Heat utilization power generation module and manufacturing method for the same

Abstract

To provide a heat utilization power generation module in which breaks and short circuits between a plurality of heat power generation elements are prevented and a manufacturing method for the same.SOLUTION: A heat utilization power generation module 10 includes a first insulating film 22 and a second insulating film 32, a plurality of heat utilization power generation elements, and a conductor. The plurality of heat utilization power generation elements are formed by stacking a semiconductor layer A, a conductive polymer layer C, and an electrolyte layer B. The semiconductor layer A generates thermally excited electrons and holes. The conductive polymer layer C includes an electron transport material. The electrolyte layer B includes a solid electrolyte or an electrolyte solution disposed between the semiconductor layer A and the conductive polymer layer, through which charge-transporting ion pairs can migrate. The plurality of heat utilization power generation elements are arranged between the first insulating film 22 and the second insulating film 32, spaced apart from each other in a plan view. The conductor connects the semiconductor layer A and the conductive polymer layer C of adjacent heat utilization power generation elements. In the pair of heat utilization power generation elements connected by the conductor, the semiconductor layer A of one heat utilization power generation element is disposed on the side of the first insulating film 22, while the semiconductor layer A of the other heat utilization power generation element is disposed on the side of the second insulating film 32.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a heat utilization power generation module and a method for manufacturing a heat utilization power generation module.

Background Art

[0002] As heat utilization power generation using geothermal heat or waste heat from factories, etc., a method using the Seebeck effect can be mentioned. Further, as heat utilization power generation that does not use the Seebeck effect, there is a heat utilization power generation element disclosed in Patent Document 1 below. Patent Document 1 below discloses converting thermal energy into electrical energy by a heat utilization power generation element that combines an electrolyte and a thermoelectric conversion material. By using such a heat utilization power generation element as a power source for electronic components, stable power can be supplied to the electronic components even in a high-temperature environment (for example, 50°C or higher) where general batteries are likely to deteriorate.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] As the practical application of the technology as in Patent Document 1, modularization of the power generation device is required. In particular, when connecting a plurality of thermoelectric power generation elements having an electrolyte and a thermoelectric conversion material, prevention of disconnection and short circuit is required.

[0005] The present invention has been made in consideration of the above facts, and an object thereof is to provide a heat utilization power generation module in which disconnection and short circuit between a plurality of thermoelectric power generation elements are suppressed, and a method for manufacturing a heat utilization power generation module.

Means for Solving the Problems

[0006] The thermoelectric power generation module according to the first aspect of the present disclosure includes 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, and 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 are arranged at intervals in a plan 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 thermoelectric power generation elements. In the thermoelectric power generation elements connected by the conductor, 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.

[0007] In the thermoelectric power generation module according to the first aspect, in the thermoelectric power generation elements connected by the conductor, 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. Therefore, a conductor that connects one thermoelectric power generation element and the other thermoelectric power generation element can be formed on one side in the stacking direction. That is, the conductor can be formed close to one of the first insulating film side or the second insulating film side. Thereby, a thermoelectric power generation module with easily suppressed disconnection and short circuit can be obtained.

[0008] The thermoelectric power generation module according to the second aspect of the present disclosure is the thermoelectric power generation module according to the first aspect, wherein in adjacent thermoelectric power generation elements, 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.

[0009] According to the thermoelectric power generation module of the second aspect, a conductor that connects adjacent thermoelectric power generation elements can be formed close to one of the first insulating film side or the second insulating film side. Thereby, adjacent thermoelectric power generation elements can be connected by a conductor on the same insulating film, and a simple connection pattern can be obtained.

[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 thermal power generation module according to a fourth aspect of the present disclosure is the 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 function 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 disconnection.

[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 method for manufacturing a thermoelectric power generation module according to the sixth aspect, a first pattern, which is a part of the power generation element pattern, is formed such that the conductive polymer layer and the conductor are disposed on the first insulating film side, and a second pattern, which is the remainder of the power generation element pattern, is formed on the second insulating film such that the conductive polymer layer and the conductor are disposed on the first insulating film side, and the first insulating film and the second insulating film are joined. Therefore, since the conductor can be formed so as to be shifted to either the first insulating film side or the second insulating film side, a thermoelectric power generation module with reduced disconnection and short circuit can be easily manufactured.

[0018] The method for manufacturing a thermoelectric power generation module according to the seventh aspect of the present disclosure is the method for manufacturing a thermoelectric power generation module according to the sixth aspect, wherein the semiconductor layer contains a polymer that thermally melts, 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 method for manufacturing a thermoelectric power generation module according to the seventh aspect, by melting the polymer contained in the semiconductor layer and welding it to the first insulating film and the second insulating film, connection with the conductor can be appropriately performed, and disconnection can be suppressed.

Advantages of the Invention

[0020] As described above, according to the present disclosure, it is possible to provide a thermoelectric power generation module in which disconnection and short circuit between a plurality of thermoelectric power generation elements are suppressed, and a method for manufacturing a thermoelectric power generation module.

Brief Description of the Drawings

[0021]

Figure 1

Figure 2

Figure 3A

Figure 3B

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10A

Figure 10B

[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 this 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 as a whole in a plan view, 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, 38, and conductors 42, 43, 44.

[0024] The first insulating film 22 and the second insulating film 32 are sheet-shaped and form the outer shape of the thermoelectric power generation module 10 in a plan view. Being sheet-shaped, the first insulating film 22 and the second insulating film 32 have insulating properties, and a sheet of metal (such as aluminum, copper, etc.) coated with a polymer 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 thermoelectric power generation elements 24, 26, 28, 34, 36, 38 include a semiconductor layer that generates thermally excited electrons and holes, an electrolyte layer including a solid electrolyte or an electrolyte solution in which charge transport ion pairs can move, and a conductive polymer layer including an electron transport material. For each of the thermoelectric power generation elements 24, 26, 28, 34, 36, 38, the semiconductor layer is indicated by the symbol with the suffix A, the electrolyte layer is indicated by the symbol with the suffix B, and the conductive polymer layer is indicated by the symbol with the suffix C. For example, in the thermoelectric power generation element 24, it is represented as the semiconductor layer 24A, the electrolyte layer 24B, and the conductive polymer layer 24C. Also, when explaining each layer in common for all the thermoelectric power generation elements 24, 26, 28, 34, 36, 38, it is simply represented 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. Note that the thermoelectric power generation element may be formed of a single layer in which the semiconductor layer A, the electrolyte layer B, and the conductive polymer layer C are laminated, or may be formed of a structure in which a plurality of layers (for example, two layers, three layers) of combinations of the semiconductor layer A, the electrolyte layer B, and the conductive polymer layer C are laminated.

[0026] As shown in FIG. 1, the thermoelectric power generation elements 24, 26, 28, 34, 36, 38 are arranged at intervals from each other in a 2×3 array, and are sandwiched between the first insulating film 22 and the second insulating film 32 as shown in FIG. 2. The thermoelectric power generation elements 24, 26, 28 are arranged at non-adjacent positions in the 2-row×3-column arrangement, and the thermoelectric power generation elements 34, 36, 38 are arranged so as to fill the intervals between the respective thermoelectric power generation elements 24, 26, 28.

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

[0028] The conductors 42A, 42B, 42C, 43A, and 43B are laminated on a part of one semiconductor layer A and a part of the other conductive polymer layer C so as to connect one semiconductor layer A and the other conductive polymer layer C of adjacent thermoelectric 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] The conductor 42A connects the semiconductor layer 34A and the conductive polymer layer 26C, the conductor 42B connects the semiconductor layer 38A and the conductive polymer layer 28C, and the conductor 42C connects the semiconductor layer 36A and the conductive polymer layer 24C. The conductor 43A connects the semiconductor layer 26A and the conductive polymer layer 38C, and the conductor 43B connects the semiconductor layer 28A and the conductive polymer layer 36C. One end of the conductor 44A is connected to the conductive polymer layer 34C. One end of the conductor 44B is connected to the semiconductor layer 24A.

[0030] They are connected in series from the conductor 44A of one terminal through the thermoelectric power generation elements 34, 26, 38, 28, 36, and 24 to the other conductor 44B.

[0031] (Semiconductor layer) Semiconductor layer A contains a semiconductor. In the present disclosure, "semiconductor" means a material capable of generating thermally excited electrons and holes by heat. Specifically, examples include metal semiconductors, telluride compounds, silicon germanium (Si-Ge) compounds, silicide compounds, skutterudite compounds, clathrate compounds, Heusler compounds, half-Heusler compounds, 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] Examples of telluride compounds include Bi-Te compounds (e.g., Bi2Te3, Sb2Te3, CsBi4Te6, Bi2Se3, Bi0.4Sb1.6Te3, Bi2(Se,Te)3, (Bi,Sb)2(Te,Se)3, (Bi,Sb)2Te3, or Bi2Te 2.95 Se 0.05 ), Pb-Te compounds (e.g., PbTe, or Pb1-xSnxTe), SnTe, Ge-Te, AgSbTe2, Ag-Sb-Ge-Te compounds (e.g., GeTe-AgSbTe2 (TAGS)), Ga2Te3, (Ga1-xInx)2Te3, Tl2Te-Ag2Te, Tl2Te-Cu2Te, Tl2Te-Sb2Te3, Tl2Te-Bi2Te3, Ti2Te-GeTe, Ag8Tl2Te5, Ag9Tl Te5, Tl9BiTe6, Tl9SbTe6, Tl9CuTe5, Tl4SnTe3, Tl4PbTe3, or Tl 0.02 Pb 0.98 Te.

[0033] Examples of silicon germanium (Si-Ge) compounds include SixGe1-x, or SiGe-GaP.

[0034] Examples of silicide compounds include β-FeSi2 compounds (e.g., β-FeSi2, Fe1-xMnxSi2, Fe 0.95 Mn 0.05 Si( 2-y )Aly, FeSi( 2-y)Al, Fe 1-y CoSi2, Mg2Si, MnSi 1.75 -x, Ba8Si 46 、Ba8Ga 16 Si 30 、or CrSi2 can be cited.

[0035] As a skutterudite compound semiconductor, a compound 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), a compound 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), YbyFe4-xCoxSb 12 , (CeFe3CoSb 12 ) 1-x (MoO2)x or (CeFe3CoSb 12 ) 1-x (WO2)x can be cited.

[0036] As a clathrate compound semiconductor, a compound represented by the formula M8X 46 (where 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 the formula (II)8(III) 16 (IV) 30 (where II is a Group II element, III is a Group III element, and IV is a Group IV element) can be cited. As the compound of the formula (II)8(III) 16 (IV) 30 , for example, Ba8GaxGe 46-x , Ba 8-x (Sr, Eu)xAu6Ge 40 , or Ba 8-x EuxCu6Si 40 ) can be cited.

[0037] Examples of the Heusler compound semiconductor include Fe2VAl, (Fe 1-x Rex)2VAl, or Fe2(V 1-x-y Ti x Ta y )Al.

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

[0039] Examples of the metal oxide semiconductor include In2O3-SnO2, (CaBi)MnO3, Ca(Mn, In)O3, NaxV2O5, V2O5, ZnMnGaO4 and its derivatives, LaRhO3, LaNiO3, SrTiO3, SrTiO3:Nb, Bi2Sr2Co2Oy, NaxCoO2, NaCo2O4, CaPd3O4, a compound represented by the formula Ca a M 1 bCo C M 2 d Ag e O f (where 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 earths, 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, 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 0.02CuO4 can be cited.

[0040] Examples of the organic semiconductor include organic perovskite, polyaniline, polyacetylene, polythiophene, polyalkylthiophene, or polypyrrole.

[0041] Examples of 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 quasicrystals, Al 82.6-x Re 17.4 Six1 / 1-legislative approximation crystals, YbAl3, YbMnxAl3, β-CuAgSe, B4C / Ba3C, (Ce 1-x La x )Ni2, or (Ce 1-x La x )In3.

[0042] The semiconductor layer can 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 an appropriate temperature is applied. Examples of such components include, but are not limited to, binders (such as polyvinyl alcohol, methyl cellulose, acrylic resin, agar, etc.) for binding thermoelectric conversion materials, and sintering aids (such as magnesium oxide, yttrium oxide, calcium oxide, etc.) for assisting in the shaping of thermoelectric conversion materials. Also, a solvent used in the manufacturing process may remain. The first layer used in the present invention substantially functions as a thermoelectric conversion layer.

[0043] The semiconductor layer of the present invention contains a resin. Examples of the resin include, but are not limited to, the above-mentioned binders.

[0044] (Electrolyte layer) The electrolyte layer contains a solid electrolyte or an electrolyte solution through which charge-transporting ion pairs can move. In this specification, "charge-transporting ion pairs" refer to two stable ions with different valences, where one ion is oxidized or reduced to become the other ion and can carry electrons and holes. They can be ions of the same element 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. Examples include copper ions, iron ions, vanadium ions, manganese ions, nickel ions, tin ions, zinc ions, aluminum ions, calcium ions, potassium ions, magnesium ions, palladium, titanium ions, alkali metal ions, and rare earth metal ions. For example, as copper ions or iron ions, monovalent copper ions, divalent copper ions, divalent iron ions, or trivalent iron ions can be mentioned. However, copper ions or iron ions are preferably two stable ions with different valences because one ion is oxidized or reduced to become the other ion and can carry electrons and holes.

[0046] Therefore, in the case of copper ions, monovalent copper ions and divalent copper ions are preferred. In the case of iron ions, divalent iron ions and trivalent iron ions are preferred. As the monovalent copper ions, for example, CuCl, CuBr, copper(I) acetate, copper(I) iodide, or copper(I) sulfate can be used. As the divalent copper ions, CuCl2, CuTSFI2, copper(II) acetate, copper(II) sulfate, or copper(II) acetylacetonate can be used. As the divalent iron ions, Fe(C5H5)2 (ferrocene), K4[Fe(CN)6], iron(II) acetylacetonate, iron(II) chloride, iron(II) sulfate, or iron(II) acetate can be used. As the trivalent iron ions, FeCl3, K3[Fe(CN)6], iron(III) acetylacetonate, or iron(III) sulfate can be used.

[0047] The concentration of the ion source is not particularly limited as long as the effects of the present invention can be obtained. However, for example, it is preferably added so as to be 0.01 to 98 mol% with respect to the polymer or the like. By being within the above range, the ion source can 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 transport ion pair.

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

[0050] As the electrolyte, depending on the difference in its aspect, it may be a solid electrolyte or an electrolyte solution (liquid electrolyte). Here, the electrolyte may be in the form of an electrolyte solution (liquid electrolyte) or a solid electrolyte depending on the temperature difference. That is, the compounds contained in the electrolyte solution (liquid electrolyte) and the compounds contained in the solid electrolyte overlap. Further, the electrolyte includes a molten salt, an ionic liquid, a deep eutectic solvent, etc. A molten salt is a salt composed of a cation and an anion and in a molten state. Among molten salts, those with a relatively low melting point (for example, those below 100 °C or those below 150 °C) are called ionic liquids. In this specification, molten salts in a solid state are regarded as solid electrolytes, and those in a solution state are regarded as electrolyte solutions (liquid electrolytes). Specific examples of the electrolyte solution (liquid electrolyte), solid electrolyte, and molten salt are given below, but these may overlap.

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

[0052] For the solid electrolyte, a solid-state one in which charge-transporting ion pairs can move internally is used at a temperature at which the semiconductors in the semiconductor layer generate a sufficient number of thermally excited electrons and holes for power generation. By using a high-temperature solid electrolyte, it can be used in a thermoelectric power generation element that generates thermally excited electrons and holes at high temperatures. Specifically, examples of the solid electrolyte 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, fluoride ion conductors, chloride ion conductors, or oxide ion conductors. Specific solid electrolytes include, for example, RbAg4I5, Li3N, Na2O·11Al2O3, Sr-β alumina, Al(WO4)3, PbF2, PbCl2, (ZrO2) 0.9 (Y2O3) 0.1 , (Bi2O3) 0.75 (Y2O3) 0.25 , CuZr2(PO4)3, CuTi2(PO4)3, CuxNb 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, Li7La3Zr2O 12 , Li7La3Zr 2-x NbxO 12 , Li7La3Zr 2-x TaxO 12 , Li5La3Ta2O 12 , Li 0.33 La 0.55 , Li 1.5 Al 0.5 G e 1.5 P3O 12 , Li 1.3 Al 0.3 Ti 1.7 P3O 12, such as Li3PO4 (LiPON), Li4SiO4-Li3PO4, Li4SiO4, or Li3BO3, etc. can be mentioned.

[0053] Also, a molten salt can be used as the solid electrolyte or the electrolyte solution. In the case of a thermoelectric power generation element used at a relatively low temperature, an ionic liquid can also be used. As the ionic liquid, a deep eutectic solvent (DES) can be used.

[0054] Examples of the molten salt include those containing at least one cation selected from the group consisting of imidazolium cation, pyridinium cation, pyrazinium cation, pyrrolidinium cation, phosphonium cation, morpholinium cation, sulfonium cation, and ammonium cation, and at least one anion selected from the group consisting of carboxylic acid anion, sulfonic acid 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 as long as it can transport the holes generated by the thermoelectric conversion material, and can contain components other than the solid electrolyte or the electrolyte solution. Examples of the components include, but are not limited to, a solvent (such as water, methanol, toluene, tetrahydrofuran, etc.) for dissolving or dispersing the electrolyte when forming the second layer, a binder (such as polyvinyl alcohol, methyl cellulose, acrylic resin, agar, etc.) for binding the electrolyte, and a sintering aid (such as magnesium oxide, yttrium oxide, calcium oxide, etc.) for assisting the molding of the hole-transporting material. The second layer used in the present invention substantially 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 described below 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 production of the thermoelectric power generation device, thermobattery, or thermoelectric power generation module. That is, the second layer can be produced 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 in the thermoelectric conversion material. Examples of such components include, but are not limited to, binders (polyvinyl alcohol, methyl cellulose, acrylic resin, agar, etc.) that bind the electron transport material, and sintering aids (magnesium oxide, yttrium oxide, calcium oxide, etc.) that help form 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 generation element of the present disclosure, the electron conduction potential of the electron transport material is the same as or positive with respect to the conduction band potential of the semiconductor in the semiconductor layer. Therefore, the electron transport material can transport thermally excited electrons.

[0062] The conductive polymer layer can be formed by, for example, a squeegee method, a screen printing method, a sputtering method, a vacuum evaporation method, a single crystal growth method, or a spin coating method. When using the spin coating method, an oxadiazole derivative is dissolved in a polar solvent such as acetone, and the solution is spin-coated onto a substrate or a first layer to form a conductive polymer layer.

[0063] <Manufacturing method> As shown in FIG. 3A, conductors 42A, 42B, and 42C are formed at predetermined positions of the first insulating film 22, and thermoelectric power generation elements 24, 26, and 28 are formed thereon. At this time, the conductive polymer layer 24C, 26C, 28C sides are joined to the first insulating film 22 and connected by overlapping one end portions of the conductors 42A, 42B, 42C. The pattern formed on the first insulating film 22 is referred to as a first pattern 20.

[0064] Further, as shown in FIG. 3B, conductors 43A, 43B, 44A, and 44B are formed at predetermined positions of the second insulating film 32, and thermoelectric power generation elements 34, 36, and 38 are formed thereon. At this time, the conductive polymer layer C side is joined to the second insulating film 32 and connected by overlapping with the conductors 43A, 43B, 44A. The pattern formed on the second insulating film 32 is referred to as a second pattern 30.

[0065] Then, so that the first pattern 20 and the second pattern 30 are mirror-matched (see FIG. 4), each semiconductor layer A is overlapped and connected to the other end portions of the conductors 42A, 42B, 42C, 43A, 43B and one end portion of the conductor 44B, and adhered to the first insulating film 22 or the second insulating film 32. The adhesion at this time melts the polymer contained in the semiconductor layer A by heating and thermally fuses it to the first insulating film 22 or the second insulating film 32.

[0066] <Effect> As described above, in the power generation module 10 using heat of the present embodiment, one semiconductor layer A and the other conductive polymer layer C of the heat utilization power generation elements connected to each other by a conductor are arranged on the same insulating film (the first insulating film 22 or the second insulating film 32). Therefore, the conductor for connection can be formed on the same insulating film, and disconnection and short circuit can be easily suppressed as compared with the case where the conductor is formed across the stacking direction.

[0067] Also, since adjacent heat utilization power generation elements are connected by conductors on the same insulating film, a simple connection pattern can be achieved.

[0068] Further, in the power generation module 10 using heat of the present embodiment, the polymer contained in the semiconductor layer A is melted and heat-sealed to the first insulating film 22 or the second insulating film 32, so that the connection between the conductor and the semiconductor layer A can be appropriately made and disconnection can be suppressed.

[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 illustrated, and detailed description thereof will be omitted.

[0070] As shown in FIG. 5, the heat utilization power generation module 12 of the second embodiment includes conductors 26D, 38D, 28D, 36D, 24D instead of conductors 42A, 43A, 42B, 43B, 42C. Other configurations are the same as those in the first embodiment.

[0071] The conductors 26D, 38D, 28D, 36D, 24D are formed by extending a part of the conductive polymer layers 26C, 38C, 28C, 36C, 24C to form a conductor D that connects to the adjacent semiconductor layer A. That is, as shown in the connection between the heat utilization power generation elements 26 and 38 in FIG. 6, a part of the conductive polymer layer 38C of the heat utilization power generation element 38 extends toward the heat utilization power generation element 26, and the semiconductor layer 26A is overlapped and stacked.

[0072] According to the power generation module 12 for heat utilization of the second embodiment, the conductive polymer layer C can also serve 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 illustrated, and detailed descriptions thereof are omitted.

[0074] As shown in FIG. 7, in the power generation module 13 for heat utilization of the third embodiment, the semiconductor layer A, the electrolyte layer B, and the conductive polymer layer C, which are the respective layers of the power generation elements 24, 26, 28, 34, 36, and 38 for heat utilization, are laminated with a shift. Specifically, the conductive polymer layer C and the semiconductor layer A connected by a conductor are arranged close to each other on the side where the conductor is arranged, and are shifted so as to be separated on the side where the conductor is not arranged.

[0075] FIG. 8 shows examples of the power generation elements 26 and 38 for heat utilization. In the power generation elements 26 and 38 for heat utilization, the conductive polymer layer 38C and the semiconductor layer 26A connected by the conductor 43A are arranged close to each other, and the conductive polymer layer 26C and the semiconductor layer 38A on the opposite side are arranged with a shift so as to be separated. The conductive polymer layer 26C is arranged close to the power generation element 34 side and is connected to the conductor 42A.

[0076] According to the power generation module 13 for heat utilization of the third embodiment, it is possible to suppress a short circuit due to contact with an unintended layer of the 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 illustrated, and detailed descriptions thereof are omitted.

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

[0079] In FIG. 9, for convenience of explanation, it is a view excluding the first insulating film 22 to be described later (the first insulating film 22 is the portion indicated by the two-dot chain line). The heat utilization power generation module 14 is generally rectangular in plan view, and includes a first insulating film 22, a second insulating film 32, a plurality (12 in total in this embodiment) of heat utilization 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, 44C.

[0080] As shown in FIG. 9, the heat utilization power generation elements are arranged at intervals of 2×6 columns, and are sandwiched between the first insulating film 22 and the second insulating film 32. In this embodiment, it is 2×6 columns, but it can be arbitrarily arranged in an n×n or m×n (m≠n) array according to the required voltage.

[0081] For the heat utilization power generation elements 24-1, 24-2, 26-1, 26-2, 28-1, 28-2, the semiconductor layer A side is adhered to the second insulating film 32, and the conductive polymer layer C side is adhered to the first insulating film 22. For the heat utilization power generation elements 34-1, 34-2, 36-1, 36-2, 38-1, 38-2, the conductive polymer layer C side is adhered to the second insulating film 32, and the semiconductor layer A side is adhered to the first insulating film 22.

[0082] The conductors 52A, 52B, 52C, 53A, and 53B connect one and the other conductive polymer layers C of the thermoelectric power generation element pair or semiconductor layers A to each other, and connect the semiconductor layer A and the conductive polymer layer C of adjacent thermoelectric power generation element pairs. They are laminated on a part of one semiconductor layer A and a part of the other conductive polymer layer C. 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 layers 34-1A and 34-2A to the conductive polymer layers 26C-1C and 26C-2C. The conductor 52B connects the semiconductor layers 38-1A and 38-2A to the conductive polymer layers 28-1C and 28-2C. The conductor 52C connects the semiconductor layers 36A-1 and 36A-2 to the conductive polymer layers 24-1C and 24-2C. The conductor 53A connects the semiconductor layers 26-1A and 26-2A to the conductive polymer layers 38-1C and 38-2C. The conductor 53B connects the semiconductor layers 28-1A and 28-2A to the conductive polymer layers 36-1C and 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] They are connected in series from the conductor 44A of one terminal through the thermoelectric power generation element pairs 34, 26, 38, 28, 36, 24 to the other conductor 44B.

[0085] <Manufacturing Method> As shown in Fig. 10A, conductors 52A, 52B, and 52C are formed at predetermined positions of the first insulating film 22, and thermoelectric power generation element pairs 24, 26, and 28 are formed thereon. At this time, the C side of the conductive polymer layer is joined to the first insulating film 22 and connected by overlapping with the connection ends of the conductors 52A, 52B, and 52C. The pattern formed on the first insulating film 22 is referred to as the first pattern 20-1.

[0086] Also, as shown in Fig. 10B, conductors 53A, 53B, 44A, 44B, and 44C are formed at predetermined positions of the second insulating film 32, and thermoelectric power generation element pairs 34, 36, and 38 are formed thereon. At this time, the C side of the conductive polymer layer is joined to the second insulating film 32 and connected by overlapping with the conductors 53A, 53B, 44A, and 44C. The pattern formed on the second insulating film 32 is referred to as the second pattern 30-1.

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

[0088] According to the thermoelectric power generation module 14 of the fourth embodiment, by changing the pattern of the conductors, the parallel connection part can be easily formed, and a desired voltage can be obtained.

[0089] As described above, the embodiments of the present invention have been described with reference to the embodiments. However, these embodiments are merely examples, and various modifications can be made without departing from the gist of the invention. Needless to say, the scope of the rights of the present invention is not limited to these embodiments.

Explanation of Reference Numerals

[0090] 10, 12, 13, 14 Thermoelectric power generation module 20 First pattern 22 First insulating film 30 Second pattern 32 Second insulating film 24, 26, 28, 34, 36, 38 Thermoelectric power generation elements 42, 43, 52, 53 Conductors A Semiconductor layer B Electrolyte layer C Conductive polymer layer

Claims

1. 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, and 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, and a plurality of thermoelectric power generation elements arranged at intervals from each other in a plan view between the first insulating film and the second insulating film; a conductor that connects the semiconductor layer and the conductive polymer layer of adjacent thermoelectric power generation elements; comprising in the thermoelectric power generation elements connected by the conductor, the semiconductor layer of one of the thermoelectric power generation elements 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; a thermoelectric power generation module.

2. Between adjacent thermoelectric power generation elements, the semiconductor layer of one of the thermoelectric power generation elements 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. The thermoelectric power generation module according to claim 1.

3. 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. The thermoelectric power generation module according to claim 1.

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

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

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 that electrically connects the plurality of thermoelectric power generation elements, forming a first pattern, which is a part of the power generation element pattern, on the first insulating film so that the conductive polymer layer and the conductor are disposed on the first insulating film side, and forming a second pattern, which is the remainder of the power generation element pattern, on the second insulating film so that the conductive polymer layer and the conductor are disposed on the second insulating film side, 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; A method for manufacturing a thermoelectric power generation module.

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

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