Patent Application
20220254979
The present disclosure relates to a thermoelectric generation device.
As elements that convert thermal energy into electrical energy, heat utilization power generation elements obtained by combining an electrolyte and a thermoelectric conversion material that generates thermally excited electrons and holes are known (see Patent Literature 1). According to a power generation system using the heat utilization power generation elements, it is possible to generate power simply by raising a temperature of the entire system without causing a temperature difference in the system.
For example, in order to achieve both high output and compactness of a power generation system using the elements described in Patent Literature 1, it is necessary to increase energy density of a thermoelectric generation device as much as possible. The present disclosure provides a thermoelectric generation device useful for increasing energy density.
A thermoelectric generation device according to an aspect of the present disclosure includes a first thermoelectric generation module having at least one heat utilization power generation element and a first housing that accommodates the heat utilization power generation element, a second thermoelectric generation module having at least one heat utilization power generation element and a second housing that accommodates the heat utilization power generation element, and an electroconductive member electrically connecting the first and second thermoelectric generation modules, wherein an outer surface of the first housing is in contact with an outer surface of the second housing. The heat utilization power generation element includes at least an electrolyte layer and a thermoelectric conversion layer. Since the outer surface of the first housing is in contact with the outer surface of the second housing, it is possible to make the thermoelectric generation device compact in size.
When the outer surface of the first housing is in contact with the outer surface of the second housing, it is advantageous in terms of compactness, but a situation in which heat is unlikely to be supplied to the thermoelectric generation module according to operating conditions of the thermoelectric generation device or the like may occur. If heat is not efficiently supplied to the thermoelectric generation module, even though the power generation system has a potential to generate high-voltage and/or high-current electricity, the potential cannot be sufficiently exhibited. From a viewpoint of efficiently supplying heat to the thermoelectric generation module and thereby realizing stable power generation, at least a part of each of the first and second housings may be formed of a material having electrical insulation properties and heat transfer properties or may be formed of a first material having electrical insulation properties and a second material having heat transfer properties embedded inside the first material.
The first and second thermoelectric generation modules may be electrically connected in parallel or may be electrically connected in series. By connecting a plurality of thermoelectric generation modules in series, it is possible to increase an electromotive force of the thermoelectric generation device. On the other hand, by connecting a plurality of thermoelectric generation modules in parallel, it is possible to increase an output current of the thermoelectric generation device.
From a viewpoint of increasing the electromotive force and/or the output current, the first and second thermoelectric generation modules may each have a plurality of the heat utilization power generation elements. The plurality of heat utilization power generation elements may be stacked to be electrically connected in series or may be stacked to be electrically connected in parallel. In a case in which the plurality of heat utilization power generation elements are electrically connected in series, from a viewpoint of further increasing the electromotive force, an electron transmission layer may be provided between the adjacent heat utilization power generation elements. In a case in which the plurality of heat utilization power generation elements are electrically connected in parallel, a collecting electrode electrically connected to the electroconductive member and an insulating layer may be provided between the adjacent heat utilization power generation elements.
According to the present disclosure, a thermoelectric generation device useful for increasing energy density is provided.
Hereinafter, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. In the following description, the same reference signs will be used for the same elements or elements having the same function and duplicate description will be omitted.
The thermoelectric generation module 10A has two heat utilization power generation elements 5a and 5b, an electron transmission layer 6, a pair of collecting electrodes 8a and 8b, and a housing 9 for accommodating them. A shape of the thermoelectric generation module 10A in a plan view is a polygonal shape such as a rectangular shape and may be a circular shape or an elliptical shape. The two heat utilization power generation elements 5a and 5b are stacked to be electrically connected in series. The heat utilization power generation elements 5a and 5b generate thermally excited electrons and holes using heat supplied from the outside. The generation of thermally excited electrons and holes by the heat utilization power generation elements 5a and 5b occurs, for example, at 25° C. or higher and 300° C. or lower. From a viewpoint of generating a sufficient number of thermally excited electrons and holes, the heat utilization power generation elements 5a and 5b may be heated to, for example, 50° C. or higher. From a viewpoint of satisfactorily preventing deterioration of the heat utilization power generation elements 5a and 5b, an upper limit of a heating temperature of each of the heat utilization power generation elements 5a and 5b is, for example, 200° C. A temperature at which a sufficient number of thermally excited electrons are generated is, for example, a temperature at which density of the thermally excited electrons of each of the heat utilization power generation elements 5a and 5b is 1015/cm3 or more.
The heat utilization power generation element 5a has a stacked structure including an electrolyte layer 1, an electron thermal excitation layer 2a, and an electron transport layer 2b in that order. A thermoelectric conversion layer 2 is constituted by the electron thermal excitation layer 2a and the electron transport layer 2b. In the present embodiment, a configuration of the heat utilization power generation element 5b is the same as that of the heat utilization power generation element 5a, and thus description thereof will be omitted.
The electrolyte layer 1 is a layer containing a solid electrolyte in which a charge transport ion pair can move under the above temperature conditions. As the charge transport ion pair moves in the electrolyte layer 1, a current flows in the electrolyte layer 1. The “charge transport ion pair” is a stable pair of ions with different valences. When one ion is oxidized or reduced, it becomes the other ion and can move electrons and holes. An oxidation-reduction potential of the charge transport ion pair in the electrolyte layer 1 is lower than a valence band potential of a thermoelectric conversion material contained in the electron thermal excitation layer 2a. Therefore, at an interface between the electron thermal excitation layer 2a and the electrolyte layer 1, an easily oxidizable ion of the charge transport ion pairs is oxidized and becomes the other ion. The electrolyte layer 1 may contain ions other than the charge transport ion pair. The electrolyte layer 1 can be formed by, for example, a squeegee method, a screen printing method, a sputtering method, a vacuum vapor deposition method, a CVD method, a sol-gel method, or a spin coating method. A thickness of the electrolyte layer 1 is, for example, 0.1 μm or more and 100 μm or less. The electrolyte layer 1 may be a hole transport semiconductor.
The solid electrolyte contained in the electrolyte layer 1 is, for example, a substance that is physically and chemically stable at the above temperatures and contains a polyvalent ion. The solid electrolyte is, for example, a sodium ion conductor, a copper ion conductor, an iron ion conductor, a lithium ion conductor, a silver ion conductor, a hydrogen ion conductor, a strontium ion conductor, an aluminum ion conductor, a fluorine ion conductor, a chlorine ion conductor, an oxide ion conductor, or the like. The solid electrolyte may be, for example, polyethylene glycol (PEG) having a molecular weight of 600,000 or less or a derivative thereof. In a case in which the solid electrolyte is PEG, for example, a polyvalent ion source such as a copper ion or an iron ion may be contained in the electrolyte layer 1. From a viewpoint of improving a life span, an alkali metal ion may be contained in the electrolyte layer 1. The molecular weight of PEG corresponds to a weight-average molecular weight measured by gel permeation chromatography in terms of polystyrene. The electrolyte layer 1 may contain materials other than the solid electrolyte. For example, the electrolyte layer 1 may contain a binder for binding the solid electrolyte, a sintering aid for assisting formation of the solid electrolyte, or the like.
The electron thermal excitation layer 2a is a layer that generates thermally excited electrons and holes and is in contact with the electrolyte layer 1. The electron thermal excitation layer 2a contains a thermoelectric conversion material. The thermoelectric conversion material is a material in which excited electrons increase in a high temperature environment and is a semiconductor material such as a metal semiconductor (Si, Ge), a tellurium compound semiconductor, a silicon-germanium (Si—Ge) compound semiconductor, a silicide compound semiconductor, a skutterudite compound semiconductor, a clathrate compound semiconductor, a Heusler compound semiconductor, a half-Heusler compound semiconductor, a metal oxide semiconductor, or an organic semiconductor. From a viewpoint of generating sufficient thermally excited electrons at a relatively low temperature, the thermoelectric conversion material may be germanium (Ge). The electron thermal excitation layer 2a may contain a plurality of thermoelectric conversion materials. The electron thermal excitation layer 2a may contain materials other than the thermoelectric conversion material. For example, the electron thermal excitation layer 2a may contain a binder for binding the thermoelectric conversion material, a sintering aid for assisting formation of the thermoelectric conversion material, or the like. The electron thermal excitation layer 2a is formed by, for example, a squeegee method, a screen printing method, a discharge plasma sintering method, a compression forming method, a sputtering method, a vacuum vapor deposition method, a chemical vapor deposition method (a CVD method), a spin coating method, or the like. A thickness of the electron thermal excitation layer 2a is, for example, 0.1 μm or more and 100 μm or less.
The electron transport layer 2b is a layer that transports the thermally excited electrons generated in the electron thermal excitation layer 2a to the outside and is located on a side opposite to the electrolyte layer 1 via the electron thermal excitation layer 2a in a stacking direction. The electron transport layer 2b contains an electron transport material. The electron transport material is a material of which a conduction band potential is the same as or higher than a conduction band potential of the thermoelectric conversion material. A difference between the conduction band potential of the electron transport material and the conduction band potential of the thermoelectric conversion material is, for example, 0.01 V or more and 0.1 V or less. The electron transport material is, for example, a semiconductor material, an electron transport organic substance, or the like. The electron transport layer 2b is formed by, for example, a squeegee method, a screen printing method, a discharge plasma sintering method, a compression forming method, a sputtering method, a vacuum vapor deposition method, a CVD method, a spin coating method, or the like. A thickness of the electron transport layer 2b is, for example, 0.1 μm or more and 100 μm or less.
The semiconductor material used for the electron transport material is, for example, the same as the semiconductor material contained in the electron thermal excitation layer 2a. The electron transport organic substance is, for example, an N-type electroconductive polymer, an N-type low-molecular-weight organic semiconductor, a 7r-electron conjugated compound, or the like. The electron transport layer 2b may contain a plurality of electron transport materials. The electron transport layer 2b may contain materials other than the electron transport material. For example, the electron transport layer 2b may contain a binder for binding the electron transport material, a sintering aid for assisting formation of the electron transport material, or the like. From a viewpoint of electron transportability, the semiconductor material may be n-type Si. The electron transport layer 2b containing n-type Si is formed, for example, by doping a silicon layer with phosphorus or the like.
The electron transmission layer 6 is a layer for conducting electrons moving in the thermoelectric generation module 10A only in a predetermined direction. The electron transmission layer 6 is a layer that exhibits electron conductivity and does not exhibit ionic conductivity. Therefore, the electron transmission layer 6 can be called an ion conduction prevention layer. The electron transmission layer 6 is interposed between the electron transport layer 2b of the heat utilization power generation element 5a and the electrolyte layer 1 of the heat utilization power generation element 5b. The heat utilization power generation elements 5a and 5b are connected in series with each other via the electron transmission layer 6.
The electron transmission layer 6 is formed by, for example, a squeegee method, a screen printing method, a discharge plasma sintering method, a compression forming method, a sputtering method, a vacuum vapor deposition method, a CVD method, a spin coating method, a plating method, or the like. In a case in which the electrolyte layer 1 is an organic electrolyte layer, the electron transmission layer 6 may be provided, for example, on a surface of the electron transport layer 2b of the heat utilization power generation element 5a. On the other hand, in a case in which the electrolyte layer 1 is an inorganic electrolyte layer, the electron transmission layer 6 may be provided, for example, on a surface of the electrolyte layer 1 of the heat utilization power generation element 5b. A thickness of the electron transmission layer 6 is, for example, 0.1 μm or more and 100 μm or less.
A work function of the electron transmission layer 6 is larger than a work function of the electron transport layer 2b. In other words, a band gap of the electron transmission layer 6 is larger than a band gap of the electron transport layer 2b. A difference between the work function or band gap of the electron transmission layer 6 and the band gap of the electron transport layer 2b is, for example, 0.1 eV or more. Further, a valence band potential of the electron transmission layer 6 may be higher than a reduction potential of the ions in the electrolyte layer 1. In this case, an oxidation reaction of the ions is unlikely to occur at an interface between the electron transmission layer 6 and the electrolyte layer 1. For example, in a case in which the electrolyte layer 1 is an organic electrolyte layer, the electron transmission layer 6 contains indium tin oxide (ITO), fluorine-doped tin oxide (FTO), an electron transmission polymer material, or the like. Further, for example, when the electrolyte layer 1 is an inorganic electrolyte layer, the electron transmission layer 6 contains platinum (Pt), gold (Au), silver (Ag), an aluminum alloy (for example, duralumin or a Si—Al alloy), an electron transmission polymer material, or the like. The electron transmission polymer material is, for example, PEDOT/PSS. A conduction band potential of the electron transmission layer 6 may be lower than a conduction band potential of the electron transport layer 2b. In this case, electrons easily move from the electron transport layer 2b to the electron transmission layer 6.
The collecting electrode 8a is a positive electrode of the thermoelectric generation module 10A and is located at one end of the thermoelectric generation module 10A in the stacking direction. The collecting electrode 8b is a negative electrode of the thermoelectric generation module 10A and is located at the other end of the thermoelectric generation module 10A in the stacking direction. Each of the collecting electrodes 8a and 8b is, for example, an electroconductive plate having a single-layer structure or a stacked structure. The electroconductive plate is, for example, a metal plate, an alloy plate, or a composite plate of a metal plate and an alloy plate. From a viewpoint of satisfactorily exhibiting performance of the thermoelectric generation module 10A, at least one of the collecting electrodes 8a and 8b may exhibit high thermal conductivity. For example, the thermal conductivity of at least one of the collecting electrodes 8a and 8b may be 10 W/m·K or more. Since no temperature difference is required in the thermoelectric generation module 10A, it is desirable that both the collecting electrodes 8a and 8b exhibit high thermal conductivity.
The housing 9 accommodates the heat utilization power generation elements 5a and 5b or the like. The housing 9 is made of, for example, a material having excellent heat transfer properties and insulation properties. Due to the high heat transfer properties of the housing 9, heat is efficiently supplied to the heat utilization power generation elements 5a and 5b from the outside. Examples of a material of the housing 9 include a resin containing Si (a Si heat transfer resin), ceramics, and high thermal conductive glass. In order to achieve more excellent heat transfer properties of the housing 9 while maintaining the insulating properties thereof, the housing 9 may be formed of one material having insulation properties and another material (for example, a metal) having heat transfer properties embedded inside the one material.
By disposing the thermoelectric generation device 50 in a high temperature environment, it is possible to generate electricity with high energy density. The thermoelectric generation device 50 can efficiently generate high-voltage and/or high-current electricity when applied to, for example, a power generation system using a high-temperature furnace, a hot spring, or geothermal heat as a heat source. The thermoelectric generation module 10A may be relatively small in scale or large in scale. A power generation output of the thermoelectric generation module 10A according to the present embodiment may be, for example, 1000 kWh or more, 10 to 1000 kWh, or 0.1 to 10 kWh.
Although the thermoelectric generation device 50 of the first embodiment has been described in detail above, the configuration of the thermoelectric generation device 50 may be changed as follows. For example, the number of heat utilization power generation elements included in each thermoelectric generation module is not limited to two and may be one or may be three or more. Further, the number of thermoelectric generation modules is not limited to three and may be two or may be four or more. Further, the electrical connection of the plurality of thermoelectric generation modules is not limited to a parallel connection and may be a serial connection (see
As in the heat utilization power generation element 5a, the heat utilization power generation elements 15a, 15b, and 15c each have the stacked structure including the electrolyte layer 1, the electron thermal excitation layer 2a, and the electron transport layer 2b in that order. The heat utilization power generation elements 15a, 15b, and 15c are each interposed by a pair of collecting electrodes 17a and 17b in the stacking direction. The three collecting electrodes 17a are electrically connected to the external electrode 18a, and the three collecting electrodes 17b are electrically connected to the external electrode 18b.
The insulating layer 16a prevents a short circuit between the heat utilization power generation elements 15a and 15b. The insulating layer 16b prevents a short circuit between the heat utilization power generation elements 15b and 15c. The insulating layer 16a includes, for example, an organic insulating material or inorganic insulating material exhibiting heat resistance. The organic insulating material is, for example, a heat resistant plastic. The inorganic insulating material is, for example, ceramics such as alumina. From a viewpoint of satisfactorily exhibiting performance of the thermoelectric generation module 20A, the insulating layers 16a and 16b may exhibit high thermal conductivity. For example, the thermal conductivity of each of the insulating layers 16a and 16b may be 10 W/m·K or more. Alternatively, the insulating layers 16a and 16b may each contain a member or particle exhibiting excellent heat transfer properties. As long as the member or particle is embedded in the insulating material, the member or particle may be electroconductive.
By disposing the thermoelectric generation device 60 in a high temperature environment, it is possible to generate electricity with high energy density. The thermoelectric generation device 60 can efficiently generate high-voltage and/or high-current electricity when applied to, for example, a power generation system using a high-temperature furnace, a hot spring, or geothermal heat as a heat source. The thermoelectric generation module 20A may be relatively small in scale or large in scale. A power generation output of the thermoelectric generation module 20A may be, for example, 1000 kWh or more, 10 to 1000 kWh, or 0.1 to 10 kWh.
Although the thermoelectric generation device 60 of the second embodiment has been described in detail above, the configuration of the thermoelectric generation device 60 may be changed as follows. For example, the number of heat utilization power generation elements included in each thermoelectric generation module is not limited to three and may be one or two or may be four or more. Further, the number of thermoelectric generation modules is not limited to three and may be two or may be four or more. The electrical connection of the plurality of thermoelectric generation modules is not limited to a parallel connection and may be a serial connection (see
According to the present disclosure, a thermoelectric generation device useful for increasing energy density is provided.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-119043 | Jun 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2020/023798 | 6/17/2020 | WO |
