All-resin thermal energy power generation element

Abstract

To provide a whole resin heat use power generation element capable of reducing a weight, having flexibility, being adopted to a place where a bent is required, reducing a size, realizing an autonomous, reducing an interface resistance, reducing a cost of an original material, simplifying a manufacturing step, being manufactured in a short time, and preventing an internal shot risk due to the break of a metal film.SOLUTION: In a whole resin heat use power generation element formed by a semiconductor film for generating a whole heat activation electron and a positive hole, an electrolyte film containing a solid electrolyte or an electrolyte solution in which a pair of electric charge transportation ions can be moved, and a conductive film containing an electron transportation material, a metal layer is not contained to each outside of the semiconductor film and the conductive film.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] This invention relates to an all-resin heat-utilizing power generation element. [Background technology]

[0002] Conventionally, thermoelectric power generation utilizing the Seebeck effect has been known as a heat-utilizing power generation method that uses geothermal energy or waste heat from factories (Patent Documents 1 and 2, and Non-Patent Document 1), and its practical application is expected in order to efficiently utilize thermal energy. Thermoelectric power generation using the Seebeck effect is a power generation principle that utilizes the fact that a voltage is generated when a temperature gradient is applied to a metal or semiconductor. Specifically, it is a thermoelectric power generation system that converts thermal energy into electrical energy by applying a temperature gradient to a thermoelectric conversion element that combines a p-type semiconductor and an n-type semiconductor.

[0003] However, conventional thermoelectric conversion elements that utilize temperature gradients have several problems, including the high cost of the semiconductors that make up the element, a wide operating temperature range, and low conversion efficiency. Furthermore, the physical durability of the coupling is weak, making it unsuitable for installation in locations subject to vibration. In addition, because a temperature gradient is required for power generation, there are limitations on the installation location, and in some cases, a cooling device for the temperature gradient is necessary. In particular, since one dimension of the thermoelectric conversion module is used for the temperature gradient, the utilization of the heat source is two-dimensional, and it is not possible to use all the surrounding heat three-dimensionally, resulting in the disadvantage of low heat utilization efficiency. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2010-147236 [Patent Document 2] Japanese Patent Publication No. 2003-219669 [Patent Document 3] International Publication No. 2017 / 038988 [Patent Document 4] International Publication No. 2020 / 031992 [Non-patent literature]

[0005] [Non-Patent Document 1] "Renewable and Sustainable Energy Reviews" (Netherlands), 2014, Vol. 33, p. 371. [Overview of the project] [Problems that the invention aims to solve]

[0006] A thermal energy generator capable of converting thermal energy into electrical energy has been developed by combining a thermoelectric conversion material that generates thermally excited electrons and holes with an electrolyte (Patent Document 3). The present inventors have further developed a more stable thermal energy generator (Patent Document 4). However, there has been a need for a thermal energy generator that can be used in a wider variety of locations and applications. Therefore, the object of the present invention is to provide a thermal power generation battery that can be used in a variety of locations and applications. [Means for solving the problem]

[0007] The inventors, through diligent research into thermal energy generators usable in various locations and applications, have surprisingly discovered that an all-resin thermal energy generation element without metal foil can be used in a wide range of applications. This invention is based on these findings. Therefore, the present invention is [1] An all-resin thermal power generation element comprising a semiconductor layer that generates thermally excited electrons and holes, an electrolyte layer containing a solid electrolyte or electrolyte solution on which charge transport ion pairs can move, and a conductive polymer layer containing an electron transport material, wherein the all-resin thermal power generation element does not have a metal layer on the outside of the semiconductor layer and the conductive polymer layer. [2][1] A laminated all-resin heat-utilizing power generation element in which two or more of the all-resin heat-utilizing power generation elements described in [2][1] are stacked, [3] The laminated all-resin thermal power generation element according to [2], having a metal layer on the outside of one semiconductor layer and on the outside of the other conductive polymer layer of the laminated all-resin thermal power generation element, A heat-utilizing power generation element described in any of [4][1] to [3], wherein the thermal excitation electron density of the semiconductor that generates thermally excited electrons and holes in the semiconductor layer is 10 15 / m 3 A method of generating electricity by placing the device in an environment with a temperature above a certain level. A thermoelectric power generation device including a heat-utilizing power generation element as described in any of [5][1] to [3], A thermocell containing a thermoelectric power generation element as described in any of [6][1]~[3], A thermoelectric power generation module including a thermoelectric power generation element as described in any of [7][1]~[3], A thermoelectric power generation method, comprising the steps of installing the thermoelectric power generation module described in [8][7] at a heat generation location, and heating the thermoelectric power generation module with heat to generate electricity, and [9] The thermoelectric power generation method according to [8], wherein the heat is geothermal or waste heat. Regarding. [Effects of the Invention]

[0008] The all-resin thermal power generation element of the present invention can be made lighter because it does not have a metal foil. The all-resin thermal power generation element of the present invention is highly flexible because it does not have a metal foil, so it can be applied to places where bending is required and can also be miniaturized. The all-resin thermal power generation element of the present invention can be made self-supporting despite not having a metal foil. The all-resin thermal power generation element of the present invention can reduce interfacial resistance because it does not have a metal foil. The all-resin thermal power generation element of the present invention can reduce raw material costs, simplify the manufacturing process, and can be manufactured in a short time because it does not have a metal foil. The all-resin thermal power generation element of the present invention can prevent the risk of internal shots caused by cracking of the metal film. [Brief explanation of the drawing]

[0009] [Figure 1] This diagram shows a conventional heat-utilizing power generation element. [Figure 2] This figure shows the all-resin heat-utilizing power generation element of the present invention. [Figure 3] This figure shows a conventional multilayer thermal power generation element (A) having a metal layer between thermal power generation elements, and a multilayer all-resin thermal power generation element of the present invention (B or C) that does not have a metal layer between all-resin thermal power generation elements. (B) has a metal layer on the outside of one semiconductor layer and on the outside of the other conductive polymer layer of the multilayer all-resin thermal power generation element. [Figure 4] Figure (A) shows the adhesion between a semiconductor layer manufactured by a conventional method and a metal foil, and Figure (B) shows the adhesion between a semiconductor layer manufactured by the method of the present invention and a metal foil. [Modes for carrying out the invention]

[0010] [1] All-resin thermoelectric power generation element The all-resin thermoelectric power generation element of the present invention comprises a semiconductor layer that generates thermally excited electrons and holes, an electrolyte layer containing a solid electrolyte or electrolyte solution on which charge-transporting ion pairs can move, and a conductive polymer layer containing an electron transport material. The all-resin thermoelectric power generation element of the present invention does not include a metal layer on the outside of the semiconductor layer and the conductive polymer layer. In this specification, "all resin" means that the internal effective cell structure does not contain a metal layer, and the semiconductor layer, electrolyte layer, and conductive polymer layer contain resin. Although no metal is used in the laminated structure, metal current collectors may be used for the positive and negative electrodes. In addition, metal wires, carbon sheets, graphene, or conductive fibers may be used as current collectors instead of the metal layer.

[0011] Semiconductor layer The semiconductor layer constituting the thermoelectric power generation element of the present invention includes a semiconductor. In the present specification, "semiconductor" means a material capable of generating 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 invention functions as a thermoelectric conversion material.

[0012] Examples of the metal semiconductor include Si semiconductors and Ge semiconductors. Examples of the tellurium compound semiconductor include Bi-Te compounds (for example, Bi2Te3, Sb2Te3, CsBi4Te6, Bi2Se3, Bi 0.4 Sb 1.6 Te3, Bi2(Se,Te)3, (Bi,Sb)2(Te,Se)3, (Bi,Sb)2Te3, or Bi2Te 2.95 Se 0.05 ), Pb-Te compounds (for example, PbTe, or Pb 1-x Sn x Te), SnTe, Ge-Te, AgSbTe2, Ag-Sb-Ge-Te compounds (for example, GeTe-AgSbTe2 (TAGS)), Ga2Te3, (Ga 1-x In x )2Te3, 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.

[0013] Examples of the silicon-germanium (Si-Ge) compound semiconductor include Si x Ge 1-x , or SiGe-GaP.

[0014] Examples of 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 Alternatively, CrSi2 can be mentioned.

[0015] Examples of skutterudite compound semiconductors include compounds represented by 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), and derivatives of the said compound, formula RM4X. 12 (wherein R is a rare earth element 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) A compound represented by Yb y Fe 4-x Co x S 12 (CeFe3CoSb 12 ) 1-x (MoO2) x or (CeFe3CoSb 12 ) 1-x (WO2) x We can list some examples.

[0016] As a clathrate compound semiconductor, formula M8X 46 A compound represented by (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), and a derivative of the said compound, formula (II)8(III) 16 (IV) 30Examples of compounds represented by the formula (II)8(III) are shown below. 16 (IV) 30 Examples of compounds include Ba8Ga x Ge 46-x Ba 8-x (Sr,Eu) x Au6Ge 40 , or Ba 8-x EU x Cu6Si 40 ) can be cited.

[0017] Examples of 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.

[0018] 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), or 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).

[0019] Examples of metal oxide semiconductors include In2O3-SnO2, (CaBi)MnO3, Ca(Mn,In)O3, and Na x V2O5, V2O5, ZnMnGaO4 and its derivatives, LaRhO3, LaNiO3, SrTiO3, SrTiO3:Nb, Bi2Sr2Co2O y na x CoO2, NaCo2O4, CaPd3O4, formula Ca a M 1 b Co c M 2 d Ag e Of (wherein, M 1 is one or two 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, 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 2.2≦a≦3.6, 0≦b≦0.8, 2≦c≦4.5, 0≦d≦2, 0≦e≦0.8, 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 exemplified.

[0020] Examples of the organic semiconductor include organic perovskites, polyaniline, polyacetylene, polythiophene, polyalkylthiophene, or polypyrrole.

[0021] Examples of other semiconductors include alloys containing Co and Sb (for example, CoSb3, CeFe3CoSb 12 , CeFe4CoSb 12 , or YbCo4Sb 12 ), alloys containing Zn and Sb (for example, ZnSb, Zn3Sb2, or Zn4Sb3), alloys containing Bi and Sb (for example, Bi 88 Sb 12 ), CeInCu2, (Cu,Ag)2Se, Gd2Se3, CeRhAs, or CeFe4Sb 12 , Li 7.9 B 105 , BaB6, SrB6, CaB6, AlPdRe compounds (for example, Al 71 Pd 20 (Re 1-x Fe x )9), AlCuFe quasicrystals, Al 82.6-x Re 17.4 Si x 1 / 1-cubic approximant crystals, YbAl3, YbMn x Al3, β-CuAgSe, B4C / Ba3C, (Ce 1-x Lax )Ni2, or (Ce 1-x La x )In3 can be cited.

[0022] The semiconductor layer may contain components other than semiconductors, insofar as the semiconductor can generate a sufficient number of thermally excited electrons and holes for power generation when subjected to an appropriate temperature. Examples of such components, though not limited to them, include binders that bind thermoelectric materials (such as polyvinyl alcohol, methylcellulose, acrylic resin, and agar), and sintering aids that assist in the molding of thermoelectric materials (such as magnesium oxide, yttrium oxide, and calcium oxide). Furthermore, residual solvents used in the manufacturing process may remain. The first layer used in this invention functions substantially as a thermoelectric layer. The semiconductor layer of the present invention includes a resin. The resin is not limited to, but examples include the binder mentioned above.

[0023] 《Electrolyte layer》 The electrolyte layer contains a solid electrolyte or electrolyte solution on which charge-transporting ion pairs can move. In this specification, “charge-transporting ion pair” means two stable ions with different valencies, where one ion is oxidized or reduced to become the other ion, and which can carry electrons and holes. These may be ions of the same element with different valencies. The ion source contained in the solid electrolyte of the present invention is not particularly limited as long as it is a metal ion, and 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 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, or trivalent iron ions. However, it is preferable to have two stable ions with different valencies, as one ion can be oxidized or reduced to become the other ion, which can carry electrons and holes. Therefore, in the case of copper ions, monovalent and divalent copper ions are preferred, and in the case of iron ions, divalent and trivalent iron ions are preferred. As monovalent copper ions, for example, CuCl, CuBr, copper(I) acetate, copper(I) iodide, or copper(I) sulfate can be used. As divalent copper ions, CuCl2, CuTSFI2, copper(II) acetate, copper(II) sulfate, or copper(II) acetylacetonate can be used. As 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 trivalent iron ions, FeCl3, K3[Fe(CN)6], iron(III) acetylacetonate, or iron(III) sulfate can be used.

[0024] The concentration of the ion source is not particularly limited as long as the effects of the present invention are obtained, but it is preferable to add it in an amount of 0.01 to 98 mol% relative to the polymer, for example. Within this range, the ion source can efficiently transport electrons and holes.

[0025] (electrolyte) The electrolyte may include a solid electrolyte or an electrolyte solution. The electrolyte is not limited in that it can transport two ions of a charge-transporting ion pair. In other words, the electrolyte used in the electrolyte layer is not particularly limited, as long as its oxidation-reduction potential is at an appropriate position relative to the valence electron charge position of the thermoelectric conversion material used in the thermoelectric power generation element, and charge transport ion pairs can move freely within the electrolyte. Preferably, the electrolyte is 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.

[0026] 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. In other words, the compounds contained in the electrolyte solution (liquid electrolyte) and the compounds contained in the solid electrolyte overlap. The electrolyte also includes molten salts, ionic liquids, or deep eutectic solvents. A molten salt is a salt composed of cations and anions that is in a molten state. Among molten salts, those with relatively low melting points (for example, those below 100°C or below 150°C) are called ionic liquids. In this specification, molten salts in a solid state are referred to as solid electrolytes, and those in solution form are referred to as electrolyte solutions (liquid electrolytes). The following are specific examples of electrolyte solutions (liquid electrolytes), solid electrolytes, and molten salts, but these may overlap.

[0027] The electrolyte solution used is in a liquid state at a temperature at which the semiconductor within the semiconductor layer generates a sufficient number of thermally excited electrons and holes for power generation. Specifically, examples of electrolyte solutions, though not limited to them, include methoxide ions, hydrogen ions, ammonium ions, pyridinium 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 bromide ions.

[0028] As the solid electrolyte, a solid-state one is used that allows charge transport ion pairs to move therethrough at a temperature at which the semiconductor in the semiconductor layer generates a sufficient number of thermally excited electrons and holes for power generation. By using the high-temperature solid electrolyte, it can be used in a thermoelectric power generation element using a thermoelectric power generation element body that generates thermally excited electrons and holes at high temperatures. Specifically, non-limiting examples of the solid electrolyte include a sodium ion conductor, a copper ion conductor, a lithium ion conductor, a silver ion conductor, a hydrogen ion conductor, a strontium ion conductor, an aluminum ion conductor, a fluorine ion conductor, a chlorine ion conductor, or an oxide ion conductor. Specific examples of the solid electrolyte include 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, 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, Li7La3Zr2O 12 , Li7La3Zr 2-x Nb x O 12 , Li7La3Zr 2-x TaxO 12 , Li5La3Ta2O 12 , Li 0.33 La 0.55 TiO3, Li 1.5 Al 0.5 Ge 1.5 P3O 12 , Li 1.3 Al 0.3 Ti 1.7 P3O 12Examples include Li3PO4 (LiPON), Li4SiO4-Li3PO4, Li4SiO4, or Li3BO3. Furthermore, molten salts can be used as solid electrolytes or electrolyte solutions. In the case of 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.

[0029] Examples of molten salts include those containing at least one cation selected from the group consisting of imidazolium cation, pyridinium cation, piperidinium 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 anions, sulfonate anions, halogen anions, tetrafluoroborate, hexafluorophosphate, bis(trifluoromethanesulfonyl)imide, and bis(fluorosulfonyl)imide. The electrolyte in the present invention functions as a hole-transfer material.

[0030] The electrolyte layer is not limited to being able to transport holes generated by the thermoelectric conversion material, and may include components other than solid electrolytes or electrolyte solutions. Examples of such components include, but are not limited to, solvents for dissolving or dispersing the electrolyte when preparing the second layer (e.g., water, methanol, toluene, tetrahydrofuran), binders for binding the electrolyte (e.g., polyvinyl alcohol, methylcellulose, acrylic resin, agar), and sintering aids for shaping the hole-transporting material (e.g., magnesium oxide, yttrium oxide, calcium oxide). The second layer used in this invention functions substantially as a hole transport layer. The electrolyte layer contains a resin. The resin is not limited to the above, but examples include the binder or metal salt (ion source), a separator (made of resin), or an insulating ceramic.

[0031] The electrolyte layer can be fabricated by methods such as squeegeeing, screen printing, sputtering, vacuum deposition, sol-gel method, or spin coating. For example, CuZr2(PO4)3, described later, was fabricated by the sol-gel method, and the resulting sol was used to prepare a layered electrolyte layer using the squeegee method. Furthermore, if the electrolyte is an electrolyte solution (liquid electrolyte), the second layer will be in the liquid phase. When the second layer is in the liquid phase, it is preferable to prepare the second layer in the thermoelectric power generation element during the manufacturing of the thermoelectric power generation device, thermocell, or thermoelectric power generation module. In other words, the second layer can be prepared by providing a tank for holding the electrolyte solution (liquid electrolyte).

[0032] Conductive polymer layer The conductive polymer layer contains an electron transport material. Examples of electron transport materials include polythiophene-based conductive polymers, polyacetylene-based conductive polymers, polyaniline-based conductive polymers, and polypyrrole-based conductive polymers. Specific examples of electron transport materials include polyacetylene, poly(p-phenylene), poly(p-phenylenevinylene), and polyaniline.

[0033] The conductive polymer layer may contain components other than electron transport materials, as long as they can transport thermally excited electrons generated by the thermoelectric conversion material. These components are not limited to, but may include binders that bind the electron transport materials (such as polyvinyl alcohol, methylcellulose, acrylic resin, and agar), and sintering aids that assist in the molding of the electron transport materials (such as magnesium oxide, yttrium oxide, and calcium oxide). Furthermore, residual solvents used in the manufacturing process may remain. The third layer used in this invention functions substantially as an electron transport layer. In the thermoelectric power generation element of the present invention, the electron conduction potential of the electron transport material is the same as, or positively positive than, the conduction charge of the semiconductor in the semiconductor layer. Therefore, the electron transport material can transport thermally excited electrons.

[0034] Conductive polymer layers can be fabricated by methods such as squeegeeing, screen printing, sputtering, vacuum deposition, single crystal growth, or spin coating. When using the spin coating method, an oxadiazole derivative is dissolved in a polar solvent such as acetone, and the conductive polymer layer is fabricated by spin coating the solution onto a substrate or a first layer.

[0035] 《Laminated all-resin thermal energy generating element》 The all-resin thermal power generation element of the present invention can be used as a laminated all-resin thermal power generation element by laminating two or more all-resin thermal power generation elements. Conventional laminated thermal power generation elements have a metal layer between the laminated thermal power generation elements, as shown in Figure 3A. In contrast, the laminated all-resin thermal power generation element of the present invention does not have a metal layer between the laminated thermal power generation elements, as shown in Figure 3B or C. As shown in Figure 3B, a metal layer may be provided as a current collector on the outside of one semiconductor layer and on the outside of the other conductive polymer layer of the laminated all-resin thermal power generation element. Furthermore, a metal wire, carbon sheet, graphene, or conductive fiber can be used as a current collector instead of a metal layer.

[0036] [2] Method for manufacturing a semiconductor layer The all-resin thermal power generation element of the present invention does not have a metal layer. Therefore, in the method for manufacturing the semiconductor layer, the semiconductor layer and the metal foil substrate are separated. Conventional manufacturing methods are coating and drying methods, and as shown in Figure 4A, the bonding area between the semiconductor layer and the metal foil is large, resulting in strong adhesion between the semiconductor film and the metal foil. Therefore, it is difficult to separate the semiconductor layer and the metal foil. According to the semiconductor layer manufacturing method of the present invention, as shown in Figure 4B, the bonding area between the semiconductor layer and the metal foil is small, and the semiconductor film and the metal foil can be easily separated.

[0037] A method for manufacturing a semiconductor layer includes the steps of (1) mixing a semiconductor material with a binder solution to obtain a semiconductor binder mixture, (2) mixing a solvent that cannot dissolve the binder to obtain a gel mixture, (3) coating a metal foil with the gel mixture and sandwiching it with another metal foil, (4) applying pressure to the gel mixture sandwiched between the metal foils, and (5) peeling off the metal foils.

[0038] In the mixing step (1) described above, the semiconductor material is mixed into the binder solution. The semiconductor material can be any semiconductor material not limited to those described in the section "Semiconductor Layer". Examples of the aforementioned binders, though not limited to them, include PVDF, PVA, PEC, PEG, PMMA, PA, PE, PPG, PP, PAI, PU, ​​PI, or PPC. The solvent used to dissolve the binder is not limited to, but may include NMP solution, DMSO solution, DMF solution, pyridine solution, toluene solution, acetone solution, or acetonitrile solution.

[0039] In step (2) of obtaining the semi-solid mixture, a solvent that cannot dissolve the binder is mixed to obtain the semi-solid mixture. By adding a solvent that cannot dissolve the binder, a semi-solid mixture can be obtained. Solvents that cannot dissolve the binder include acetone, alcohols (e.g., methanol, ethanol, propanol, etc.), water, ether, or THF. The amount of solvent that cannot dissolve the binder added is not particularly limited as long as a semi-solid mixture can be obtained, but if the semiconductor binder mixture is 100 parts by volume, for example, 1 to 50 parts by volume, preferably 5 to 30 parts by volume, and more preferably 10 to 15 parts by volume can be added.

[0040] In step (3) above, the semi-solid mixture is applied to a metal foil and then sandwiched between two metal foils. That is, the semi-solid mixture is sandwiched between two metal foils. The aforementioned metal foil is not particularly limited, but examples include stainless steel foil, copper foil, aluminum foil, titanium foil, gold foil, silver foil, platinum foil, nickel foil, zinc foil, or brass foil. However, instead of using metal foil, the semi-solid mixture may be placed in a hydraulic press or the like in the following pressure application step (4) and pressure may be applied. The hydraulic press or the like may become contaminated with the semi-solid mixture, but the present invention can still be fully implemented.

[0041] In the pressure application step (4), pressure is applied to the semi-solid mixture. The pressure applied to the semi-solid mixture is not particularly limited as long as the effects of the present invention are obtained, but for example, it should be in the range of 0.01 to 200 MPa, with a preferred range of 0.1 MPa to 20 MPa. However, a more preferred range is 1 to 10 MPa. The method of applying pressure is not particularly limited, but pressure can be applied using a hydraulic press or a hand press.

[0042] If metal foil is used in step (3) above, the metal foil is removed in the metal foil removal step (5). Specifically, the upper metal foil is slowly removed so as not to break the film, and then vacuum dried at, for example, 25°C to 80°C, preferably 50°C to 70°C. After vacuum drying, the lower metal foil is slowly removed so as not to break the self-supporting film.

[0043] [3] Method for manufacturing a conductive polymer layer A conductive polymer dispersion is dropped onto a metal foil. After uniform dispersion to the required thickness, it is dried at a high temperature. The dried polymer metal foil is left in an inert gas atmosphere. A conductive polymer layer is obtained. The aforementioned metal foil is not particularly limited, but examples include stainless steel foil, copper foil, aluminum foil, titanium foil, gold foil, silver foil, platinum foil, nickel foil, zinc foil, or brass foil. Examples of the aforementioned conductive polymers include polythiophene-based conductive polymers, polyacetylene-based conductive polymers, polyaniline-based conductive polymers, and polypyrrole-based conductive polymers. Specific examples of electron transport materials include polyacetylene, poly(p-phenylene), poly(p-phenylenevinylene), and polyaniline.

[0044] [4] Power generation method The power generation method of the present invention relates to a thermoelectric power generation element in which the thermally excited electron density of the semiconductor that generates thermally excited electrons and holes in the semiconductor layer is 10 15 / cm 3 The power generation is performed in an environment with a temperature above which this occurs. In the power generation method of the present invention, the thermally excited electron density is preferably 10 15 / cm 3 That is all, more 10 18 / cm 3 The above is true, and more preferably 10 20 / cm 3 The above is the most preferred, and most preferably 10 22 / cm 3 That concludes the explanation. The higher the thermally excited electron density, the higher the power generation efficiency that can be obtained. The temperature applied to the semiconductor can be appropriately selected to generate a sufficient number of thermally excited electrons and holes for power generation in each semiconductor. In other words, in this invention, a voltage can be generated in a thermoelectric power generation element by applying a temperature to the semiconductor that generates a sufficient number of thermally excited electrons and holes for power generation. The number of thermally excited electrons and holes sufficient for power generation is actually expressed in terms of electron density, and it is sufficient if it is about the same as the number of photoexcited electrons in the semiconductor used in solar cells, for example, the number of photoexcited electrons in amorphous silicon used in solar cells is 10⁻¹⁰. 15 / cm 3 For example, in the thermoelectric conversion material used in the present invention, the thermal excitation electron density is 10 15 / cm 3 At temperatures above this level, it is possible to generate a sufficient number of thermally excited electrons and holes for power generation, and power generation can be performed at temperatures above that level.

[0045] [5] Thermoelectric power generation device, thermocell and thermoelectric power generation module The thermoelectric power generation device of the present invention includes the thermoelectric power generation element of the present invention, preferably including a positive electrode and / or a negative electrode. Furthermore, the thermocell of the present invention includes the thermoelectric power generation element of the present invention, preferably including a positive electrode and / or a negative electrode. Moreover, the thermoelectric power generation module of the present invention includes the thermoelectric power generation element of the present invention, preferably including a positive electrode and / or a negative electrode. In this specification, "thermocell" means a battery that includes the thermoelectric power generation element of the present invention and generates electricity when a temperature capable of generating thermally excited electrons and holes is applied to the semiconductor (thermoelectric conversion material) of the thermoelectric power generation element. In other words, a thermocell is a "battery that generates electricity if there is a heat source" and differs from conventional "batteries that generate electricity using a high-temperature part and a low-temperature part".

[0046] "electrode" The positive and negative electrodes are not limited in that they can transport electrons, but examples include titanium, gold, platinum, silver, copper, tin, tungsten, niobium, tantalum, stainless steel, aluminum, graphene, molybdenum, indium, vanadium, rhodium, niobium, chromium, nickel, carbon, alloys thereof, or combinations thereof. The same material may be used for both the positive and negative electrodes. The positive electrode and negative electrode may be provided in the form of a wire, or they may be provided as a positive electrode layer or a negative electrode layer. In the case of a positive electrode layer or a negative electrode layer, they can be manufactured by methods such as vacuum deposition or spin coating. By providing the negative electrode on the third layer side and the positive electrode on the second layer side of the thermoelectric power generation element, electrons can move from the negative electrode to the positive electrode, generating electricity.

[0047] [6] Thermoelectric power generation method The thermoelectric power generation method of the present invention includes the steps of installing the thermoelectric power generation module in a heat-generating location and heating the thermoelectric power generation module with heat to generate electricity.

[0048] 《Thermoelectric Power Generation Module Installation Process》 In the thermoelectric power generation module installation process, the thermoelectric power generation module of the present invention is installed at the heat generation location. The heat generation location is not particularly limited, as long as it is a location that generates heat above the temperature required to produce a sufficient number of excited electrons and holes for power generation in the thermoelectric conversion material. However, a location with a relatively high temperature is preferred for efficient power generation, and therefore, examples of heat generation locations include geothermal energy sources or waste heat sources such as factories. Geothermal energy is not limited to heat in the soil, but also includes hot water or steam heated by geothermal energy. Furthermore, geothermal energy includes hot water or steam from seas, lakes, or rivers that are heated by geothermal energy. Waste heat is not particularly limited, but examples include waste heat from steel furnaces, waste incinerators, substations, subways, or automobiles. In particular, waste heat from steel furnaces and waste incinerators, which have large amounts of energy, is released without utilizing that energy, and it is preferable to reuse it using the thermoelectric power generation method of the present invention.

[0049] Power generation process In the power generation process, electricity is generated by heating the thermoelectric power generation module of the present invention. The heat generated from the heat generation location heats the thermoelectric conversion material of the thermoelectric power generation module to a temperature above which a sufficient number of excited electrons and holes are generated for power generation, thereby enabling the thermoelectric power generation module to generate electricity. [Examples]

[0050] The present invention will be specifically described below with reference to examples, but these examples are not intended to limit the scope of the present invention.

[0051] Example 1 (PEDOT: Self-supporting membrane creation for PSS) A conductive polymer layer was prepared. 1 mL of PEDOT / PSS dispersion was coated and dispersed onto a mirror-finished copper foil, and dried at 120°C. After that, it was left in an argon gas atmosphere for several hours, and the PEDOT / PSS self-supporting film was peeled off.

[0052] (Electrolyte preparation) An electrolyte layer was prepared. A 5% polyvinylidene fluoride (PVDF) solution was prepared by dissolving 5% PVDF in N-methyl-2-pyrrolidone (NMP) by heating at 60°C. 166 mg of lithium chloride (LiCl) was dissolved in 8 g of this solvent by heating at 60°C. 68 mg of copper(I) chloride and 94 mg of copper(II) chloride were added and dissolved by heating at 60°C. The resulting electrolyte solution was added dropwise to a separator. Once the separator was immersed in the electrolyte solution, it was heated at 60°C and vacuum-dried.

[0053] (Creation of self-supporting semiconductor films) A semiconductor layer was prepared. 200 mg of Ge was placed in a mortar and ground. 2.0 g of binder solution (PVDF NMP solution) was added and stirred. Next, 1 mL of acetone, a solvent that cannot dissolve the binder, was added to make the semiconductor mixture semi-solid. A stainless steel foil was laid down, the semiconductor mixture was placed on top of it, and then sandwiched with another stainless steel foil. It was clamped in a vise (universal angle vise, manufactured by Palmgren) at a pressure of 2 MPa for 1 hour at room temperature. After removing it from the pressure machine, the top and bottom stainless steel foils were peeled off, and it was vacuum-dried at 60°C to obtain a self-supporting semiconductor film.

[0054] The conductive polymer layer, electrolyte layer, and semiconductor layer obtained in the above process were stacked as follows to obtain the all-resin thermal power generation element of the present invention. A power generation unit for an all-resin thermal power generation element was obtained by stacking a "conductive polymer layer" (positive electrode), an "electrolyte layer," and a "semiconductor layer" (negative electrode) in that order (Figure 2). Furthermore, multiple of the above units can be stacked to fabricate an all-resin thermal power generation element.

[0055] Example 2 In this embodiment, the operation of Example 1 was repeated, except that PVA was used instead of PVDF as the binder, to obtain the all-resin thermal power generation element of the present invention. In the fabrication of a self-supporting semiconductor film, the stainless steel foil could be easily peeled off from the semiconductor layer.

[0056] Example 3 In this embodiment, the operation of Example 1 was repeated, except that PEC was used instead of PVDF as the binder, to obtain the all-resin thermal power generation element of the present invention. In the fabrication of a self-supporting semiconductor film, the stainless steel foil could be easily peeled off from the semiconductor layer.

[0057] Comparative Example 1 In this embodiment, a lumen-fired power generation element having a metal layer was fabricated according to a conventional method. (PEDOT: Creation of PSS membrane) A conductive polymer layer was prepared. 1 mL of PEDOT / PSS dispersion was coated and dispersed onto a mirror-finished copper foil, and dried at 120°C. It was then left in an argon gas atmosphere for several hours. A PEDOT / PSS film with a mirror-finished copper foil was obtained.

[0058] (Electrolyte preparation) An electrolyte layer was prepared. A 5% polyvinylidene fluoride (PVDF) solution was prepared by dissolving 5% PVDF in N-methyl-2-pyrrolidone (NMP) by heating at 60°C. 166 mg of lithium chloride (LiCl) was dissolved in 8 g of this solvent by heating at 60°C. 68 mg of copper(I) chloride and 94 mg of copper(II) chloride were added and dissolved by heating at 60°C. The resulting electrolyte solution was added dropwise to a separator. Once the separator was immersed in the electrolyte solution, it was heated at 60°C and vacuum-dried.

[0059] (Fabrication of semiconductor layers containing metal foil) A semiconductor layer was created. 200 mg of Ge was placed in a mortar and ground. 2.0 g of binder solution (PVDF NMP solution) was added and stirred. The mixture was dropped onto stainless steel foil, and a film was formed using an applicator. The coated metal foil was vacuum-dried at 60°C. The metal foil could not be peeled off from the semiconductor layer.

[0060] The conductive polymer layer, electrolyte layer, and semiconductor layer obtained in the above process were stacked as follows to obtain a conventional heat-utilizing power generation element. The power generation unit of a conventional heat-utilizing power generation element was obtained by stacking the conductive polymer layer (positive electrode) / electrolyte layer / semiconductor layer (negative electrode) in that order (Figure 1). [Industrial applicability]

[0061] The all-resin thermal power generation element of the present invention does not contain metal foil, so it is highly flexible and can be applied to locations where bending is required, and can also be miniaturized.

Claims

1. A semiconductor layer that generates thermally excited electrons and holes. An electrolyte layer containing a solid electrolyte or electrolyte solution on which charge-transporting ion pairs can move, and A conductive polymer layer containing electron transport material, A total resin heat-utilizing power generation element that includes these elements in this order, An all-resin thermal power generation element that does not contain a metal layer on the outside of either the semiconductor layer or the conductive polymer layer.

2. A laminated all-resin thermal power generation element, wherein two or more all-resin thermal power generation elements described in claim 1 are laminated together, and each all-resin thermal power generation element is laminated by a semiconductor layer and a conductive polymer layer.

3. The heat-utilizing power generation element according to claim 1, wherein the thermally excited electron density of the semiconductor that generates thermally excited electrons and holes in the semiconductor layer is 10 １５ / cm ３ A method of generating electricity by placing the device in an environment with a temperature above a certain level.

4. A thermoelectric power generation device including the heat-utilizing power generation element described in claim 1.

5. A thermocell comprising the thermoelectric power generation element described in claim 1.

6. A thermoelectric power generation module including the thermoelectric power generation element described in claim 1.

7. A step of installing the thermoelectric power generation module described in claim 6 at a heat generation location, and A process of heating the thermoelectric power generation module with heat to generate electricity, A thermoelectric power generation method, including...

8. The thermoelectric power generation method according to claim 7, wherein the heat is geothermal or waste heat.

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