Heat-utilizing power generation module and method for manufacturing heat-utilizing power generation module

Abstract

This heat-utilizing power generation module comprises: a first insulating film and a second insulating film; a plurality of heat-utilizing power generation elements which are each obtained by laminating a semiconductor layer that generates thermally-excited electrons and holes, a conductive polymer layer that contains an electron transport material, and an electrolyte layer that is disposed between the semiconductor layer A and the conductive polymer layer and that contains a solid electrolyte or electrolyte solution in which charge-transporting ion pairs can move, the plurality of heat-utilizing power generation elements being disposed between the first insulating film and the second insulating film so as to be spaced apart from each other in a plan view; and a conductor that connects the conductive polymer layers and the semiconductor layers of adjacent heat-utilizing power generation elements. The heat-utilizing power generation elements connected by the conductor are such that the semiconductor layer of one heat-utilizing power generation element is disposed at the first insulating film side and the semiconductor layer of the other heat-utilizing power generation element is disposed at the second insulating film side.

Description

Thermal power generation module and method for manufacturing the thermal power generation module

[0001] The present disclosure relates to a thermal power generation module and a method for manufacturing the thermal power generation module.

[0002] Examples of thermal power generation using geothermal energy or factory waste heat include a method using the Seebeck effect. Examples of thermal power generation that does not use the Seebeck effect include the thermal power generation element disclosed in International Publication No. 2017 / 038988.

[0003] International Publication No. 2017 / 038988 discloses a method for converting thermal energy into electrical energy using a thermoelectric power generation element that combines an electrolyte and a thermoelectric conversion material. By using such a thermoelectric power generation element as a power source for electronic components, it is possible to supply stable power to the electronic components, even in high-temperature environments (e.g., 50°C or higher) where general batteries are prone to degradation.

[0004] As a practical application of the technology disclosed in International Publication No. 2017 / 038988, there is a demand for modularization of power generation devices, and in particular, when connecting multiple thermoelectric generation elements having an electrolyte and a thermoelectric conversion material, there is a demand for preventing disconnections and short circuits.

[0005] The present disclosure has been made in consideration of the above facts, and aims to provide a thermal power generation module in which disconnections and short circuits between multiple thermoelectric power generation elements are suppressed, and a method for manufacturing a thermal power generation module.

[0006] A thermal power generation module according to a first aspect of the present disclosure includes a stack of first and second insulating films, a semiconductor layer that generates thermally excited electrons and holes, a conductive polymer layer containing an electron transport material, and an electrolyte layer that is disposed between the semiconductor layer and the conductive polymer layer and contains a solid electrolyte or an electrolyte solution in which charge-transporting ion pairs can move, the thermal power generation module comprising: a plurality of thermal power generation elements that are spaced apart from each other in a planar view between the first insulating film and the second insulating film; and a conductor that connects the semiconductor layer and the conductive polymer layer of adjacent thermal power generation elements, wherein the thermal power generation elements connected by the conductor have the semiconductor layer of one of the thermal power generation elements disposed on the first insulating film side and the semiconductor layer of the other of the thermal power generation elements disposed on the second insulating film side.

[0007] In the thermal power generation module of the first aspect, the thermal power generation elements connected by a conductor have the semiconductor layer of one thermal power generation element arranged on the first insulating film side and the semiconductor layer of the other thermal power generation element arranged on the second insulating film side. Therefore, the conductor connecting one thermal power generation element to the other can be formed on one side in the stacking direction. That is, the conductor can be formed closer to either the first insulating film side or the second insulating film side. This makes it possible to easily obtain a thermal power generation module that is less susceptible to breaks and short circuits.

[0008] A second aspect of the thermal power generation module of the present disclosure is a thermal power generation module of the first aspect, in which adjacent thermal power generation elements have the semiconductor layer of one of the thermal power generation elements arranged on the first insulating film side, and the semiconductor layer of the other thermal power generation element arranged on the second insulating film side.

[0009] According to the thermal power generation module of the second aspect, the conductors connecting adjacent thermal power generation elements can be formed closer to either the first insulating film side or the second insulating film side, which allows adjacent thermal power generation elements to be connected by conductors on the same insulating film, resulting in a simple connection pattern.

[0010] A third aspect of the present disclosure is a thermal power generation module in which, in the thermal power generation module of the first or second aspect, one end of the conductor is overlapped with a portion of the semiconductor layer and the other end is overlapped with a portion of the conductive polymer layer.

[0011] The thermal power generation module of the third aspect can be easily formed by laminating a part of the conductor on the thermal power generation element.

[0012] A fourth aspect of the present disclosure is a thermal power generation module according to the first or second aspect, wherein the conductor is formed by extending a portion of the conductive polymer layer.

[0013] According to the thermal power generation module of the fourth aspect, the conductive polymer layer can also serve as a conductor.

[0014] In a thermal power generation module according to a fifth aspect of the present disclosure, the semiconductor layer includes a thermally meltable polymer.

[0015] According to the fifth aspect of the thermal power generation module, the polymer contained in the semiconductor layer is melted and thermally fused to the first insulating film and the second insulating film, thereby appropriately connecting the conductor and the semiconductor layer and preventing breakage.

[0016] A sixth aspect of the present disclosure provides a method for manufacturing a thermal power generation module having a power generation element pattern including a plurality of thermal power generation elements each having a semiconductor layer, an electrolyte layer, and a conductive polymer layer stacked thereon, and a conductor electrically connecting the plurality of thermal power generation elements, the method comprising the steps of: forming a first pattern that is a part of the power generation element pattern on a first insulating film such that the conductive polymer layer and the conductor are arranged on the first insulating film side; forming a second pattern that is a remainder of the power generation element pattern on a second insulating film such that the conductive polymer layer and the conductor are arranged on the second insulating film side; and joining the first insulating film and the second insulating film such that the first pattern and the second pattern form the power generation element pattern.

[0017] In the sixth aspect of the method for manufacturing a thermal power generation module, a first pattern that is a part of the power generation element pattern is formed so that the conductive polymer layer and the conductor are located on the first insulating film side, a second pattern that is the remainder of the power generation element pattern is formed on the second insulating film so that the conductive polymer layer and the conductor are located on the first insulating film side, and the first insulating film and the second insulating film are joined together. Therefore, the conductor can be formed closer to either the first insulating film side or the second insulating film side, making it possible to easily manufacture a thermal power generation module that is suppressed from breaking or shorting.

[0018] A seventh aspect of the present disclosure relates to a method for manufacturing a thermal power generation module, and in the method for manufacturing a thermal power generation module of the sixth aspect, the semiconductor layer includes a thermally meltable polymer, and when joining the first insulating film and the second insulating film, the semiconductor layer of the first pattern is welded to the second insulating film of the second pattern by thermal melting, and the semiconductor layer of the second pattern is welded to the first insulating film of the first pattern by thermal melting.

[0019] According to the seventh aspect of the manufacturing method for a thermal power generation module, the polymer contained in the semiconductor layer is melted and welded to the first insulating film and the second insulating film, thereby making it possible to properly connect with the conductor and suppress breakage.

[0020] As described above, the present disclosure can provide a thermal power generation module in which disconnections and short circuits between multiple thermoelectric power generation elements are suppressed, and a method for manufacturing the thermal power generation module.

[0021] FIG. 1 is a schematic plan view of a thermal power generation module of a first embodiment. FIG. 2 is a cross-sectional view taken along line II-II in FIG. 1. FIG. 3 is a schematic plan view of a first pattern of the thermal power generation module of the first embodiment. FIG. 4 is a schematic plan view of a second pattern of the thermal power generation module of the first embodiment. FIG. 5 is a schematic plan view of a thermal power generation module of a second embodiment. FIG. 6 is a cross-sectional view taken along line 6-6 in FIG. 5. FIG. 7 is a schematic plan view of a thermal power generation module of a third embodiment. FIG. 8 is a cross-sectional view taken along line 8-8 in FIG. 7. FIG. 8 is a schematic plan view of a thermal power generation module of a fourth embodiment. FIG. 9 is a cross-sectional view of a thermal power generation module of a fourth embodiment. FIG. 10 is a cross-sectional view of a thermal power generation module of a fourth embodiment. FIG. 11 is a cross-sectional view of a thermal power generation module of a fourth embodiment.

[0022] Hereinafter, a thermal power generation module and a method for manufacturing a thermal power generation module according to an embodiment of the present disclosure will be described with reference to the drawings.

[0023] <First Embodiment> Fig. 1 shows a schematic plan view of a thermal power generation module 10 according to a first embodiment (hereinafter referred to as the present embodiment). For ease of explanation, Fig. 1 does not show a first insulating film 22 (described later) (the first insulating film 22 is indicated by a two-dot chain line). The thermal power generation module 10 has a rectangular shape in plan view as a whole, and includes the first insulating film 22, a second insulating film 32, a plurality of (six in total in this embodiment) thermal power generation elements 24, 26, 28, 34, 36, and 38, and conductors 42, 43, and 44.

[0024] The first insulating film 22 and the second insulating film 32 are sheet-shaped and form the outer shape of the thermal power generation module 10 in a plan view. The first insulating film 22 and the second insulating film 32 are sheet-shaped and have insulating properties, and a polymer-coated metal (aluminum, copper, etc.) sheet or the like can be used. The thickness of the first insulating film 22 and the second insulating film 32 is preferably, for example, 0.1 μm or more and 5000 μm or less.

[0025] The thermal energy harvesters 24, 26, 28, 34, 36, and 38 each include a semiconductor layer that generates thermally excited electrons and holes, an electrolyte layer containing a solid electrolyte or electrolyte solution through which charge-transporting ion pairs can migrate, and a conductive polymer layer containing an electron transport material. For each of the thermal energy harvesters 24, 26, 28, 34, 36, and 38, the semiconductor layer is designated with a symbol ending in A, the electrolyte layer is designated with a symbol ending in B, and the conductive polymer layer is designated with a symbol ending in C. For example, the layers of the thermal energy harvester 24 are designated as the semiconductor layer 24A, the electrolyte layer 24B, and the conductive polymer layer 24C. Furthermore, when describing each layer commonly across all of the thermal energy harvesters 24, 26, 28, 34, 36, and 38, they are simply referred to as the semiconductor layer A, the electrolyte layer B, and the conductive polymer layer C. The electrolyte layer B is disposed between the semiconductor layer A and the conductive polymer layer C. The thermal power generation element may be formed as a single layer of a semiconductor layer A, an electrolyte layer B, and a conductive polymer layer C, or may be formed as a multiple layer (e.g., two or three layers) of a combination of a semiconductor layer A, an electrolyte layer B, and a conductive polymer layer C.

[0026] The thermal power generation elements 24, 26, 28, 34, 36, and 38 are arranged spaced apart from one another in a 2×3 array, as shown in Fig. 1, and are sandwiched between a first insulating film 22 and a second insulating film 32, as shown in Fig. 2. The thermal power generation elements 24, 26, and 28 are arranged in positions that are not adjacent to one another in the 2×3 array, and the thermal power generation elements 34, 36, and 38 are arranged so as to fill the spaces between the thermal power generation elements 24, 26, and 28.

[0027] The thermal power generation elements 24, 26, and 28 have the semiconductor layer A side bonded to the second insulating film 32 and the conductive polymer layer C side bonded to the first insulating film 22. The thermal power generation elements 34, 36, and 38 have the conductive polymer layer C side bonded to the second insulating film 32 and the semiconductor layer A side bonded to the first insulating film 22. In other words, the stacking order of the semiconductor layer A, electrolyte layer B, and conductive polymer layer C is reversed between the thermal power generation elements 24, 26, and 28 and the thermal power generation elements 34, 36, and 38.

[0028] The conductors 42A, 42B, 42C, 43A, and 43B are laminated on a portion of one semiconductor layer A and on a portion of the other conductive polymer layer C so as to connect one semiconductor layer A and the other conductive polymer layer C of adjacent thermal power generation elements. The conductors 42A, 42B, and 42C are formed on the first insulating film 22, and the conductors 43A, 43B, 44A, and 44B are formed on the second insulating film 32.

[0029] Conductor 42A connects semiconductor layer 34A and conductive polymer layer 26C, conductor 42B connects semiconductor layer 38A and conductive polymer layer 28C, and conductor 42C connects semiconductor layer 36A and conductive polymer layer 24C. Conductor 43A connects semiconductor layer 26A and conductive polymer layer 38C, and conductor 43B connects semiconductor layer 28A and conductive polymer layer 36C. One end of conductor 44A is connected to conductive polymer layer 34C. One end of conductor 44B is connected to semiconductor layer 24A.

[0030] The conductor 44A at one terminal is connected in series through the thermoelectric power generating elements 34, 26, 38, 28, 36, and 24 to the conductor 44B at the other terminal.

[0031] (Semiconductor Layer) The semiconductor layer A includes a semiconductor. In the present disclosure, "semiconductor" refers to a material that can generate thermally excited electrons and holes by heat. Specific examples include metal semiconductors, tellurium compound semiconductors, silicon germanium (Si-Ge) compound semiconductors, silicide compound semiconductors, skutterudite compound semiconductors, clathrate compound semiconductors, Heusler compound semiconductors, half-Heusler compound semiconductors, metal oxide semiconductors, organic semiconductors, and other semiconductors. The semiconductor used in the present disclosure functions as a thermoelectric conversion material. Examples of metal semiconductors include Si semiconductors and Ge semiconductors.

[0032] Tellurium compound semiconductors include Bi-Te compounds (e.g., Bi2Te3, Sb2Te3, CsBi4Te6, Bi2Se3, Bi o .4Sb 1.6 Te3, Bi2(Se,Te)3, (Bi,Sb)2(Te,Se)3, (Bi,Sb)2Te3, or Bi2Te2.95 Se 0.05 ), Pb-Te compounds (e.g., PbTe or Pb 1-x Sn x Te), SnTe, Ge-Te, AgSbTe2, Ag-Sb-Ge-Te compounds (e.g., GeTe-AgSbTe2 (TAGS)), Ga2Te3, (Ga 1-x In x )2 Te3, Tl2Te-Ag2Te, Tl2Te-Cu2Te, Tl2Te-Sb2Te3, Tl2Te-Bi2Te3, Ti2Te-GeTe, Ag8Tl2Te5, Ag9TlTe5, Tl9BiTe6, Tl9SbTe6, Tl9CuTe5, Tl4SnTe3, Tl4PbTe3, or Tl 0.02 Pb 0.98 Te can be mentioned.

[0033] Silicon germanium (Si-Ge) compound semiconductors include Si x Ge 1-x or SiGe-GaP.

[0034] Silicide compound semiconductors include β-FeSi2 compounds (e.g., β-FeSi2, Fe 1-x Mn x Si2, Fe 0.95 Mn 0.05 Si ( 2-y )Al y , FeSi ( 2-y )Al y , Fe 1-y Co y Si2), Mg2Si, MnSi 1.75-x , Ba8Si 46 , Ba8Ga 16 Si 30 , or CrSi2.

[0035] Skutterudite compound semiconductors include compounds represented by the formula TX3 (wherein T is a transition metal selected from the group consisting of Co, Fe, Ru, Os, Rh, and Ir, and X is a pnictogen selected from the group consisting of P, As, and Sb), derivatives of the compounds represented by the formula RM4X 12(wherein R is a rare earth selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; M is selected from the group consisting of Fe, Ru, Os, and Co; and X is selected from the group consisting of P, As, and Sb), y Fe 4-x Co x Sb 12 , (CeFe3CoSb 12 ) 1-x (MoO2) x or (CeFe3CoSb 12 ) 1-x (WO2) x Examples include:

[0036] Clathrate compound semiconductors include those with the formula M8X 46 (M is selected from the group consisting of Ca, Sr, Ba, and Eu, and X is selected from the group consisting of Si, Ge, and Sn), a compound represented by formula (II)8(III) 16 (IV) 30 (wherein II is a group II element, III is a group III element, and IV is a group IV element) 16 (IV) 30 As a compound of the formula, for example, Ba8Ga x Ge 46-x , Ba 8-x (Sr,Eu) x Au6Ge 40 , or Ba 8-x EU x Cu6Si 40 ) can be mentioned.

[0037] Heusler compound semiconductors include Fe2VAl, (Fe 1-x Re x )2VAl, or Fe2(V 1-x-y Ti x Ta y )Al can be mentioned.

[0038] Examples of half-Heusler compound semiconductors include compounds represented by the formula MSiSn (wherein M is selected from the group consisting of Ti, Zr, and Hf), compounds represented by the formula MNiSn (wherein M is Ti or Zr), compounds represented by the formula MCoSb (wherein M is selected from the group consisting of Ti, Zr, and Hf), and compounds represented by the formula LnPdX (wherein Ln is selected from the group consisting of La, Gd, and Er, and X is Bi or Sb).

[0039] Metal oxide semiconductors include In2O3-SnO2, (CaBi)MnO3, Ca(Mn, In)O3, Na x V2O5, V2O5, ZnMnGaO4 and its derivatives, La RhO3, LaNiO3, SrTiO3, SrTiO3:Nb, Bi2Sr2Co2O y , Na x CoO2, NaCo2O4, CaPd3O4, formula Ca a M 1 b Co C M 2 d Ag e O f (In the formula, M 1 is one or more elements selected from the group consisting of Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and rare earth elements, and M 2 is one or two elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Mo, W, Nb, Ta and Bi, and the ranges are 2.2≦a≦3.6, 0≦b≦0.8, 2≦c≦4.5, 0≦d≦2, 0≦e≦0.8, and 8≦f≦10), ZnO, Na(Co,Cu)2O4, ZnAlO, Zn 1-x Al x O or La 1.98 Sr 0.02 CuO4 can be mentioned.

[0040] The organic semiconductor may include organic perovskite, polyaniline, polyacetylene, polythiophene, polyalkylthiophene, or polyhyrol.

[0041] Other semiconductors include alloys containing Co and Sb (e.g., CoSb3, CeFe3CoSb 12 , CeFe4CoSb 12 , or YbCo4Sb 12 ), alloys containing Zn and Sb (e.g., ZnSb, Zn3Sb2, or Zn4Sb3), alloys containing Bi and Sb (e.g., Bi 88 Sb 12 ), CeInCu2, (Cu,Ag)2Se, Gd2Se3, CeRhAs, or CeFe4Sb 12 , Li 7.9 B 105 , BaB6, SrB6, CaB6, AlPdRe compounds (e.g., Al 71 Pd 20 (Re 1-x Fe x )9), AlCuFe quasicrystal, Al 82.6-x Re 17.4 Si x 1 / 1-cubic approximation crystal, YbAl3, YbMn x Al3, β-CuAgSe, B4C / Ba3C, (Ce 1-x La x )Ni2, or (Ce 1-x La x )In3 can be mentioned.

[0042] The semiconductor layer may contain components other than the semiconductor, as long as the semiconductor can generate a sufficient number of thermally excited electrons and holes for power generation when heated to an appropriate temperature. Examples of such components include, but are not limited to, binders (polyvinyl alcohol, methyl cellulose, acrylic resin, agar, etc.) that bind the thermoelectric conversion material, and sintering aids (magnesium oxide, yttrium oxide, calcium oxide, etc.) that help form the thermoelectric conversion material. Solvents used in the manufacturing process may also remain. The first layer used in the present invention essentially functions as a thermoelectric conversion layer.

[0043] The semiconductor layer of the present invention contains a resin, which may include, but is not limited to, the binder described above.

[0044] (Electrolyte Layer) The electrolyte layer contains a solid electrolyte or an electrolyte solution in which a charge-transporting ion pair can move. As used herein, the term "charge-transporting ion pair" refers to two stable ions with different valences, in which one ion is oxidized or reduced to become the other ion, and which can transport electrons and holes. The ions may be of the same element but with different valences.

[0045] The ion source contained in the solid electrolyte of the present disclosure is not particularly limited as long as it is a metal ion, and examples thereof include copper ions, iron ions, vanadium ions, manganese ions, nickel ions, tin ions, zinc ions, aluminum ions, calcium ions, potassium ions, magnesium ions, palladium ions, titanium ions, alkali metal ions, and rare earth metal ions. For example, copper ions or iron ions include monovalent copper ions, divalent copper ions, divalent iron ions, and trivalent iron ions. However, two stable types of copper ions or iron ions with different valences are preferred. This is because one ion can be oxidized or reduced to become the other ion, which can transport electrons and holes.

[0046] Therefore, in the case of copper ions, monovalent copper ions and divalent copper ions are preferred, and in the case of iron ions, divalent iron ions and trivalent iron ions are preferred. Examples of monovalent copper ions that can be used include CuCl, CuBr, copper(I) acetate, copper(I) iodide, and copper(I) sulfate. Examples of divalent copper ions that can be used include CuCl, CuTSFI, copper(II) acetate, copper(II) sulfate, and copper(II) acetylacetonate. Examples of divalent iron ions that can be used include Fe(C5H5)2 (ferrocene), K4[Fe(CN)6], iron(II) acetylacetonate, iron(II) chloride, iron(II) sulfate, and iron(II) acetate. Examples of trivalent iron ions that can be used include FeCl3, K3[Fe(CN)6], iron(III) acetylacetonate, and iron(III) sulfate.

[0047] The concentration of the ion source is not particularly limited as long as the effects of the present invention can be obtained, but it is preferable to add the ion source so that the concentration is, for example, 0.01 to 98 mol % relative to the polymer, etc. This range allows the ion source to efficiently transport electrons and holes.

[0048] (Electrolyte) The electrolyte includes a solid electrolyte or an electrolyte solution. The electrolyte is not limited as long as it can transport two ions of a charge-transporting ion pair.

[0049] That is, the electrolyte used in the electrolyte layer is not particularly limited as long as its redox potential is in an appropriate position relative to the valence electron charge potential of the thermoelectric conversion material used in the thermoelectric power generation element and charge-transporting ion pairs can move back and forth within the electrolyte. Note that the electrolyte is preferably physically and chemically stable at a temperature at which the thermoelectric conversion material generates a sufficient number of thermally excited electrons and holes for power generation.

[0050] The electrolyte may be a solid electrolyte or an electrolyte solution (liquid electrolyte) depending on its form. Here, the electrolyte may be in the form of an electrolyte solution (liquid electrolyte) or a solid electrolyte depending on the temperature. That is, the compounds contained in an electrolyte solution (liquid electrolyte) and the compounds contained in a solid electrolyte overlap. Furthermore, electrolytes include molten salts, ionic liquids, deep eutectic solvents, and the like. A molten salt is a salt composed of cations and anions in a molten state. Molten salts with relatively low melting points (e.g., below 100°C or below 150°C) are referred to as ionic liquids. However, in this specification, molten salts in a solid state are referred to as solid electrolytes, and those in a solution state are referred to as electrolyte solutions (liquid electrolytes). Specific examples of electrolyte solutions (liquid electrolytes), solid electrolytes, and molten salts are provided below, but these terms may overlap.

[0051] The electrolyte solution used is in a solution (liquid) state at a temperature at which the semiconductor in the semiconductor layer generates a sufficient number of thermally excited electrons and holes for power generation.Specific examples of the electrolyte solution include, but are not limited to, methoxide ions, hydrogen ions, ammonium ions, hydridinium ions, lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, aluminum ions, iron ions, copper ions, zinc ions, cobalt ions, fluoride ions, cyanide ions, thiocyanate ions, chloride ions, acetate ions, sulfate ions, carbonate ions, phosphate ions, bicarbonate ions, and bromine ions.

[0052] The solid electrolyte is in a solid state where charge-transporting ion pairs can move inside at a temperature at which the semiconductor in the semiconductor layer generates a sufficient number of thermally excited electrons and holes for power generation. High-temperature solid electrolytes can be used in thermoelectric power generation elements that generate thermally excited electrons and holes at high temperatures. Specific examples of solid electrolytes include, but are not limited to, sodium ion conductors, copper ion conductors, lithium ion conductors, silver ion conductors, hydrogen ion conductors, strontium ion conductors, aluminum ion conductors, fluorine ion conductors, chloride ion conductors, and oxide ion conductors. Specific examples of solid electrolytes include RbAg4I5, Li3N, Na2O·11Al2O3, Sr-β alumina, Al(WO4)3, PbF2, PbCl2, and (ZrO2). 0.9 (Y2O3) 0.1 , (Bi2O3) 0.75 (Y2O3) 0.25 , CuZr2(PO4)3, CuTi2(PO4)3, Cu x Nb 1-x Ti 1+x (PO4)3, H 0.5 Cu 0.5 Zr2(PO4)3, Cu 1+x Cr x Ti 2-x (PO4)3, Cu 0.5 TiZr(PO4)3, CuCr2Zr(PO4)3, Cu2SCZr(PO4)3, CuSn2(PO4)3, CuHf2(PO4)3, Li7La3Zr2O12 , Li7La3Zr 2-x Nb x O 12 , Li7La3Zr 2-x Ta x O 12 , Li5La3Ta2O 12 , Li 0.33 La 0.55 TiO3, Li 1.5 Al 0.5 G e 1.5 P3O 12 , Li 1.3 Al 0.3 Ti 1.7 P3O 12 , Li3PO4 (LiPON), Li4SiO4-Li3PO4, Li4SiO4, or Li3BO3.

[0053] Molten salts can be used as solid electrolytes or electrolyte solutions. For thermoelectric power generation elements used at relatively low temperatures, ionic liquids can also be used. Deep eutectic solvents (DES) can be used as ionic liquids.

[0054] The molten salt may include a molten salt containing at least one cation selected from the group consisting of imidazolium cation, hydridinium cation, hyperidinium cation, hydrolidinium cation, phosphonium cation, morpholinium cation, sulfonium cation, and ammonium cation, and at least one anion selected from the group consisting of carboxylate anion, sulfonate anion, halogen anion, tetrafluoroborate, hexafluorophosphate, bis(trifluoromethanesulfonyl)imide, and bis(fluorosulfonyl)imide. The electrolyte in the present invention functions as a hole transporting material.

[0055] The electrolyte layer is not limited to any particular material, as long as it can transport holes generated in the thermoelectric conversion material. It can contain components other than a solid electrolyte or an electrolyte solution. Examples of such components include, but are not limited to, a solvent (e.g., water, methanol, toluene, tetrahydrofuran) that dissolves or disperses the electrolyte when forming the second layer, a binder (e.g., polyvinyl alcohol, methyl cellulose, acrylic resin, agar), and a sintering aid (e.g., magnesium oxide, yttrium oxide, calcium oxide) that helps form the hole-transporting material. The second layer used in the present invention essentially functions as a hole-transporting layer.

[0056] The electrolyte layer contains a resin, which may be, but is not limited to, the binder or metal salt (ion source), a separator (made of resin), or an insulating ceramic.

[0057] The electrolyte layer can be prepared by, for example, the squeegee method, screen printing method, sputtering method, vacuum deposition method, sol-gel method, or spin coating method. For example, CuZr2(PO4)3, which will be described later, was prepared by the sol-gel method, and the resulting sol was used to prepare a layered electrolyte layer by the squeegee method.

[0058] Furthermore, when the electrolyte is an electrolyte solution (liquid electrolyte), the second layer is in a liquid phase. When the second layer is in a liquid phase, the second layer in the thermoelectric power generation element is preferably prepared during the fabrication of the thermoelectric power generation device, thermobattery, or thermoelectric power generation module. That is, the second layer can be prepared by providing a tank for holding the electrolyte solution (liquid electrolyte).

[0059] (Conductive Polymer Layer) The conductive polymer layer contains an electron transport material. Examples of the electron transport material include polythiophene-based conductive polymers, polyacetylene-based conductive polymers, polyaniline-based conductive polymers, and polyhyrol-based conductive polymers. Specific examples of the electron transport material include polyacetylene, poly(p-phenylene), poly(p-phenylenevinylene), and polyaniline.

[0060] The conductive polymer layer may contain components other than the electron transport material, as long as they can transport thermally excited electrons generated by the thermoelectric conversion material. Examples of such components include, but are not limited to, binders (such as polyvinyl alcohol, methyl cellulose, acrylic resin, and agar) that bind the electron transport material, and sintering aids (such as magnesium oxide, yttrium oxide, and calcium oxide) that help mold the electron transport material. Solvents used in the manufacturing process may also remain. The third layer used in the present invention essentially functions as an electron transport layer.

[0061] In the thermoelectric power generating element of the present disclosure, the electron transport material has an electron conduction potential that is the same as or positive to the conduction potential of the semiconductor in the semiconductor layer, and therefore can transport thermally excited electrons.

[0062] The conductive polymer layer can be prepared by, for example, a squeegee method, a screen printing method, a sputtering method, a vacuum deposition method, a single crystal growth method, or a spin coating method. When using the spin coating method, the conductive polymer layer can be prepared by dissolving the oxadiazole derivative in a polar solvent such as acetone and spin coating the solution onto the substrate or the first layer.

[0063] 3A, conductors 42A, 42B, and 42C are formed at predetermined positions on the first insulating film 22, and then the thermal power generation elements 24, 26, and 28 are formed thereon. At this time, the conductive polymer layers 24C, 26C, and 28C are bonded to the first insulating film 22 and are overlapped and connected to one ends of the conductors 42A, 42B, and 42C. The pattern formed on the first insulating film 22 is referred to as a first pattern 20.

[0064] 3B, conductors 43A, 43B, 44A, and 44B are formed at predetermined positions on the second insulating film 32, and the thermal power generation elements 34, 36, and 38 are formed thereon. At this time, the conductive polymer layer C side is bonded to the second insulating film 32 and is overlapped and connected to the conductors 43A, 43B, and 44A. The pattern formed on the second insulating film 32 is referred to as a second pattern 30.

[0065] Then, each semiconductor layer A is connected to overlap with the other end of the conductors 42A, 42B, 42C, 43A, and 43B and one end of the conductor 44B so that the first pattern 20 and the second pattern 30 are mirror-imaged (see FIG. 4 ), and is bonded to the first insulating film 22 or the second insulating film 32. The bonding at this time is performed by melting the polymer contained in the semiconductor layer A by heating, and thermally fusing it to the first insulating film 22 or the second insulating film 32.

[0066] <Effects> In this way, in the thermal power generation module 10 of this embodiment, the semiconductor layer A on one side and the conductive polymer layer C on the other side of the thermal power generation element, which are connected to each other by a conductor, are arranged on the same insulating film (first insulating film 22 or second insulating film 32). Therefore, the connecting conductors can be formed on the same insulating film, and breaks and short circuits can be easily prevented compared to when conductors are arranged across the stacking direction.

[0067] Furthermore, since adjacent heat-utilizing power generation elements are connected to each other by the conductor on the same insulating film, a simple connection pattern can be achieved.

[0068] Furthermore, in the thermal power generation module 10 of this embodiment, the polymer contained in the semiconductor layer A is melted and thermally fused to the first insulating film 22 or the second insulating film 32, thereby properly connecting the conductor and the semiconductor layer A and preventing breakage.

[0069] Second Embodiment Next, a second embodiment of the present disclosure will be described. In the second embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted.

[0070] 5, the thermal power generation module 12 of the second embodiment includes conductors 26D, 38D, 28D, 36D, and 24D instead of the conductors 42A, 43A, 42B, 43B, and 42C. The other configurations are the same as those of the first embodiment.

[0071] The conductors 26D, 38D, 28D, 36D, and 24D form conductors D that extend from portions of the conductive polymer layers 26C, 38C, 28C, 36C, and 24C to connect to the adjacent semiconductor layer A. That is, as shown by the connection between the thermal power generation elements 26 and 38 in Fig. 6, a portion of the conductive polymer layer 38C of the thermal power generation element 38 extends toward the thermal power generation element 26, and the semiconductor layer 26A is layered on top of it.

[0072] According to the thermal power generation module 12 of the second embodiment, the conductive polymer layer C can also function as a conductor.

[0073] Third Embodiment Next, a third embodiment of the present disclosure will be described. In the third embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted.

[0074] 7, the thermal power generation module 13 of the third embodiment is stacked with a staggered arrangement of the semiconductor layer A, electrolyte layer B, and conductive polymer layer C, which are the layers of the thermal power generation elements 24, 26, 28, 34, 36, and 38. Specifically, the conductive polymer layer C and the semiconductor layer A, which are connected by a conductor, are positioned close to each other on the side where the conductor is located, and are positioned apart on the side where the conductor is not located.

[0075] 8 shows examples of thermal power generation elements 26 and 38. In the thermal power generation elements 26 and 38, the conductive polymer layer 38C and the semiconductor layer 26A, which are connected by a conductor 43A, are close to each other, and the conductive polymer layer 26C and the semiconductor layer 38A on the opposite side are offset so as to be farther apart. The conductive polymer layer 26C is positioned closer to the thermal power generation element 34 and is connected to a conductor 42A.

[0076] The thermal power generation module 13 of the third embodiment can prevent short circuits caused by contact with an unintended layer of a conductor.

[0077] Fourth Embodiment Next, a fourth embodiment of the present disclosure will be described. In the fourth embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted.

[0078] 9 shows a schematic plan view of a thermal power generation module 14 according to the fourth embodiment. In the fourth embodiment, each of the thermal power generation elements 24, 26, 28, 34, 36, and 38 of the first embodiment is divided into two, and a pair of thermal power generation elements is connected in parallel. The divided thermal power generation elements are distinguished by the suffixes -1 and -2, and a pair of thermal power generation elements is collectively referred to as a thermal power generation element pair. For example, a pair of thermal power generation elements 24-1 and 24-2 is referred to as a thermal power generation element pair 24.

[0079] 9 does not include the first insulating film 22 (described later) for ease of explanation (the first insulating film 22 is indicated by the dashed double-dashed line). The thermal power generation module 14 is rectangular in plan view as a whole and includes the first insulating film 22, the second insulating film 32, a plurality of (a total of 12 in this embodiment) thermal power generation elements 24-1, 24-2, 26-1, 26-2, 28-1, 28-2, 34-1, 34-2, 36-1, 36-2, 38-1, 38-2, and conductors 52A, 52B, 52C, 53A, 53B, 44A, 44B, and 44C.

[0080] 9, the thermoelectric power generation elements are arranged in a 2×6 array with a space between them, and are sandwiched between the first insulating film 22 and the second insulating film 32. Although the 2×6 array is used in this embodiment, an n×n or m×n (m≠n) array can be used as desired depending on the required voltage.

[0081] The thermal power generation elements 24-1, 24-2, 26-1, 26-2, 28-1, and 28-2 have the semiconductor layer A side bonded to the second insulating film 32 and the conductive polymer layer C side bonded to the first insulating film 22. The thermal power generation elements 34-1, 34-2, 36-1, 36-2, 38-1, and 38-2 have the conductive polymer layer C side bonded to the second insulating film 32 and the semiconductor layer A side bonded to the first insulating film 22.

[0082] The conductors 52A, 52B, 52C, 53A, and 53B connect the conductive polymer layers C or the semiconductor layers A of one and the other of the heat power generation element pair, and are laminated on part of one semiconductor layer A and part of the other conductive polymer layer C so as to connect the semiconductor layer A and the conductive polymer layer C of adjacent heat power generation element pairs. The conductors 52A, 52B, and 52C are formed on the first insulating film 22, and the conductors 53A, 53B, 44A, 44B, and 44C are formed on the second insulating film 32.

[0083] The conductor 52A connects the semiconductor layer 34-1A and the semiconductor layer 34-2A with the conductive polymer layer 26C-1C and the conductive polymer layer 26C-2C. The conductor 52B connects the semiconductor layer 38-1A and the semiconductor layer 38-2A with the conductive polymer layer 28-1C and the conductive polymer layer 28-2C. The conductor 52C connects the semiconductor layer 36A-1 and the semiconductor layer 36A-2 with the conductive polymer layer 24-1C and the conductive polymer layer 24-2C. The conductor 53A connects the semiconductor layer 26-1A and the semiconductor layer 26-2A with the conductive polymer layer 38-1C and the conductive polymer layer 38-2C. The conductor 53B connects the semiconductor layer 28-1A and the semiconductor layer 28-2A with the conductive polymer layer 36-1C and the conductive polymer layer 36-2C. One end of the conductor 44A is connected to the conductive polymer layer 34-1C. The conductor 44C connects the conductive polymer layer 34-1C and the conductive polymer layer 34-2C. One end of the conductor 44A is connected to the conductive polymer layer 34-1C. One end of the conductor 44B is connected to the semiconductor layer 24-1A.

[0084] The conductor 44A at one terminal is connected in series through the pairs of thermoelectric generator elements 34, 26, 38, 28, 36, 24 to the conductor 44B at the other terminal.

[0085] 10A, conductors 52A, 52B, and 52C are formed at predetermined positions on the first insulating film 22, and then the thermal power generation element pairs 24, 26, and 28 are formed thereon. At this time, the conductive polymer layer C side is bonded to the first insulating film 22 and is connected to and overlaps the connection ends of the conductors 52A, 52B, and 52C. The pattern formed on the first insulating film 22 is referred to as a first pattern 20-1.

[0086] 10B, conductors 53A, 53B, 44A, 44B, and 44C are formed at predetermined positions on the second insulating film 32, and then the thermal power generation element pairs 34, 36, and 38 are formed thereon. At this time, the conductive polymer layer C side is bonded to the second insulating film 32 and is overlapped and connected to the conductors 53A, 53B, 44A, and 44C. The pattern formed on the second insulating film 32 is referred to as second pattern 30-1.

[0087] Then, each semiconductor layer A is connected to overlapping connection ends of the conductors 52A, 52B, 52C, 53A, 53B, 44B, and 44C so that the first pattern 20-1 and the second pattern 30-1 are mirror images, and is bonded to the first insulating film 22 or the second insulating film 32. The bonding at this time is performed by melting the polymer contained in the semiconductor layer A by heating, and thermally fusing it to the first insulating film 22 or the second insulating film 32.

[0088] According to the thermal power generation module 14 of the fourth embodiment, by changing the pattern of the conductor, it is possible to easily form parallel connection portions and obtain a desired voltage.

[0089] Although the present invention has been described above by way of examples, these examples are merely examples and can be modified in various ways without departing from the spirit of the invention. It goes without saying that the scope of the present invention is not limited to these examples.

[0090] The disclosure of Japanese Patent Application No. 2024-006277 (write the application number of the basic Japanese application) is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual publication, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A thermoelectric power generation module comprising: a first insulating film and a second insulating film; a semiconductor layer that generates thermally excited electrons and holes; a conductive polymer layer containing an electron transport material; an electrolyte layer disposed between the semiconductor layer and the conductive polymer layer and containing a solid electrolyte or an electrolyte solution through which charge transport ion pairs can move; a plurality of thermoelectric power generation elements arranged at intervals in a plan view between the first insulating film and the second insulating film; and a conductor connecting the semiconductor layer and the conductive polymer layer of adjacent thermoelectric power generation elements, wherein the thermoelectric power generation elements connected by the conductor are such that the semiconductor layer of one thermoelectric power generation element is disposed on the first insulating film side and the semiconductor layer of the other thermoelectric power generation element is disposed on the second insulating film side.

2. The thermoelectric power generation module according to claim 1, wherein the adjacent thermoelectric power generation elements are such that the semiconductor layer of one thermoelectric power generation element is disposed on the first insulating film side and the semiconductor layer of the other thermoelectric power generation element is disposed on the second insulating film side.

3. The thermoelectric power generation module according to claim 1, wherein one end of the conductor overlaps with a part of the semiconductor layer and the other end overlaps with a part of the conductive polymer layer.

4. The thermoelectric power generation module according to claim 1, wherein the conductor is formed by extending a part of the conductive polymer layer.

5. The thermoelectric power generation module according to any one of claims 1 to 4, wherein the semiconductor layer contains a polymer that melts upon heating.

6. A method for manufacturing a thermoelectric power generation module having a power generation element pattern including a plurality of thermoelectric power generation elements in which a semiconductor layer, an electrolyte layer, and a conductive polymer layer are laminated, and a conductor for electrically connecting the plurality of thermoelectric power generation elements, the method comprising: forming a first pattern, which is a part of the power generation element pattern, on a first insulating film such that the conductive polymer layer and the conductor are disposed on the first insulating film side; forming a second pattern, which is the remainder of the power generation element pattern, on a second insulating film such that the conductive polymer layer and the conductor are disposed on the second insulating film side; and joining the first insulating film and the second insulating film so that the power generation element pattern is formed by the first pattern and the second pattern.

7. The semiconductor layer contains a polymer that thermally melts. When joining the first insulating film and the second insulating film, the semiconductor layer of the first pattern is welded to the second insulating film of the second pattern by thermal melting, and the semiconductor layer of the second pattern is welded to the first insulating film of the first pattern by thermal melting. The method for manufacturing a thermoelectric power generation module according to claim 6.

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