor.
  • the element may be fixed so as to sandwich the element.
  • a P-type thermoelectric semiconductor element similarly to the embodiment of Fig. 2, thin layers of a P-type thermoelectric semiconductor element, an electrode, an N-type thermoelectric semiconductor element, and an electrode are arranged in a row to form a three-dimensional zigzag.
  • the row is a plurality of rows, and electrodes for turning the current direction at both ends of the row are provided. I am.
  • the base sheet shall be spread in two dimensions such as a square.
  • the electrodes are used to join the P-type thermoelectric semiconductor elements on both sides of the same row to the N-type thermoelectric semiconductor elements or from the N-type thermoelectric semiconductor elements to the P-type thermoelectric semiconductor elements. It is the same.
  • the high-temperature side and low-temperature side are positioned above the dashed-dotted lines 6 and 7 across the row. It must be formed alternately (up and down) side by side. Therefore, in the pattern of FIG. 3A, the current is alternately turned on the left end and the right end. At the beginning and end of each row, a pattern is deposited so that it can be connected to the next row. When such a pattern is formed and bent in a zigzag (bellows or wavy shape) along the horizontal broken line in FIG.
  • thermoelectric units a large number of ⁇ -structure thermoelectric units are formed as a three-dimensional structure vertically and horizontally, and the low-temperature side is formed, for example.
  • the high temperature side can be aligned with the upper surface where the bent curves are gathered, and the lower surface where the opposite bent lines are gathered.
  • the module shown in FIG. 3 is also provided with the heat transfer plate 4 and sandwiched from both sides, and is set in the insulating casing with both ends of the electrode side being slightly spaced. Then, lead wires are drawn out from the electrodes at both ends to form a high-density integrated thin-layer thermoelectric module.
  • Figure 3c shows the sheet pattern before zig-zag shading (left in the figure), its cross section (lower left in the figure), and the dimensions (mm) of the enlarged zig-zag processed part (right in the figure). It is described.
  • Embodiment 4 of the present invention in Fig. 4 further enhances the effect of accumulation. That is, the embodiment of the present invention, in which the current density is increased by substantially increasing the contact area between the electrode and the thermoelectric semiconductor element, is sliced along the thickness of the thin layer of the thermoelectric semiconductor element. I'm drawing. In the embodiment of FIG. 4 (a), when joining the thin-layer electrodes to the thermoelectric semiconductor element, the end face force of the thermoelectric semiconductor element is also applied to the side surfaces by the electrodes that are simply joined at both ends so that the thermoelectric semiconductor element is sandwiched or surrounded. To
  • Example 4 of FIGS. 4 (b), (c), (d) and (e) when the thin-layer electrode is joined to the thermoelectric semiconductor element, the surface of the portion in contact with the electrode of the thermoelectric semiconductor element is made non-planar. Then, the current density was increased by substantially increasing the contact area between the thermoelectric semiconductor element and the electrode. That is, as shown in Figs. 4 (b), (c), and (e), the shape of the junction of the thermoelectric The electrodes have a shape or a structure with holes (dot holes) as shown in (d), and the electrodes are joined in conformity with the non-planar surfaces.
  • the embodiments of (b) to (e) of FIG. 4 can be arbitrarily combined. It can also be combined with the seventh embodiment (FIGS. 7, 8, and 9) described later.
  • the integrated thin-layer thermoelectric module of the first embodiment shown in FIG. 1 is patterned as a square sheet as in the fifth embodiment shown in FIG. 5 and cut along a dashed line 8 in FIG. By doing so, it can be mass-produced.
  • Example 2 in FIG. 2 for mass production, as in Example 6 in FIGS. 6 (a) and 6 (b), a plurality of rows are arranged on a square sheet, before or after zigzag processing.
  • the dash-dot line 6 can be cut at the point 8.
  • Example 3 The same manufacturing procedure is possible in Example 3.
  • thermoelectric module has a total cross-sectional area that is at least 1.2 times larger than that of conventional rigid-structured devices compared to conventional rigid-structured products of almost the same size, and the thermoelectric semiconductor device
  • the contact area between the electrode and the electrode can be about 4 to 6 times larger than before.
  • thermoelectric semiconductor element in the thermoelectric unit In order to extract power efficiently, the resistance of the thermoelectric semiconductor element in the thermoelectric unit must be optimized. Therefore, as in Embodiment 7 (a) of FIG. 7, a slit 71 or a dot hole 72 can be provided at an arbitrary position of the thermoelectric semiconductor element to adjust the resistance value to a desired value.
  • each thermoelectric semiconductor element needs to insulate the low-temperature side and the high-temperature side. Therefore, as shown in FIG. 7 (b), the middle of both sides can be formed into a constricted shape 73 like a thread winding.
  • FIG. 8 is a view similar to Embodiment 7 (b) in Examples 1 and 5 in which a three-dimensional spiral is formed in a spiral. This is a reduction of the heat loss between the side and the low-temperature side.
  • FIG. 9 also shows a constricted shape between the electrodes of the thermoelectric semiconductor element 1 in Example 2 or Examples 3 and 6 in which zigzag solidification is performed similarly to Example 7 (b). As 73, the heat loss between the hot side and the cold side is reduced.
  • thermoelectric semiconductor elements that are adjacent to each other by being processed into a three-dimensional shape. Therefore, it is necessary to enhance the thermal insulation inside the solid.
  • a layer with high thermal insulation that shuts off heat between internal cuts a layer of air or a layer of heat-blocking material with the best vacuum is provided. Is also good.
  • the gap between the units can be naturally formed during ordinary three-dimensional shading, and is rather inevitable. In the present invention, this force is actively used for heat insulation. can do.
  • the high-density integrated thin-layer thermoelectric module of the present invention can have a heat insulating property and an electric insulating property by sealing or coating a part or the entire periphery. At the same time, it has both moisture and dust proof effects.
  • the high-density integrated thin-layer thermoelectric module has a moisture- and dust-proof coating layer that has electrical insulation, heat insulation, and moisture-proof properties, such as POM (polyacetal), TPX (poly 4-methylpentene), and PP. (Polypropylene), PC (polycarbonate), PPO (polyoxide), closed cell urethane, organic nanofoam resin, etc. are suitable. These materials can be used in any of the above and below examples.
  • the high-density integrated thin-layer thermoelectric module of the present invention can be generally applied as a power generator using waste heat.
  • FIG. 10 also serves as a description and an application to a solar cell power generation device according to an embodiment described below.
  • 10A is a schematic diagram 100 of a known solar cell
  • FIG. 10B is a schematic diagram of a thin-layer thermoelectric module
  • FIG. 10C is a diagram in which the solar cell power generation device 100 and the thin-layer thermoelectric module 10 are combined. The details of the combination with the solar cell are described below. I will describe.
  • FIG. 11 is a schematic rear view (a) and a cross-sectional view (b) of a combined power generation system of the present invention in which the high-density integrated thin-layer thermoelectric module 10 of the present invention is attached to the back of a solar cell power generator 100.
  • the solar cell power generation device has a PN junction 103 on a bottom base 105, which receives sunlight energy via a strengthened glass 101 and a transparent electrode 102, and a transparent electrode 102 and the other electrode.
  • An electromotive force is generated between 104.
  • the heat collecting part generally generates heat by solar energy, which reduces the efficiency of the solar power generation.
  • the high-density integrated thin-layer thermoelectric module 10 of the present invention generates electromotive force by receiving thermal energy via the high-temperature base 106 and the electrically insulating thermal conductor 107.
  • thermoelectric modules 10-power solar cells for example, residential roof building materials called “solar tiles”. Then, heat is collected from a heat source of around 70 ° C generated by the heat of the sun, and power is generated by the Seebeck effect. At the same time, it also plays a role in helping the power generation efficiency of the solar cell system itself.
  • thermoelectric element 10 of the present invention When the above-described high-density integrated thin-layer thermoelectric element 10 of the present invention is attached to a heat-generating portion of a solar cell power generation system (solar tile) 100, the high-density integrated thin-layer thermoelectric module responds to the temperature difference ⁇ by the Seebeck effect. A considerable part of the heat generated by solar power generation is transmitted through the high-density integrated thin-layer thermoelectric module, and is radiated from the electric energy generated by the module, the heat radiation part 4 of the module, and the low-temperature base 108. The heat escapes as heat energy, and as a result, the temperature of the solar cell 100 decreases. This is equivalent to adding efficient and small heat dissipating means to the solar cell.
  • the decrease in efficiency due to the heat generated by the solar cell can be prevented by a considerable amount of heat generated by the high-density integrated thin-film thermoelectric element of the present invention, and the power generation operation can be performed more stably even when there is fluctuation in sunlight.
  • a solar cell system in which heating water is supplied to a heat-generating portion of the solar cell system or cooling is performed using a fan to improve efficiency. Constructing an effective system that solves heat generation and power generation at once by utilizing the heat generation effect that cannot be avoided in a solar power generation system To do.
  • thermoelectric tile in which a solar cell is applied to a roof material of a house, and a low-cost high-density integrated thin-layer thermoelectric module according to the present invention are combined with a solar power generation system to improve the efficiency and the total power generation.
  • Power generation system can be improved. It is said that the introduction cost advantage of the solar-one power generation system is 2.5 million yen / per house.
  • the combined use of the thermoelectric power generation proposed by the present invention improves the power generation amount by the synergistic effect of the high-density integrated thermoelectric semiconductor element based on the flexible film sheet.
  • the high-density integrated thin-layer thermoelectric element module of the present invention is set on the back side of the solar cell as shown in Fig. 11 to reduce the power generation efficiency of the solar cell. Is used to generate power by the heat receiving Seebeck effect.
  • This high-density integrated thin-layer thermoelectric element module can be manufactured integrally with the solar cell power generation system. However, even if it is used in addition to the existing solar power generation system, significant improvement in efficiency can be achieved. Can be obtained.
  • the present invention can also be applied to a system in which the temperature changes over a wide range.
  • Figure 12 shows an example. As described above, there are various relations between the power generation amount and the temperature depending on the thermoelectric material.
  • the present invention has a multi-stage configuration using a plurality of thermoelectric materials having different temperature ranges, and can be used in a wide temperature range.
  • the high-density integrated thin-layer thermoelectric element module 10A is used at about 800 to 600 ° C
  • the SiGe compound is used as the thermoelectric semiconductor element
  • the thermoelectric semiconductor element is used at about 600 to 200 ° C for module 10B.
  • modules 10C is about 200 ⁇ 25 ° C
  • BiTe compounds can be used respectively.
  • Each module has a stepped structure through 107 of electrically insulating heat conduction, and a casing can be constituted by the moisture-proof, electric insulating, and heat insulating layers 5.
  • the high-density integrated thin-layer thermoelectric element module of the present invention can be manufactured in various shapes and sizes. A variety of shapes and sizes can be prepared, combined, and adapted to various applications.
  • the high-density integrated thin-layer thermoelectric module of the present invention can also be used as an efficient Peltier effect cooling device. Even if the Z value of the thermoelectric semiconductor element remains at the current capacity, the power generation capacity by the Seebeck effect per unit area or the cooling capacity by the Peltier effect is improved.
  • the high-density integrated thin-layer thermoelectric module of the present invention can be added to a power generation system using waste heat, and can perform environmentally friendly thermoelectric generation using the Seebeck effect.
  • the present invention relates to a thin-layer thermoelectric element module using an integrated technology.
  • By improving applicability by a flexible structure it is possible to utilize only the Seebeck effect or Peltier effect to generate electricity. It will be possible to combine modules that meet the conditions of the user, even in applications such as cooling and heating. Functionally, changing the thin layer pattern can easily contribute to customization and expand the range of use. Of course, if a technology to improve the Z value is developed, it can be expected to improve efficiency by applying it.
  • thermoelectric semiconductor element and the electrode are formed into thin layers to realize a flexible structure. Therefore, when this is added to various devices, the size, shape, and number of modules are appropriately selected. It could be well adapted to various equipment applications. Regardless of the size and unevenness of the device, the number of high-density integrated thin-layer thermoelectric modules of the present invention is manufactured and prepared in various sizes. Can be arranged in combination so as to meet the requirements.
  • the present invention greatly contributes to the global environment not only as a measure against power demand.
  • the Seebeck effect takes advantage of the improved adaptability of the present invention to application equipment and further enhances the manufacturing method. If it is changed appropriately, it can contribute greatly to the field of waste heat utilization of furnace heat. Peltier effects will not only greatly contribute to the deadlock of technology to improve efficiency, but also improve the difficulty of manufacturing and can provide significant cost benefits.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Il est prévu une unité de paires d’éléments thermoélectriques à couche mince modularisée en type intégré haute densité pour ainsi améliorer son adaptabilité à diverses applications. De nombreuses unités de paires d’éléments semi-conducteurs thermoélectriques à couche mince de type P et de type N et des électrodes à couche mince sont formées sur une feuille isolante thermiquement/isolante électriquement souple, des électrodes sont également formées pour maintenir les unités de paires d’éléments semi-conducteurs thermoélectriques par rapport aux côtés opposés et permettre au côté basse température de chevaucher le côté haute température pour améliorer un effet thermoélectrique et fournir une zone de contact plus importante entre les électrodes et les unités de paires de semi-conducteurs thermoélectriques, puis l’on recourbe ou l’on enroule la feuille en spirale pour effectuer un travail en trois dimensions, pour ainsi obtenir un module thermoélectriqueà couche mince de type intégré haute densité. On peut intercaler une couche d’air ou une couche d’élément isolant thermiquement entre des unités d’éléments thermoélectriques adjacents, ou bien on peut utiliser un film sous forme de feuille pour sceller la périphérie contre l’humidité et les taches.
PCT/JP2005/009864 2004-05-31 2005-05-30 Module thermoélectrique à couche mince de type intégré haute densité et système de production d’énergie hybride Ceased WO2005117154A1 (fr)

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JP2007103879A (ja) * 2005-10-07 2007-04-19 Univ Kanagawa 熱電素子
JP2008130594A (ja) * 2006-11-16 2008-06-05 Tokai Rika Co Ltd 熱電変換デバイス及びその製造方法
WO2009045862A3 (fr) * 2007-09-28 2009-11-05 Battelle Memorial Institute Dispositifs thermoélectriques
US7834263B2 (en) 2003-12-02 2010-11-16 Battelle Memorial Institute Thermoelectric power source utilizing ambient energy harvesting for remote sensing and transmitting
US7851691B2 (en) 2003-12-02 2010-12-14 Battelle Memorial Institute Thermoelectric devices and applications for the same
JP2011520252A (ja) * 2008-04-28 2011-07-14 ビーエーエスエフ ソシエタス・ヨーロピア 熱磁気発生機
JP2013062370A (ja) * 2011-09-13 2013-04-04 Daikin Ind Ltd 平面型薄膜熱電モジュール
US8455751B2 (en) 2003-12-02 2013-06-04 Battelle Memorial Institute Thermoelectric devices and applications for the same
WO2013185903A1 (fr) 2012-06-13 2013-12-19 Karlsruher Institut für Technologie Systèmes thermoélectriques enroulés et pliés et procédés de fabrication
JP2014209840A (ja) * 2013-03-22 2014-11-06 独立行政法人国立高等専門学校機構 中空管、及び発電装置
US9281461B2 (en) 2003-12-02 2016-03-08 Battelle Memorial Institute Thermoelectric devices and applications for the same
WO2016203939A1 (fr) * 2015-06-17 2016-12-22 富士フイルム株式会社 Élément de conversion thermoélectrique et module de conversion thermoélectrique
WO2019082986A1 (fr) * 2017-10-26 2019-05-02 株式会社デンソー Dispositif de conversion thermoélectrique et son procédé de fabrication
JPWO2018042708A1 (ja) * 2016-08-30 2019-06-24 国立大学法人東京工業大学 熱電変換装置および電子装置
JP2020140985A (ja) * 2019-02-26 2020-09-03 日本ゼオン株式会社 熱電変換モジュール
WO2021149770A1 (fr) * 2020-01-24 2021-07-29 国立大学法人筑波大学 Élément semi-conducteur et son procédé de fabrication, et dispositif de conversion thermoélectrique et son procédé de fabrication
US11374533B2 (en) 2018-05-31 2022-06-28 Mitsubishi Electric Corporation Solar power generation paddle, method of manufacturing the same, and space structure
CN114883475A (zh) * 2022-03-24 2022-08-09 嘉兴学院 一种可穿戴热电手环及其制备方法
US11832518B2 (en) 2021-02-04 2023-11-28 Purdue Research Foundation Woven thermoelectric ribbon

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JPH08153898A (ja) * 1994-11-28 1996-06-11 Matsushita Electric Ind Co Ltd 熱電素子
JP2001053322A (ja) * 1999-05-31 2001-02-23 Sony Corp 発電装置及び情報処理機器
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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9281461B2 (en) 2003-12-02 2016-03-08 Battelle Memorial Institute Thermoelectric devices and applications for the same
US7834263B2 (en) 2003-12-02 2010-11-16 Battelle Memorial Institute Thermoelectric power source utilizing ambient energy harvesting for remote sensing and transmitting
US7851691B2 (en) 2003-12-02 2010-12-14 Battelle Memorial Institute Thermoelectric devices and applications for the same
US8455751B2 (en) 2003-12-02 2013-06-04 Battelle Memorial Institute Thermoelectric devices and applications for the same
JP2007103879A (ja) * 2005-10-07 2007-04-19 Univ Kanagawa 熱電素子
JP2008130594A (ja) * 2006-11-16 2008-06-05 Tokai Rika Co Ltd 熱電変換デバイス及びその製造方法
WO2009045862A3 (fr) * 2007-09-28 2009-11-05 Battelle Memorial Institute Dispositifs thermoélectriques
JP2011520252A (ja) * 2008-04-28 2011-07-14 ビーエーエスエフ ソシエタス・ヨーロピア 熱磁気発生機
JP2013062370A (ja) * 2011-09-13 2013-04-04 Daikin Ind Ltd 平面型薄膜熱電モジュール
DE102012105086B4 (de) * 2012-06-13 2014-02-13 Karlsruher Institut für Technologie Gewickeltes und gefaltetes thermoelektrisches System und Verfahren zu dessen Herstellung
WO2013185903A1 (fr) 2012-06-13 2013-12-19 Karlsruher Institut für Technologie Systèmes thermoélectriques enroulés et pliés et procédés de fabrication
US9660167B2 (en) 2012-06-13 2017-05-23 Karlsruher Institut Fuer Technologie Wound and folded thermoelectric systems and method for producing same
DE102012105086A1 (de) * 2012-06-13 2013-12-19 Karlsruher Institut für Technologie Gewickeltes und gefaltetes thermoelektrisches System und Verfahren zu dessen Herstellung
JP2014209840A (ja) * 2013-03-22 2014-11-06 独立行政法人国立高等専門学校機構 中空管、及び発電装置
WO2016203939A1 (fr) * 2015-06-17 2016-12-22 富士フイルム株式会社 Élément de conversion thermoélectrique et module de conversion thermoélectrique
JPWO2016203939A1 (ja) * 2015-06-17 2018-04-19 富士フイルム株式会社 熱電変換素子および熱電変換モジュール
JPWO2018042708A1 (ja) * 2016-08-30 2019-06-24 国立大学法人東京工業大学 熱電変換装置および電子装置
JP6995370B2 (ja) 2016-08-30 2022-02-04 国立研究開発法人科学技術振興機構 熱電変換装置および電子装置
JP2019079991A (ja) * 2017-10-26 2019-05-23 株式会社デンソー 熱電変換装置およびその製造方法
WO2019082986A1 (fr) * 2017-10-26 2019-05-02 株式会社デンソー Dispositif de conversion thermoélectrique et son procédé de fabrication
US11374533B2 (en) 2018-05-31 2022-06-28 Mitsubishi Electric Corporation Solar power generation paddle, method of manufacturing the same, and space structure
JP2020140985A (ja) * 2019-02-26 2020-09-03 日本ゼオン株式会社 熱電変換モジュール
JP7363052B2 (ja) 2019-02-26 2023-10-18 日本ゼオン株式会社 熱電変換モジュール
WO2021149770A1 (fr) * 2020-01-24 2021-07-29 国立大学法人筑波大学 Élément semi-conducteur et son procédé de fabrication, et dispositif de conversion thermoélectrique et son procédé de fabrication
JPWO2021149770A1 (fr) * 2020-01-24 2021-07-29
US11832518B2 (en) 2021-02-04 2023-11-28 Purdue Research Foundation Woven thermoelectric ribbon
CN114883475A (zh) * 2022-03-24 2022-08-09 嘉兴学院 一种可穿戴热电手环及其制备方法

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