Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect

Definitions

• the present invention relates to a thermoelectric laminate and a thermoelectric device.
• thermoelectric conversion devices that can generate electricity from waste heat or the environment.
• many ⁇ -type structures have been proposed in which p-type and n-type thermoelectric materials are alternately connected in series to obtain a high electromotive force as a power generation device.
• Patent Document 1 discloses a thermoelectric element in which a thermoelectric layer made of a first thermoelectric material and a conductive layer made of a second thermoelectric material are alternately stacked with an insulating layer sandwiched between them. It is said that a thermoelectric element with improved thermoelectric performance can be realized by making the absolute value of the Seebeck coefficient of the first thermoelectric material constituting the thermoelectric layer larger than the absolute value of the Seebeck coefficient of the second thermoelectric material constituting the conductive layer, making the conductivity of the first thermoelectric material smaller than the conductivity of the second thermoelectric material, and providing an insulating layer between the thermoelectric layer and the conductive layer.
• Patent Document 2 proposes a structure in which a horizontal thermoelectric material with magnetization perpendicular to the surface is electrically connected to a vertical thermoelectric material via an insulating layer. It is said that this will realize a new thermoelectric conversion element that can increase the thermoelectric power generated in a direction perpendicular to both the temperature gradient and magnetization while retaining the thermoelectric conversion characteristics of the magnetic material.
• Patent Document 3 proposes a thin-film laminate structure of a ferromagnetic film/insulator film/thermoelectric material film/insulator film/ferromagnetic film formed on a substrate. It is said that it is possible to realize a thermoelectric conversion device that is small yet capable of generating a large electromotive force.
• JP 2016-213455 A International Publication WO2021/187347A1 JP 2020-098860 A
• thermoelectric modules are formed by stacking block-shaped p-type and n-type thermoelectric materials and electrodes that connect the thermoelectric materials in three dimensions while precisely positioning them, and then bonding them through processes such as applying pressure and heat. This requires highly accurate positioning and process control technology.
• the object of the present invention is to provide a thermoelectric device and a thermoelectric laminate therefor that are easy to position and bond.
• the first embodiment of the present invention is a thermoelectric laminate having a thermoelectric material layer having a first surface and a second surface opposed to each other, and an isolation layer laminated on the first surface of the thermoelectric material layer, the thermoelectric material layer having a magnetization component perpendicular to the first surface and the second surface, and the isolation layer having an insulating region that electrically insulates the thermoelectric material layer from the thermoelectric material layer of the other thermoelectric laminate when another thermoelectric laminate is laminated on the surface opposite to the surface laminated with the thermoelectric material layer, and an electrode region that electrically connects the thermoelectric material layer to the thermoelectric material layer of the other thermoelectric laminate.
• the second embodiment of the present invention is a thermoelectric stack as described in the first embodiment above, in which the isolation layer extends from the end of the first surface to the side of the thermoelectric material layer, and the electrode region is provided in the extended region.
• the third embodiment of the present invention is a thermoelectric laminate described in the first embodiment above, in which the electrode region of the isolation layer is sandwiched between the thermoelectric material layer and the thermoelectric material layer of the other thermoelectric laminate when another thermoelectric laminate is laminated on the surface opposite to the surface laminated with the thermoelectric material layer.
• the fourth embodiment of the present invention is a thermoelectric laminate as described in any one of the first to third embodiments above, in which the thermoelectric material layer has a three-dimensional shape that fits into the isolation layer on the surface that contacts the isolation layer.
• the fifth embodiment of the present invention is a thermoelectric laminate described in any one of the first to fourth embodiments, in which when the isolation layer is a first isolation layer, the insulating region is a first insulating region, and the electrode region is a first electrode region, the second isolation layer has a second isolation layer laminated on the second surface, and the second isolation layer has a second insulating region that electrically insulates the thermoelectric material layer from the other thermoelectric laminate when another thermoelectric laminate is laminated on the surface opposite to the surface laminated with the thermoelectric material layer by the magnetic force of the magnetization component, and a second electrode region that electrically connects the thermoelectric material layer to the thermoelectric material layer of the other thermoelectric laminate.
• the sixth embodiment of the present invention is a thermoelectric stack as described in the fifth embodiment, in which the first electrode region and the second electrode region are disposed at positions spaced apart from each other in a plane in which the first surface and the second surface are viewed in plan.
• the seventh embodiment of the present invention is a thermoelectric stack as described in the third embodiment above, in which the insulating region has adhesive properties.
• the eighth embodiment of the present invention is a thermoelectric stack as described in the seventh embodiment above, in which the insulating region is peelable.
• the ninth embodiment of the present invention is a thermoelectric laminate as described in any one of the first to eighth embodiments above, in which the thermoelectric material layer is made of two or more thermoelectric materials.
• the tenth embodiment of the present invention is a thermoelectric laminate as described in the ninth embodiment above, in which the thermoelectric material layer is formed by stacking unit thermoelectric material layers of each of the two or more thermoelectric materials.
• the eleventh embodiment of the present invention is a thermoelectric laminate comprising one or more first thermoelectric laminates as described in any one of the first to tenth embodiments above, the thermoelectric material layer having a positive horizontal thermoelectric power, and one or more second thermoelectric laminates as described in any one of the first to tenth embodiments above, the thermoelectric material layer having a negative horizontal thermoelectric power, which are alternately bonded together by the magnetic forces of their magnetized components, sandwiching their respective isolation layers, and are electrically connected by the electrode regions of the isolation layers.
• thermoelectric material of the first thermoelectric stack is a magnetic material mainly composed of at least one selected from the group consisting of a samarium-cobalt (Sm-Co) alloy, a cobalt manganese gallium ( Co2MnGa ) alloy, a cobalt manganese aluminum/silicon ( Co2Mn (Al,Si)) alloy, cobalt (Co), an iron-gallium (Fe-Ga) alloy, an iron-aluminum (Fe-Al) alloy, an iron-platinum (FePt) alloy, an iron-lead ( FePd ) alloy, an iron-tin ( Fe3Sn2 ) alloy, and an iron nitride ( Fe4N ), and the thermoelectric material of the second thermoelectric stack is a magnetic material mainly composed of at least one selected from the group consisting of a ne
• the thirteenth embodiment of the present invention is a thermoelectric device in which one or more first thermoelectric material layers having positive transverse thermoelectric power and one or more second thermoelectric material layers having negative transverse thermoelectric power are alternately stacked with an isolation layer sandwiched therebetween, the first and second thermoelectric material layers have magnetization components perpendicular to the stacking surface and in the same direction, the isolation layer has an electrode region that electrically insulates the first and second thermoelectric material layers that are in close contact with each other due to the magnetic force of the magnetization components and that provides electrical conductivity, and the electrode regions that contact both sides of each of the first and second thermoelectric material layers are arranged at positions in each thermoelectric material layer that are spaced apart in a direction perpendicular to both the stacking direction and the direction in which a temperature gradient is applied.
• the 14th embodiment of the present invention is a thermoelectric device as described in the 13th embodiment above, in which the isolation layer extends from the end of the laminated surface to the side of the thermoelectric material layer, and the electrode region is located in the extended region.
• the fifteenth embodiment of the present invention is a thermoelectric device as described in the thirteenth embodiment, in which the first and second adjacent thermoelectric material layers are stacked with the isolation layer in between, so as to be detachable by the magnetic force of the magnetized component.
• the 16th embodiment of the present invention is a thermoelectric device as described in any one of the 13th to 15th embodiments above, in which the first and second thermoelectric material layers have a three-dimensional shape that fits into the isolation layer on at least one surface that is in close contact with the electrode region of the isolation layer.
• the 17th embodiment of the present invention is a thermoelectric device described in any of the 13th to 16th embodiments, wherein the first thermoelectric material is a magnetic material mainly composed of at least one selected from the group consisting of Sm-Co alloy, Co2MnGa alloy, Co2Mn (Al,Si) alloy, Co, Fe-Ga alloy, Fe-Al alloy, FePt alloy, FePd alloy, Fe3Sn2 alloy , and iron nitride ( Fe4N ), and the second thermoelectric material is a magnetic material mainly composed of at least one selected from the group consisting of NdFeB alloy, MnGa alloy, Fe, and Co-Gd alloy.
• the first thermoelectric material is a magnetic material mainly composed of at least one selected from the group consisting of Sm-Co alloy, Co2MnGa alloy, Co2Mn (Al,Si) alloy, Co, Fe-Ga alloy, Fe-Al alloy, FePt alloy, FePd alloy, Fe3Sn2
• the 18th embodiment of the present invention is a thermoelectric device according to any one of the 13th to 16th embodiments, in which at least one of the first and second thermoelectric material layers is a laminate consisting of multiple layers of mutually different thermoelectric materials.
• thermoelectric device and a thermoelectric laminate therefor that are easy to position and bond.
• FIG. 1 is an explanatory diagram showing a schematic diagram of the basic structure of a thermoelectric laminate of the present invention.
• FIG. 2 is an explanatory diagram that illustrates the operating principle of the thermoelectric device of the present invention.
• FIG. 3 is an explanatory diagram showing a configuration example of a thermoelectric device according to an embodiment of the present invention.
• FIG. 4 is an explanatory diagram of a modified example of the electrode region.
• FIG. 5 is an explanatory diagram of another modified example of the electrode region.
• FIG. 6 is an explanatory diagram of another electrode structure.
• FIG. 7 is a graph showing the measurement results confirming the power generation behavior of the thermoelectric material produced as an example.
• FIG. 8 is a graph showing the power generation performance of the horizontal thermoelectric module produced as an example.
• FIG. 9 is an explanatory diagram showing another example of the configuration of the thermoelectric device of the present invention.
• thermoelectric stacks with magnetization components perpendicular to the contact surface and electrically connected through a portion of the isolation layer ( Figures 1 to 6)
• a representative embodiment disclosed in the present application is a thermoelectric stack (10) having a thermoelectric material layer (1) having a first surface and a second surface opposed to each other, and an isolation layer (2) laminated on the first surface of the thermoelectric material layer, wherein the thermoelectric material layer has a magnetization component (5) perpendicular to the first and second surfaces, and the isolation layer has an insulating region (3) that electrically insulates the thermoelectric material layer from a thermoelectric material layer of another thermoelectric stack when another thermoelectric stack is laminated on a surface opposite to the surface laminated with the thermoelectric material layer, and an electrode region (4) that electrically connects the thermoelectric material layer to a thermoelectric material layer of the other thermoelectric stack.
• thermoelectric laminate that is easy to position and bond to form a thermoelectric device.
• the electrode area extends to the side of the thermoelectric material layer (Figs. 4 and 5)
• thermoelectric material layer (1) e.g., FIG. 5
• the entire thermoelectric material layer can be configured to contribute to thermoelectric conversion.
• thermoelectric material layer is the region sandwiched between the thermoelectric material layers ( Figures 1 and 4)
• thermoelectric laminate as described above, wherein when another thermoelectric laminate is laminated on a surface opposite to the surface laminated with the thermoelectric material layer, the electrode region of the isolation layer is sandwiched between the thermoelectric material layer and a thermoelectric material layer of the other thermoelectric laminate.
• thermoelectric material layer in the area through which the heat flow passes can be maximized. Note that the contribution of the thermoelectric material layer to thermoelectric conversion also depends on the position and area of the electrode region.
• thermoelectric material layer interlocks with the electrodes ( Figure 6)
• thermoelectric material layer has a three-dimensional shape that fits with the isolation layer on a surface that contacts the isolation layer.
• thermoelectric material layer and electrodes This allows the thermoelectric material layer and electrodes to be positioned in a self-aligning manner, making the wiring process even easier.
• thermoelectric laminate (12) according to any one of items [1] to [4], wherein the isolation layer is a first isolation layer (2-2), the insulating region is a first insulating region (3-2), and the electrode region is a first electrode region (4-3), the thermoelectric laminate has a second isolation layer (2-1) laminated on the second surface, and the second isolation layer has a second insulating region (3-1) that electrically insulates the thermoelectric material layer from a thermoelectric material layer of the other thermoelectric laminate when another thermoelectric laminate is laminated on a surface opposite to the surface laminated with the thermoelectric material layer by a magnetic force of the magnetization component, and a second electrode region (4-2) that electrically connects the thermoelectric material layer to a thermoelectric material layer of the other thermoelectric laminate.
• thermoelectric material layer As a result, an electrical connection is formed through close contact caused by the magnetic force of the magnetized component of the thermoelectric material layer, eliminating the need for any further wiring process.
• thermoelectric stack described in [5] wherein the first electrode region and the second electrode region are arranged at positions separated from each other in a plane when the first surface and the second surface are viewed in a plan view.
• the first electrode region (4-3) and the second electrode region (4-2) are preferably located on both sides of the stacking direction in the thermoelectric material layer (1-2) of the thermoelectric stack (12), and are each located at a position where the potential difference (electromotive force) generated by the driving electric field generated in the direction of the cross product of the applied temperature gradient and the residual magnetization component is maximum.
• the first electrode region (4-3) and the second electrode region (4-2) may be composed of multiple electrode regions each located at approximately the same potential.
• the symbols in parentheses are examples adopted by citing FIG. 2, and are not limited to this.
• thermoelectric laminate according to [3] Adhesiveness
• the insulating region has adhesiveness.
• thermoelectric stack according to [7] Ease of Peeling
• the insulating region is peelable.
• thermoelectric conversion element that is made up of this thermoelectric laminate.
• thermoelectric Laminate Made of Two or More Thermoelectric Materials
• thermoelectric laminate according to any one of claims 1 to 8, wherein the thermoelectric material layer is made of two or more thermoelectric materials.
• thermoelectric materials This allows for greater freedom in the selection of thermoelectric materials.
• thermoelectric laminate according to the present invention, wherein the thermoelectric material layer is formed by stacking unit thermoelectric material layers of the two or more thermoelectric materials.
• thermoelectric material layer in which p-type and n-type thermoelectric materials are alternately layered with a gradient as the thermoelectric material layer.
• gradient laminate is a multi-layer structure in which two or more types of thermoelectric material layers (the above-mentioned “unit thermoelectric material layers”) are layered, and the “lamination” referred to here is different from the “lamination” referred to in [1].
• thermoelectric device that is easy to position and bond.
• thermoelectric material of the first thermoelectric laminate is a magnetic material mainly composed of at least one selected from the group consisting of Sm-Co alloy, Co2MnGa alloy, Co2Mn (Al,Si) alloy, Co, Fe-Ga alloy, Fe- Al alloy, FePt alloy, FePd alloy, Fe3Sn2 alloy, and iron nitride ( Fe4N ), and the thermoelectric material of the second thermoelectric laminate is a magnetic material mainly composed of at least one selected from the group consisting of NdFeB alloy, MnGa alloy, Fe, and Co-Gd alloy.
• thermoelectric device This allows the identification of a suitable thermoelectric material for constructing the thermoelectric device described in [11].
• thermoelectric device connected in series by the magnetic force of magnetized components (Figs. 2 and 3)
• a representative embodiment disclosed in the present application is a thermoelectric device in which one or more first thermoelectric material layers (1-2) having positive lateral thermoelectric power and one or more second thermoelectric material layers (1-1) having negative lateral thermoelectric power are alternately stacked with isolation layers (2-1, 2-2) sandwiched therebetween, and is configured as follows.
• the first and second thermoelectric material layers have magnetization components (5-1, 5-2) perpendicular to the lamination plane and in the same direction.
• the isolation layer has insulating regions (3-1, 3-2) that electrically insulate the adjacent first and second thermoelectric material layers by the magnetic force of the magnetization components, and electrode regions (4-2, 4-3) that conduct electricity.
• the electrode regions (4-1 and 4-2, 4-2 and 4-3) that contact both sides of each of the first and second thermoelectric material layers are arranged in positions in each thermoelectric material layer that are spaced apart in a direction perpendicular to both the lamination direction and the direction in which a temperature gradient is applied.
• each electrode region may be composed of multiple electrode regions that are arranged at positions of approximately the same potential.
• Electrode areas extend to the sides of the thermoelectric material layer (Figs. 4 and 5) The thermoelectric device according to [13], wherein the isolation layer extends from an end of the laminated surface to a side surface of the thermoelectric material layer, and the electrode region is provided in the extended region.
• thermoelectric material layer (1) e.g., Figure 5
• the entire thermoelectric material layer can be configured to contribute to thermoelectric conversion.
• thermoelectric device Easy attachment and detachment by magnetic adhesion.
• a thermoelectric device according to any one of [13] to [15], wherein the first and second thermoelectric material layers adjacent to each other are stacked with the isolation layer in between so as to be detachable by the magnetic force of the magnetization component.
• thermoelectric stacks This makes the positioning and bonding process easier and allows for flexible response, for example by adjusting the number of thermoelectric stacks to be stacked according to the size of the object to be installed at the installation site.
• thermoelectric material layer interlocks with the electrodes (Fig. 4) [13] to [15], wherein the first and second thermoelectric material layers have a three-dimensional shape that fits with the isolation layer on at least one surface that is in close contact with the electrode region of the isolation layer.
• thermoelectric material layer and the electrodes This allows the thermoelectric material layer and the electrodes to be positioned in a self-aligning manner, making the wiring process even easier.
• thermoelectric material is a magnetic material mainly composed of at least one selected from the group consisting of Sm-Co alloy, Co2MnGa alloy, Co2Mn (Al,Si) alloy, Co, Fe-Ga alloy, Fe-Al alloy, FePt alloy, FePd alloy, Fe3Sn2 alloy, and iron nitride ( Fe4N ), and the second thermoelectric material is a magnetic material mainly composed of at least one selected from the group consisting of NdFeB alloy, MnGa alloy, Fe, and Co-Gd alloy.
• thermoelectric materials for constructing the thermoelectric devices described in [13] to [16].
• thermoelectric device according to any one of [13] to [16], wherein at least one of the first and second thermoelectric material layers is a stack composed of multiple layers of thermoelectric materials different from each other.
• thermoelectric material in which p-type and n-type thermoelectric materials are alternately graded and multi-layered as the thermoelectric material layers.
• grade laminate is a multi-layer structure in which two or more types of thermoelectric material layers (the above-mentioned “unit thermoelectric material layers”) are laminated, and the “lamination” referred to here is different from the “lamination” referred to in [13].
• Fig. 1 is an explanatory diagram showing a schematic diagram of the basic structure of a thermoelectric laminate 10 of the present invention.
• the thermoelectric laminate 10 has a thermoelectric material layer 1 and an isolation layer 2.
• the isolation layer 2 is laminated on one of two mutually opposing surfaces of the thermoelectric material layer 1 (the +x side of the y-z plane in Fig. 1).
• the thermoelectric material layer 1 has a magnetization component 5 perpendicular to the above-mentioned two surfaces (in the x-axis direction).
• the isolation layer 2 has, within a surface that contacts the thermoelectric material layer 1 when laminated, an insulating region 3 that insulates between two adjacent thermoelectric material layers 1 and an electrode region 4 that electrically connects the two adjacent thermoelectric material layers 1.
• thermoelectric laminate 10 that can be easily positioned and bonded to form a thermoelectric device.
• the two thermoelectric material layers 1 are tightly attached with the isolation layer 2 in between due to the magnetic force of the magnetization component perpendicular to the lamination surface, and are electrically connected at the electrode region 4 that is part of the isolation layer 2.
• FIG. 2 is an explanatory diagram showing the operating principle of the thermoelectric device of the present invention.
• the thermoelectric laminate 1 of the present invention has a magnetization component perpendicular to the lamination surface, so if they are aligned in the same direction, they will be bonded by magnetic force.
• FIG. 2 shows a state in which another thermoelectric laminate 11 is laminated on the other surface of a thermoelectric laminate 12 having an insulating region 3-2 and an electrode region 4-3 in an isolation layer 2-2 on one surface.
• the thermoelectric laminate 11 and the thermoelectric laminate 12 have magnetization components 5-1 and 5-2 in the same direction perpendicular to the lamination surface, and are bonded by magnetic force in the left-right direction of the paper.
• thermoelectric laminate 12 When viewed from the thermoelectric laminate 12, the surface on which the other thermoelectric laminate 11 is laminated has an isolation layer 2-1, and when the thermoelectric laminate 11 is attached by magnetic force, it is electrically insulated in the insulating region 3-1 and connected so as to be electrically conductive in the electrode region 4-2.
• thermoelectric laminates 11 and 12 when the thermoelectric laminates 11 and 12 are constructed using thermoelectric materials with positive and negative lateral thermoelectric power, respectively, the electromotive forces of the thermoelectric laminates 11 and 12 are integrated by electrically connecting them in series, and a high voltage can be output. If the direction of the temperature gradient 30 is perpendicular to the paper surface and runs from front to back as shown in Fig. 2, in the thermoelectric laminate 11 with positive lateral thermoelectric power, a driving electric field E ANE 20-1 is generated from the bottom to the top of the paper surface as the cross product component of the temperature gradient 30 and the magnetic force of the magnetization component 5-1.
• the ratio of the potential gradient and the temperature gradient generated from the bottom to the top of the paper surface in the open voltage state is defined as the anomalous Nernst coefficient S ANE .
• the thermoelectric stack 12 has a negative anomalous Nernst coefficient S ANE of the opposite sign to that of the thermoelectric stack 11 and is considered to be a thermoelectric stack with so-called negative lateral thermoelectric power, then in the thermoelectric stack 12, a driving electric field E ANE 20-2 is generated in the downward direction from the top of the page as the cross product component of the temperature gradient 30 and the magnetic force of the magnetization component 5-2.
• the electrode regions 4-1 and 4-2 in contact with both sides of the thermoelectric material layer 1-1, and the electrode regions 4-2 and 4-3 in contact with both sides of the thermoelectric material layer 1-2 are disposed at positions in each thermoelectric material layer that are spaced apart in a direction perpendicular to both the stacking direction and the direction in which the temperature gradient 30 is applied. It is most preferable to dispose them at the two ends that are the furthest apart.
• a driving electric field E ANE 20-2 is generated in a direction perpendicular to the temperature gradient 30 and the magnetization component 5-2, and the potential difference is maximized at both ends, so that the maximum value of the generated electromotive force can be extracted.
• the electrode regions 4-2 and 4-3 are disposed at positions with approximately the same potential, and may be divided into a plurality of electrode regions.
• thermoelectric stacks 11 and 12 are insulated in the insulating region 3-2 and are conductive in the electrode region 4-2, and are therefore connected in series between the electrodes 4-3 and 4-1, and the sum of the potential difference due to the driving electric field E ANE 20-2 and the potential difference due to the driving electric field E ANE 20-1 is output.
• materials having anomalous Nernst coefficients S ANE with opposite signs are brought into close contact with each other alternately by magnetic force while maintaining electrical insulation, and then electrically connected in series, thereby making it possible to obtain a high-density horizontal thermoelectric module.
• thermoelectric element of the present invention is also highly efficient in terms of volume utilization.
• p-type and n-type thermoelectric materials are each formed into a columnar shape and placed apart from each other.
• the columnar thermoelectric materials are spaced apart by alignment, so the gaps become a volume that does not directly contribute to thermoelectric conversion.
• thermoelectric element of the present invention when viewed from the vector direction of the temperature gradient 30, the area through which the heat flow passes is composed only of the thermoelectric material layer 1 and the isolation layer 2.
• the isolation layer 2 only needs to be insulated when it is brought into close contact with a magnetic force, and since the potential difference is low, it does not need to be thick enough to consider the insulation voltage, and a thin film-like thickness is sufficient. Therefore, the thermoelectric material layer 1 occupies most of the area through which the heat flow passes, and most of the heat flow can be directly contributed to thermoelectric conversion.
• no electrodes or substrates are required, and a structure occupied only by the thermoelectric material layer 1 can be formed. In this way, there is very little presence of substances other than thermoelectric materials on the surface through which the heat flow passes and on the path in the direction through which the heat flow passes, and the thermoelectric element of the present invention can be said to be highly efficient in terms of volume utilization.
• FIG. 2 shows a simple thermoelectric device in which one thermoelectric laminate 11 and one thermoelectric laminate 12 are laminated, but the number of laminated layers is arbitrary.
• thermoelectric device 100 is configured by alternately stacking five thermoelectric laminates 11 and 12.
• the thermoelectric material layers having positive horizontal thermoelectric power included in the thermoelectric laminate 11 and the thermoelectric material layers having negative horizontal thermoelectric power included in the thermoelectric laminate 12 are alternately stacked with an isolation layer sandwiched between them.
• the thermoelectric material layers of the thermoelectric laminates 11 and 12 have magnetization components in the same direction perpendicular to the stacking surface (x-axis direction), and the isolation layer insulates the adjacent thermoelectric material layers in the insulating region by the magnetic force of the magnetization component and electrically conducts them in the electrode region.
• This magnetization component not only brings the thermoelectric laminates into close contact with each other, but also generates a driving electric field E ANE in the thermoelectric material layers due to the anomalous Nernst effect. That is, when a temperature gradient is applied in the y-axis direction, a driving electric field E ANE due to the anomalous Nernst effect is generated in each thermoelectric material layer between adjacent thermoelectric material layers in opposite directions.
• the electrode regions electrically connecting adjacent thermoelectric material layers are alternately arranged at the furthest positions in the direction perpendicular to both the temperature gradient and the stacking direction (z-axis direction), so that the potential differences alternately generated in opposite directions can be connected in series, and a large potential difference integrated across both ends can be output as an electromotive force.
• thermoelectric laminates 11 and 12 have magnetization components in the same direction in the lamination direction, so simply lining them up next to each other allows them to adhere to each other through magnetic force and to be electrically connected, making the positioning and joining process extremely easy in the thermoelectric device 100.
• thermoelectric material layer 1 (1-1, 1-2) and the isolation layer 2 (2-1, 2-2) overlap with the same area when viewed from the x-axis direction.
• the thermoelectric material layer 1 (1-1, 1-2) and the isolation layer 2 (2-1, 2-2) overlap with the same area when viewed from the x-axis direction.
• the structure of the electrode region 4 is not limited to this, and a part or the whole of the electrode region 4 may extend to the side wall of the thermoelectric material layer 1, and further may be formed away from the insulating region 3 of the isolation layer 2.
• thermoelectric material layer 1 As shown in FIG. 4, a part of the electrode region 4 may extend to the side (z side or -z side) of the thermoelectric material layer 1. By extending to the side, the entire thermoelectric material can be configured to contribute to thermoelectric conversion, and an ideal thermoelectromotive force can be obtained. For example, as shown in FIG. 5, by forming the electrode region 4 at the end of the thermoelectric material layer 1, all electromotive forces generated anywhere from one end to the other end of the thermoelectric material layer 1 can be extracted by flowing them to the electrode region 4. Electrical connection between the thermoelectric material layers 1 of adjacent thermoelectric stacks 10 may be formed at the contact surfaces as in Fig.
• thermoelectric material layer 1 1, or another wiring, for example, a crimped wiring made of indium, may be added.
• the entire electrode region 4 may be formed on the side surface of the thermoelectric material layer 1 as shown in Fig. 5.
• a crimped wiring made of indium is formed to electrically connect the adjacent thermoelectric material layers 1 so that a series circuit is formed overall.
• FIG. 6 is an explanatory diagram of another electrode structure.
• the thermoelectric material layer 1 has a three-dimensional shape that fits into the isolating layer 2 on the surface that contacts the isolating layer 2. This allows the thermoelectric material layer and the electrode to be positioned in a self-aligning manner, making the wiring process even easier.
• FIG. 6 shows an example.
• the thermoelectric material layer 1 on the left side has notches 41 and 42.
• the isolating layer 2 laminated from the right side of the figure has an electrode region 4 that is thicker than the insulating region 3.
• the electrode region 4 of the isolating layer fits into the notches 41 and 42 of the thermoelectric material layer 1.
• the size of the electrode region 4 that protrudes toward the thermoelectric material layer 1 side from the insulating region 3 is preferably designed so that it fits snugly into the notches 41 and 42. This also makes it easier to align the thermoelectric material layer and the isolating layer.
• the increase in the contact area between the thermoelectric material layer and the electrode region 4 also produces the effect of reducing the contact resistance. In this example, a simple cutout is used, but by adopting a shape that increases the contact area, it is possible to further reduce the electrical contact resistance.
• the electrode region 4 can be structured to protrude on both sides beyond the leading edge region 3, and can also be configured to engage with another thermoelectric material layer 1 that is attached from the opposite side (further to the right in FIG. 6). Furthermore, the thermoelectric material layer 1 can also be provided with notches 43 and 44, and 45 and 46, respectively, on both sides that are laminated, as shown in the right edge of FIG. 6.
• the thermoelectric material layer 1 can be a layer that utilizes various transverse thermoelectric conversion phenomena.
• transverse thermoelectric materials such as magnetic materials that exhibit the anomalous Nernst effect or the spin Seebeck effect, and goniopolar materials with anisotropic Seebeck coefficients can be used.
• a geometrically induced transverse thermoelectric material can be used, which is configured by alternately laminating p-type and n-type Seebeck materials obliquely to the temperature gradient direction. By using such a composite material, various transverse thermoelectric conversion phenomena can be superimposed to increase the output.
• FIG. 9 is an explanatory diagram showing another example of the configuration of the thermoelectric device of the present invention.
• the thermoelectric laminates 11 and 12 are respectively composed of a thermoelectric material layer 1-1 and an isolation layer 2-1, and a thermoelectric material layer 1-2 and an isolation layer 2-2, and are similar to the second embodiment in that they are closely attached to each other to form an electric heating device.
• the thermoelectric material layers 1-1 and 1-2 are each composed of two types of thermoelectric material layers 1a and 1b, and 1c and 1d, which are alternately stacked, and the stacking direction is inclined from the temperature gradient 30.
• thermoelectric material layers 1a and 1b, and 1c and 1d p-type and n-type thermoelectric materials, they can function as horizontal thermoelectric material layers, and the sign of the driving electric field can be reversed by reversing the inclination angle with respect to the temperature gradient (y-axis direction).
• thermoelectric material layers 1a or 1b, 1c or 1d can be made to be magnetic materials to generate magnetization components 5-1 and 5-2.
• thermoelectric module As an example of a thermoelectric device capable of connecting laminates by magnetic force, a horizontal thermoelectric module was fabricated consisting of two types of permanent magnets with different signs of the anomalous Nernst effect, which is one type of horizontal thermoelectric power, and its characteristics were evaluated.
• the operating principle of the horizontal thermoelectric module of this example is as explained in embodiment 2.
• a total of 24 disc-shaped SmCo 5 magnets and Nd 2 Fe 14 B magnets were stacked alternately in the same magnetization direction, 12 of each, to create a laminate.
• a paper towel manufactured by AS ONE
• instant adhesive Aron Alpha Tough Power, manufactured by Toagosei Co., Ltd.
• the next magnet a magnet with an anomalous Nernst coefficient S ANE of the opposite sign
• the obtained laminate was cut into a rectangular parallelepiped shape using a diamond wire saw (DWS100 manufactured by Sakae Research Co., Ltd.) Furthermore, the sides of the material were crimped and wired with indium (manufactured by Nilaco Corporation) to form a circuit in which SmCo 5 magnets and Nd 2 Fe 14 B magnets were alternately connected in series, completing a horizontal thermoelectric module.
• thermoelectric materials SmCo 5 magnets and Nd 2 Fe 14 B magnets
• the area ratio of the thermoelectric materials, SmCo 5 magnets and Nd 2 Fe 14 B magnets, to the heat-receiving surface of the module exceeds 81%, an occupation density unparalleled compared to conventional ⁇ -type thermoelectric modules.
• the isolation film having an insulating region and an electrode region can be formed, for example, by a film forming process, a coating process, a bonding process, etc., as described below.
• a metal such as aluminum (Al) is formed on the magnet, which is the thermoelectric material.
• the electrode area is covered with an anti-oxidation film such as resist, and the other parts are oxidized to form an insulating area.
• the anti-oxidation film is then removed using an organic solvent, etc.
• Application process Silver paste or indium is applied to the electrode area, and high-heat resistant adhesive or Aron ceramic is applied to the insulating area.
• An adhesive tape with a conductive area is attached.
• An adhesive tape with a conductive area is, for example, an adhesive tape with a conductive circuit section that penetrates the surface and an insulating section other than that, and becomes electrically conductive when attached to a magnet.
• the power generation performance of the horizontal thermoelectric module was evaluated by applying a temperature difference ⁇ T to both sides of the module and measuring the current-voltage characteristics of the two copper wires using four-terminal measurements. That is, one of the copper wires was defined as a positive voltage (V+) and a negative current (I-), and the other was defined as a negative voltage (V-) and a positive current (I+).
• the load current I load was swept and the voltage V was measured. At this time, the power generation output P is expressed as the product of the load current I load and the voltage V.
• Figure 7 is a graph showing the measurement results confirming the power generation behavior of the thermoelectric material produced as an example.
• the open circuit voltage V was measured using the following procedure to confirm that the output generated by the temperature difference ⁇ T is due to the anomalous Nernst effect.
• Figure 8 is a graph showing the power generation performance of the horizontal thermoelectric module fabricated as an example.
• thermoelectric material layer 1 1, 1-1, 1-2 Thermoelectric material 2, 2-1, 2-2 Isolation layer 3, 3-1, 3-2 Insulation region 4, 4-1, 4-2, 4-3 Electrode region 5, 5-1, 5-2 Magnetization component perpendicular to the lamination plane 10, 11, 12 Thermoelectric laminate 20-1, 20-2 Driving electric field 30 Temperature gradient 41 to 46 Notches in thermoelectric material layer 100 Thermoelectric device

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• 2024
  • 2024-08-22 WO PCT/JP2024/029879 patent/WO2025062936A1/ja active Pending
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