Thermoelectric battery

Abstract

This invention provides a thermoelectric battery that is advantageous in that it suppresses performance degradation due to changes in the thickness of the electrolyte layer. [Solution] The thermoelectric battery 1a comprises a thermoelectric element 10, a first member 21, a second member 22, an insulating member 30, a pressurizing member 40, and an elastic member 50. The thermoelectric element 10 comprises a thermoelectric conversion layer 13 and an electrolyte layer 14, and converts thermal energy into electrical energy. The thermoelectric conversion layer 13 comprises an electron thermal excitation layer 11 and an electron transport layer 12. In the electron thermal excitation layer 11, excited electrons are generated by heat. The pressurizing member 40 pressurizes the electrolyte layer 14 in the thickness direction. The elastic member 50 is arranged along the same plane as the electrolyte layer 14 and is compressible and deformable by thermal expansion in a direction perpendicular to the thickness direction of the electrolyte layer 14.

Description

[Technical Field]

[0001] This disclosure relates to thermoelectric batteries. [Background technology]

[0002] Conventionally, thermoelectric batteries, which generate electricity using heat, are known.

[0003] Patent Document 1 describes a thermoelectric battery that includes a thermoelectric generator that converts thermal energy into electrical energy, comprising a plurality of thermal power generation elements in which a thermoelectric conversion layer and a solid electrolyte layer are laminated. In addition to the thermoelectric generator, this thermoelectric battery includes a conductive case, an insulating member, and a compressible conductor. The thermoelectric conversion layer has an electron thermal excitation layer and an electron transport layer. The compressible conductor is housed in the case and compressed between the thermoelectric generator and the case. This prevents unnecessary pressure from being applied to the thermoelectric generator and suppresses damage to the thermoelectric generator.

[0004] Patent Document 2 describes a battery including a thermoelectric power generation element in which a first part containing a semiconductor that generates thermally excited electrons and holes, a second part containing an electrolyte to which charge-transporting ion pairs can move, and a third part containing a material that serves as an electrode are in contact in this order. In this thermoelectric power generation element, the valence electron charge of the semiconductor in the first part is positive compared to the redox potential of the charge-transporting ion pair. At the interface between the first and second parts, an oxidation reaction occurs between the ion that is more easily oxidized than the other ion, and at the interface between the third and second parts, a reduction reaction occurs between the ion that is more easily reduced than the other ion. This thermoelectric power generation element does not require a temperature gradient. The shortest distance L and ion diffusion thickness IDT between the first and third parts satisfy predetermined conditions. Patent Document 2 explains that it has been found that the battery characteristics can be improved by optimizing the thickness of the electrolyte between the semiconductor and the electrode according to the electrolyte. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-108315 [Patent Document 2] International Publication No. 2022 / 191101 [Overview of the project] [Problems that the invention aims to solve]

[0006] The description in the above-mentioned patent document warrants reconsideration from the viewpoint of suppressing performance degradation due to changes in the thickness of the electrolyte layer. Therefore, this disclosure provides a novel thermoelectric battery that is advantageous from the viewpoint of suppressing performance degradation due to changes in the thickness of the electrolyte layer. [Means for solving the problem]

[0007] This disclosure is, A thermoelectric power generator comprising a thermoelectric conversion layer including an electron thermal excitation layer and an electron transport layer that generate excited electrons by heat, and an electrolyte layer laminated with the thermoelectric conversion layer, which converts thermal energy into electrical energy, A first member having conductivity, A second member is electrically conductive, electrically insulated from the first member, and together with the first member, constitutes a case for housing the thermoelectric generator. An insulating member that electrically insulates the first member or the second member from the electrolyte layer and the thermoelectric conversion layer in a direction perpendicular to the thickness direction of the electrolyte layer, A pressurizing member electrically connects the thermoelectric generator and the first member and pressurizes the electrolyte layer in the thickness direction, The system comprises an elastic member disposed along the same plane as the electrolyte layer and capable of compression deformation by thermal expansion in a direction perpendicular to the thickness direction of the electrolyte layer, We provide thermoelectric power generation batteries. [Effects of the Invention]

[0008] According to this disclosure, it is possible to provide a novel thermoelectric battery that is advantageous in that it suppresses performance degradation due to changes in the thickness of the electrolyte layer. [Brief explanation of the drawing]

[0009] [Figure 1] Figure 1 is a cross-sectional view showing an example of a thermoelectric battery according to this disclosure. [Figure 2] Figure 2 is a plan view showing an example of an electrolyte layer and an elastic member. [Figure 3] Figure 3 is a plan view showing the electrolyte layer and elastic member when the electrolyte layer undergoes thermal expansion. [Figure 4] Figure 4 is a plan view showing another example of the electrolyte layer and elastic member. [Modes for carrying out the invention]

[0010] (Knowledge that forms the basis of this disclosure) Thermoelectric batteries, which utilize excited electrons generated by heat and oxidation-reduction reactions in the electrolyte, can generate electricity even without a temperature difference and are expected to be used in a variety of applications. In particular, batteries in which a thermoelectric generator equipped with a thermoelectric conversion layer and an electrolyte layer is housed in a case have the potential to broaden the applications of such thermoelectric batteries.

[0011] In the thermoelectric battery described in Patent Document 1, the deformation of the compressive conductor sandwiched between the thermoelectric element and the case reduces the pressure applied to the thermoelectric element from the case via the compressive conductor, thereby suppressing damage to the thermoelectric element. When the temperature of the thermoelectric element rises, the electrolyte layer may expand due to thermal expansion. Since the compressive conductor can reduce the pressure applied to the thermoelectric element from the case, it is thought that it can also deform to reduce the pressure generated due to the thermal expansion of the electrolyte layer. In this case, the thickness of the electrolyte layer may increase. According to Patent Document 2, the thickness of the electrolyte layer can have a significant impact on the performance of the thermoelectric battery. Therefore, if the thickness of the electrolyte layer increases due to thermal expansion, the performance of the thermoelectric battery may deteriorate.

[0012] Therefore, the inventors of the present invention have been intensively studying day and night whether it is possible to realize a configuration in which the thickness of the electrolyte layer is difficult to change even when the temperature of the thermoelectric element rises and thermal expansion of the electrolyte layer occurs. As a result, it has newly been found that it is important to pressurize the electrolyte layer in the thickness direction to make thermal expansion in the thickness direction of the electrolyte layer difficult to occur. In addition, by providing an elastic member that allows thermal expansion of the electrolyte layer in a direction perpendicular to the thickness direction of the electrolyte layer, it has newly been found that the thickness of the electrolyte layer is difficult to change even when the temperature of the thermoelectric element rises. Based on this new finding, the inventors of the present invention have completed the thermoelectric battery of the present disclosure.

[0013] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. The present disclosure is not limited to the following embodiments. Note that each of the embodiments described below shows an inclusive or specific example. Therefore, numerical values, shapes, materials, components, arrangement positions of the components, connection forms, and the like shown in the following embodiments are merely examples and are not intended to limit the present disclosure. In addition, among the components in the following embodiments, components not described in the independent claims indicating the most superior concept are described as optional components. In the drawings, components with the same reference numerals may be omitted from the description. In addition, the drawings schematically show each component for easy understanding, and the shape, dimensional ratio, and the like may not be accurately shown.

[0014] (Embodiment) FIG. 1 is a cross-sectional view showing an example of the thermoelectric battery of the present disclosure. As shown in FIG. 1, the thermoelectric battery 1a includes a thermoelectric element 10, a first member 21, a second member 22, an insulating member 30, a pressurizing member 40, and an elastic member 50. The thermoelectric element 10 includes a thermoelectric conversion layer 13 and an electrolyte layer 14, and converts thermal energy into electrical energy. In the thermoelectric element 10, the thermoelectric conversion layer 13 and the electrolyte layer 14 are laminated. The thermoelectric conversion layer 13 includes an electron thermal excitation layer 11 and an electron transport layer 12. In the electron thermal excitation layer 11, excited electrons are generated by heat. In addition, in the electron thermal excitation layer 11, holes are generated in pairs with the excited electrons. The electron thermal excitation layer 11 is in contact with the electrolyte layer 14, for example.

[0015] The holes generated in the electron thermal excitation layer 11 are released at the interface between the electron thermal excitation layer 11 and the electrolyte layer 14, into ions M contained in the electrolyte layer 14. m+ This oxidizes the ion M. m+ Aeon M n+ This results in the following: Here, m and n are positive integers, and the condition n > m is satisfied. For example, the condition n = m + 1 is satisfied. Excited electrons generated in the electron thermal excitation layer 11 move to the electron transport layer 12. When there is an excess of electrons in the electron transport layer 12, the electrons move to the outside of the thermoelectric generator 10, pass through the electrical resistance (not shown) outside the thermoelectric cell 1a, and reach the electrolyte layer 14. The electrons that reach the electrolyte layer 14 form ions M in the electrolyte layer 14. n+ This reduces ion M n+ Aeon M m+ It will become. Aeon M n+ Ions M produced by reduction m+ These electrons diffuse toward the interface between the electron thermal excitation layer 11 and the electrolyte layer 14. Through the generation of excited electrons due to this heat and the oxidation-reduction reaction originating from the electrolyte contained in the electrolyte layer 14, the thermoelectric power generator 10 converts thermal energy into electrical energy to generate electricity.

[0016] As shown in Figure 1, in the thermoelectric battery 1a, for example, multiple thermoelectric elements 10 are stacked. The thermoelectric battery 1a may also have only one thermoelectric element 10. As shown in Figure 1, no current collectors are placed between the thermoelectric elements 10. Even in this case, the thermoelectric battery 1a can exhibit the desired performance. Current collectors may be placed between the thermoelectric elements 10. For example, in two adjacent thermoelectric elements 10, electrons that have passed through the electron transport layer 12 of one thermoelectric element 10 can be supplied to the electrolyte layer 14 of the other thermoelectric element 10.

[0017] The electron thermal excitation layer 11 is positioned between the electron transport layer 12 and the electrolyte layer 14 in its thickness direction. The electron thermal excitation layer 11 is not limited to a specific layer as long as excited electrons are generated by heat. The electron thermal excitation layer 11 contains, for example, a predetermined thermoelectric conversion material. Examples of thermoelectric conversion materials include metal semiconductors such as Si and Ge, tellurium compound semiconductors, silicon germanium compound semiconductors, silicide compound semiconductors, skutterudite compound semiconductors, clathrate compound semiconductors, Heusler compound semiconductors, half-Heusler compound semiconductors, metal oxide semiconductors, and organic semiconductors. The electron thermal excitation layer 11 may contain germanium (Ge) as the thermoelectric conversion material. In this case, a large number of excited electrons are easily generated by relatively low-temperature heat. The electron thermal excitation layer 11 may contain a binder, a sintering aid, and additives. The binder binds the thermoelectric conversion material. The sintering aid assists in the molding of the precursor of the electron thermal excitation layer 11 containing the thermoelectric conversion material. The electron thermally excited layer 11 is formed by methods such as squeegeeing, screen printing, discharge plasma sintering, compression molding, sputtering, vacuum deposition, chemical vapor deposition (CVD), and spin coating.

[0018] As described above, the electron transport layer 12 transports excited electrons generated in the electron thermal excitation layer 11 to the outside of the thermoelectric power generator 10. The electron transport layer 12 includes, for example, a predetermined electron transport material. The electron transport material is a material whose conduction charge is the same as or more positive than the conduction charge of the thermoelectric conversion material. The difference between the conduction charge of the electron transport material and the conduction charge of the thermoelectric conversion material is, for example, 0.01V or more and 0.1V or less. Examples of electron transport materials include semiconductor materials, metallic materials, and electron-transporting organic materials. The electron transport layer 12 is formed by methods such as the squeegee method, screen printing method, discharge plasma sintering method, compression molding method, sputtering method, vacuum deposition method, CVD method, and spin coating method.

[0019] Examples of semiconductor materials as electron transport materials are the same as the semiconductors exemplified as the semiconductor materials included in the electron thermal excitation layer 11, for example. Examples of metal-containing materials as electron transport materials are metals, alloys, N-type metal oxides, N-type metal sulfides, alkali metal halides, and alkali metals, etc. Examples of metals included in N-type metal oxides or sulfides are niobium, titanium, zinc, tin, vanadium, indium, tungsten, tantalum, zirconium, molybdenum, and manganese. Examples of electron-transporting organic substances are N-type conductive polymers, N-type low-molecular organic semiconductors, and π-electron conjugated compounds, etc. The electron transport layer 12 may contain a plurality of electron transport materials. The electron transport layer 12 may contain materials other than electron transport materials. The electron transport layer 12 may contain, for example, a binder for bonding electron transport materials, a sintering aid for assisting the molding of the precursor of the electron transport layer 12, and additives.

[0020] The electron transport layer 12 may have a single-layer structure or a multilayer structure. For example, the electron transport layer 12 may be a laminate including a metal layer and a semiconductor layer. In this case, the semiconductor layer may be in contact with the electron thermal excitation layer 11. Examples of metals included in the metal layer are titanium, gold, platinum, silver, tungsten, and tantalum. In this case, chemical reactions of the metal layer are likely to be prevented. The metal layer may be, for example, a platinum layer (Pt layer), and the semiconductor layer may be an N-type Si layer. The N-type Si layer is, for example, a silicon layer doped with phosphorus or the like.

[0021] In the electrolyte layer 14, for example, at the temperature at which excited electrons are generated in the thermoelectric generator 10, a predetermined charge-transporting ion pair can move inside it. The above ions M m+ and ions M n+This can correspond to a charge-transporting ion pair. Current flows through the electrolyte layer 14 as the charge-transporting ion pair moves across it. A "charge-transporting ion pair" is a stable pair of ions with different valencies. When one ion is oxidized or reduced, it becomes the other ion. This allows for the transfer of electrons and holes. The redox potential of the charge-transporting ion pair contained in the electrolyte layer 14 is negative compared to the valence potential of the thermoelectric conversion material contained in the electron-thermal-excitation layer 11. Therefore, at the interface between the electron-thermal-excitation layer 11 and the electrolyte layer 14, the ion in the charge-transporting ion pair that is more easily oxidized is oxidized and becomes the other ion. An example of a charge-transporting ion pair is Fe. 2+ and Fe 3+ , and also, Cu + and Cu 2+ The electrolyte layer 14 may contain ions other than charge transport ion pairs. The electrolyte layer 14 can be formed, for example, by squeegeeing, screen printing, sputtering, vacuum deposition, CVD, sol-gel, or spin coating.

[0022] The electrolyte contained in the electrolyte layer 14 is, for example, a substance that is physically and chemically stable at a desired temperature and contains polyvalent ions. Examples of polyvalent ions are copper ions and iron ions. The electrolyte layer 14 may contain a solid electrolyte, a gel electrolyte, or an electrolyte solution as the electrolyte.

[0023] Examples of solid electrolytes include sodium ion conductors, copper ion conductors, iron ion conductors, lithium ion conductors, silver ion conductors, hydrogen ion conductors, strontium ion conductors, aluminum ion conductors, fluoride ion conductors, chloride ion conductors, and oxide ion conductors. The solid electrolyte is, for example, polyethylene glycol (PEG) or its derivatives having a molecular weight of 600,000 or less. The molecular weight of PEG is the weight-average molecular weight measured in polystyrene terms by gel permeation chromatography. When the solid electrolyte is PEG, for example, polyvalent ion sources such as copper ions and iron ions may be included in the electrolyte layer 14. The electrolyte layer 14 may also contain alkali metal ions. In this case, the lifespan of the thermoelectric battery 1a tends to be longer. The electrolyte layer 14 may also contain materials other than the solid electrolyte. For example, the electrolyte layer 14 may contain a binder for binding the solid electrolyte and a sintering aid for assisting in the molding of the precursor containing the solid electrolyte.

[0024] If the electrolyte layer 14 contains an electrolyte solution, the electrolyte solution may be impregnated into a porous resin membrane, nonwoven fabric, paper, etc., which functions as a separator. The solvent of the electrolyte solution may be water or a non-aqueous solvent.

[0025] An example of a gel electrolyte is a polymer gel. Examples of polymers contained in polymer gels include polyethylene oxide (PEO) polymers, polyacrylonitrile (PAN) polymers, polymethyl methacrylate (PMMA) polymers, and vinylidene fluoride (VDF) copolymers.

[0026] As described above, since the thermoelectric generator 10 converts thermal energy into electrical energy, the temperature around the electrolyte layer 14 may rise. Therefore, thermal expansion may occur in the electrolyte layer 14.

[0027] The first member 21 is electrically conductive. The second member 22 is electrically insulated from the first member 21 and together with the first member 21 constitutes a case 20 that houses the thermoelectric generator 10. The case 20 is, for example, a hollow container. For example, the first member 21 forms the lid of the case 20, and the second member 22 forms the body of the case 20. The first member 21 and the second member 22 are, for example, made of metal or an alloy. An example of an alloy is austenitic stainless steel.

[0028] The first member 21 includes, for example, one of the positive and negative electrodes in the thermoelectric battery 1a. The first member 21 has, for example, a bottom wall 21a and a side wall 21b. The bottom wall 21a is, for example, circular, elliptical, or polygonal in plan view.

[0029] The second member 22 includes, for example, the other of the positive and negative electrodes in the thermoelectric battery 1a. The thermoelectric body 10, insulating member 30, pressurizing member 40, and elastic member 50 are housed inside the second member 22. At least a portion of the side wall 21b of the first member 21 is also located inside the second member 22. The second member 22 has, for example, a bottom wall 22a and side walls 22b. The bottom wall 22a is, for example, circular, elliptical, or polygonal in plan view. For example, in the plurality of electron transport layers 12 contained in the plurality of thermoelectric bodies 10, the electron transport layer 12 closest to the bottom wall 22a of the second member 22 is in contact with the bottom wall 22a.

[0030] The insulating member 30 electrically insulates the first member 21 or the second member 22 from the electrolyte layer 14 and the thermoelectric conversion layer 13 in a direction perpendicular to the thickness direction of the electrolyte layer 14 (z-axis direction). This prevents short circuits in the thermoelectric cell 1a. The insulating member 30 electrically insulates, for example, the first member 21 and the second member 22. The insulating member 30 electrically insulates, for example, the first member 21 or the second member 22 from the entire thermoelectric body 10. The insulating member 30 fills gaps inside the case 20, for example. For example, the insulating member 30 is positioned in contact with the inner surface of the side wall of the first member 21, and the side wall of the second member 22 is surrounded by the insulating member 30. The gap between the side wall 21b of the first member 21 and the side wall 22b of the second member 22 is sealed by the insulating member 30. The insulating member 30 includes, for example, a resin having heat resistance and electrical insulation properties. An example of this resin is a fluorine-containing resin.

[0031] The pressurizing member 40 electrically connects the thermoelectric generator 10 and the first member 21, and pressurizes the electrolyte layer 14 in the thickness direction. The pressurizing member 40 is, for example, conductive and is positioned between the thermoelectric generator 10 and the first member 21. The pressurizing member 40 is made of, for example, metal or an alloy. An example of an alloy is austenitic stainless steel.

[0032] The pressurizing member 40 includes, for example, an elastically deformable member. The repulsive force resulting from the elastic deformation of such a member can pressurize the electrolyte layer 14 in the thickness direction. The pressurizing member 40 may also include a spring. As shown in Figure 1, the pressurizing member 40 includes, for example, a spring 41 and a spacer 42. The spring 41 is elastically deformed while in contact with, for example, the inner surface of the bottom wall 21a of the first member 21. The spacer 42 is positioned between the spring 41 and the thermoelectric generator 10, and uniformly applies the repulsive force generated by the elastic deformation of the spring 41 to the thermoelectric generator 10. The spring 41 is, for example, a spring washer.

[0033] As shown in Figure 1, an electrode plate 16 is positioned between the pressurizing member 40 and the thermoelectric generator 10. One main surface of the electrode plate 16 is in contact with the spacer 42. The other main surface of the electrode plate 16 is in contact with the thermoelectric generator 10. The other main surface of the electrode plate 16 is in contact with the electrolyte layer 14. The electrode plate 16 is made of, for example, metal or an alloy. The spacer 42 may also serve as the electrode plate 16, and the spacer 42 may be in contact with the electrolyte layer 14.

[0034] Figure 2 is a plan view showing an example of the electrolyte layer 14 and the elastic member 50. As shown in Figures 1 and 2, the elastic member 50 is arranged along the same plane (a plane perpendicular to the z-axis) as the electrolyte layer 14 and is a member that can be compressed and deformed by thermal expansion in a direction perpendicular to the thickness direction of the electrolyte layer 14. The elastic member 50 is arranged so as to overlap the electrolyte layer 14 in its thickness direction.

[0035] When the thermoelectric generator 10 converts thermal energy into electrical energy, the temperature around the electrolyte layer 14 rises, causing the electrolyte layer 14 to attempt thermal expansion. On the other hand, when the electrolyte layer 14 attempts thermal expansion in a direction perpendicular to its thickness, the elastic member 50 is compressible and can therefore expand in the same direction. As a result, when the thermoelectric generator 10 converts thermal energy into electrical energy, the thickness of the electrolyte layer 14 does not change easily, and the performance of the thermoelectric battery 1a does not deteriorate easily. In addition, the thermal stress generated in the electrolyte layer 14 tends to be lower, and the durability of the electrolyte layer 14 tends to be higher. Even when the electrolyte layer 14 is not thermally expanding, the elastic member 50 helps prevent the electrolyte layer 14 from shifting in a direction perpendicular to its thickness.

[0036] Figure 3 is a plan view showing the electrolyte layer 14 and the elastic member 50 when the electrolyte layer 14 undergoes thermal expansion. In Figure 3, the dashed line indicates the outline of the electrolyte layer 14 before thermal expansion. As shown in Figure 3, the electrolyte layer 14 expands thermally in a direction perpendicular to its thickness direction (z-axis direction), and its diameter increases in a plan view. On the other hand, as the electrolyte layer 14 expands thermally, the elastic member 50 in the direction perpendicular to the thickness direction of the electrolyte layer 14 undergoes compressive deformation, and its dimensions decrease. When the temperature around the electrolyte layer 14 decreases, the amount of thermal expansion in the direction perpendicular to the thickness direction of the electrolyte layer 14 decreases, and the amount of compressive deformation of the elastic member 50 also decreases.

[0037] The elastic member 50 is adjacent to the electrolyte layer 14 in a direction perpendicular to the thickness direction of the electrolyte layer 14. The elastic member 50 may be in constant contact with the electrolyte layer 14, or it may not be in contact when the amount of thermal expansion of the electrolyte layer 14 is small or when the electrolyte layer 14 is not expanding due to heat.

[0038] The elastic member 50 is not limited to any particular member, as long as it is arranged along the same plane as the electrolyte layer 14 and is a member that can be compressed and deformed by thermal expansion in a direction perpendicular to the thickness direction of the electrolyte layer 14. The elastic member 50 includes, for example, at least one selected from the group consisting of a cavity and an anisotropically elastic polymer material. In this case, the elastic member 50 is easily compressed and deformed by thermal expansion in a direction perpendicular to the thickness direction of the electrolyte layer 14. If the elastic member 50 has a cavity, the cavity may be in communication with the outside of the elastic member 50 or may be formed as a sealed space. The elastic member 50 may be a porous body having open cells. The solid material contained in the elastic member 50 having a cavity may be a resin material or a rubber material.

[0039] An example of anisotropically elastic polymer material is a polymer material in which fillers oriented in a predetermined direction are dispersed in the matrix. The compressive modulus in the direction perpendicular to the thickness direction of the electrolyte layer 14 of an elastic member 50 containing anisotropically elastic polymer material is lower than the compressive modulus in the thickness direction of the elastic member 50.

[0040] As shown in Figure 2, the elastic member 50 is arranged, for example, around the electrolyte layer 14 in a plan view. With this configuration, when the electrolyte layer 14 undergoes thermal expansion in a direction perpendicular to its thickness, it tends to expand uniformly towards the periphery of the electrolyte layer 14. This makes it easier to prevent high thermal stress at specific points in the electrolyte layer 14. The elastic member 50 may also be arranged so that its periphery is in contact with the inner surface of the case 20. The elastic member 50, for example, has an opening in a plan view that conforms to the shape of the electrolyte layer 14, and the electrolyte layer 14 is positioned in that opening.

[0041] As shown in Figure 2, for example, the electrolyte layer 14 is circular in plan view, and the elastic member 50 is annular in plan view. In this case, the center of the elastic member 50 and the center of the electrolyte layer 14 may coincide in plan view. The electrolyte layer 14 may also be elliptical or polygonal in shape, for example.

[0042] As shown in Figures 1 and 2, the elastic member 50 is preferably layered. In this case, the amount of compressive deformation of the elastic member 50 in the direction perpendicular to the thickness direction of the electrolyte layer 14 tends to be large, making it easier to cope with the large amount of thermal expansion in the direction perpendicular to the thickness direction of the electrolyte layer 14.

[0043] Figure 4 is a plan view showing another example of the electrolyte layer 14 and the elastic member 50. As shown in Figure 4, the electrolyte layer 14 is arranged in a ring shape around the elastic member 50 in a plan view. With this configuration, the area of ​​the electrolyte layer 14 in a plan view tends to be large, making it easier to improve the performance of the thermoelectric battery 1a. In this case, the electrolyte layer 14 has an opening in a plan view that conforms to the shape of the elastic member 50, and the elastic member 50 is arranged in that opening.

[0044] (Note) Based on the above description, the following technologies are disclosed. (Technology 1) A thermoelectric power generator comprising a thermoelectric conversion layer including an electron thermal excitation layer and an electron transport layer that generate excited electrons by heat, and an electrolyte layer laminated with the thermoelectric conversion layer, which converts thermal energy into electrical energy, A first member having conductivity, A second member is electrically conductive, electrically insulated from the first member, and together with the first member, constitutes a case for housing the thermoelectric generator. An insulating member that electrically insulates the first member or the second member from the electrolyte layer and the thermoelectric conversion layer in a direction perpendicular to the thickness direction of the electrolyte layer, A pressurizing member electrically connects the thermoelectric generator and the first member and pressurizes the electrolyte layer in the thickness direction, The system comprises an elastic member disposed along the same plane as the electrolyte layer and capable of being compressed and deformed by thermal expansion in a direction perpendicular to the thickness direction of the electrolyte layer, Thermoelectric battery. (Technology 2) Multiple of the aforementioned thermoelectric generators are stacked, A thermoelectric battery as described in Technology 1. (Technology 3) The elastic member includes at least one selected from the group consisting of polymer materials having cavities and anisotropic elasticity. A thermoelectric battery as described in Technology 1 or 2. (Technology 4) The elastic member is positioned around the electrolyte layer in a plan view, or positioned so that the periphery of the elastic member is in contact with the inner surface of the case. A thermoelectric battery as described in any one of the three technical specifications. (Technology 5) The electrolyte layer includes a solid electrolyte, a gel electrolyte, or an electrolyte solution. A thermoelectric battery as described in any one of the technical specifications 1 to 4. [Industrial applicability]

[0045] The thermoelectric battery described herein can be used in a variety of applications, including those of conventional batteries. [Explanation of Symbols]

[0046] 1a Thermoelectric battery 10 Thermoelectric power generators 11 Electron thermal excitation layer 12 Electron transport layer 13 Thermoelectric conversion layer 14 Electrolyte layer 20 cases 21 First component 22 Second component 30 Insulating material 40 Pressurizing member 50 Elastic members

Claims

1. A thermoelectric power generator comprising a thermoelectric conversion layer including an electron thermal excitation layer and an electron transport layer that generate excited electrons by heat, and an electrolyte layer laminated with the thermoelectric conversion layer, which converts thermal energy into electrical energy, A first member having conductivity, A second member is electrically conductive, electrically insulated from the first member, and together with the first member, constitutes a case for housing the thermoelectric generator. An insulating member that electrically insulates the first member or the second member from the electrolyte layer and the thermoelectric conversion layer in a direction perpendicular to the thickness direction of the electrolyte layer, A pressurizing member electrically connects the thermoelectric generator and the first member and pressurizes the electrolyte layer in the thickness direction, The system comprises an elastic member disposed along the same plane as the electrolyte layer and capable of compression deformation by thermal expansion in a direction perpendicular to the thickness direction of the electrolyte layer, Thermoelectric battery.

2. Multiple of the aforementioned thermoelectric generators are stacked, The thermoelectric battery according to claim 1.

3. The elastic member includes at least one selected from the group consisting of polymer materials having cavities and anisotropic elasticity. The thermoelectric battery according to claim 1.

4. The elastic member is positioned around the electrolyte layer in a plan view, or positioned so that the periphery of the elastic member is in contact with the inner surface of the case. The thermoelectric battery according to claim 1.

5. The electrolyte layer includes a solid electrolyte, a gel electrolyte, or an electrolyte solution. The thermoelectric battery according to claim 1.

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