Laminated battery and method for manufacturing a laminated battery

Abstract

The laminated battery 1 comprises a heat-utilizing power generation element 3 that is independent of temperature gradients, and a packaging body 5 in which the heat-utilizing power generation element 3 is enclosed. The manufacturing method of the laminated battery 1 includes a placement step of placing a laminated electrode 4 on a first sheet 51, which is formed by laminating a first electrode 41 containing a current collector and a semiconductor material, and a second electrode 45 containing a current collector, with a separator 48 in between; a welding step of placing a second sheet 52 on the first sheet 51 on which the laminated electrode 4 is placed, and welding the edges of the first sheet 51 and the second sheet 52 to form a bag body 50 having an opening OP; an injection step of injecting an electrolyte solution EL into the bag body 50 through the opening OP; and a sealing step of sealing the opening OP to form a packaging body 5.

Description

[Technical Field]

[0001] This invention relates to a laminated battery and a method for manufacturing a laminated battery. [Background technology]

[0002] One method of generating electricity using thermal energy is the Seebeck effect. In this method, thermal energy is converted into electrical energy through thermoelectric conversion using a temperature gradient.

[0003] Patent documents 1 and 2 propose a semiconductor-sensitized thermal cell that generates electricity using oxidation-reduction reactions caused by thermally excited charges in semiconductors and the like. Hereafter, this thermal cell will also be referred to as "STC". [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 6803076 [Patent Document 2] International Publication No. 2022 / 191101 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] STC is a thermal power generation element that does not depend on temperature gradients and can generate electricity even under isothermal conditions. Compared to thermal power generation elements that require a temperature gradient, STC can be made smaller and lighter because it does not require cooling equipment, and is expected to be used in a variety of situations. [Means for solving the problem]

[0006] The laminated battery in this disclosure is A heat-utilizing power generation element that is independent of the temperature gradient, The package comprises the aforementioned heat-generating power generation element and, The aforementioned heat-utilizing power generation device is A current collector, which serves as an electron transport layer, and a semiconductor layer, which serves as a thermoelectric conversion material, are in contact with each other. A laminated electrode is formed by stacking a first electrode and a second electrode including a current collector with a spacer in between. The packaging comprises an electrolyte solution sealed inside the packaging body together with the stacked electrodes and impregnated into the spacer. 、 The electron conduction band level of the electron transport material in the electron transport layer is the same as or positive to the conduction band level of the thermoelectric conversion material. The spacer is in contact with the semiconductor layer of the first electrode and the second electrode. The electrolyte solution impregnated in the spacer is an electrolyte that allows two ions of a charge-transporting ion pair to move, The valence band level of the thermoelectric conversion material is more positive than the redox level of the charge transport ion pair. .

[0007] Furthermore, this disclosure is, A method for manufacturing a laminate-type battery in which a heat-utilizing power generation element that does not depend on a temperature gradient is enclosed in a package, The arrangement step involves placing a laminated electrode on a first sheet, which is formed by stacking a first electrode containing a current collector and a semiconductor material, and a second electrode containing a current collector, with an electrolyte solution-impregnable spacer in between. A welding step involves placing a second sheet on the first sheet on which the stacked electrodes are arranged, welding the edges of the first and second sheets together to form a bag with an opening, An injection step of injecting the electrolyte solution into the inside of the bag through the opening, The method includes a sealing step of sealing the opening to form the package. [Effects of the Invention]

[0008] According to this disclosure, a thermal power generation element that does not depend on a temperature gradient can be applied to a laminate-type battery that is easy to manufacture and has a compact configuration, making it usable in a variety of situations. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic diagram illustrating the structure of a laminated battery. [Figure 2]This is a schematic diagram illustrating the configuration of a heat-utilizing power generation element and the mechanism of power generation. [Figure 3] This diagram illustrates the distribution of ions within the electrolyte layer. [Figure 4] This is a schematic diagram showing an example of the output voltage waveform of a heat-utilizing power generation element. [Figure 5] This is an exploded perspective view of the multilayer electrodes that make up a heat-generating power generation element. [Figure 6] This is a schematic diagram showing a cross-section of a laminate-type battery along line AA in Figure 1. [Figure 7] This flowchart shows an example of the manufacturing process for laminated batteries. [Figure 8] This is a diagram illustrating the placement steps. [Figure 9] This diagram illustrates the application of the tab film during the placement step. [Figure 10] This is a diagram illustrating the welding step and the injection step. [Figure 11] This is a diagram illustrating the sealing step. [Figure 12] This flowchart shows another example of a manufacturing method for laminated batteries. [Figure 13] This is a schematic diagram showing another example of a separator configuration used in multilayer electrodes. [Figure 14] This diagram illustrates an example of a method for forming the containment section of a separator. (a) shows multiple regions that partition the separator, and (b) shows the state in which the multiple regions are folded over. [Figure 15] This figure illustrates another example of a method for forming the containment area of ​​a separator, where (a) shows multiple regions that partition the separator, and (b) shows the multiple regions overlapped. [Modes for carrying out the invention]

[0010] Figure 1 is a schematic diagram illustrating the structure of laminate-type battery 1. Laminate-type battery 1 is also called a "pouch-type battery." As shown in Figure 1, the laminated battery 1 comprises a heat-utilizing power generation element 3 and a packaging body 5 in which the heat-utilizing power generation element 3 is enclosed. The laminated battery 1 also includes tab leads 7, which are terminals. The tab leads 7 are arranged to extend from the inside to the outside of the packaging body 5 and are connected to the heat-utilizing power generation element 3 inside the packaging body 5. As shown in Figure 1, a circuit can be configured to supply power to a load R by connecting the heat-generating power element 3 to the load R via tab leads 7 and connecting wires L1 and L2. A switch SW is provided on connecting wire L1. The switch SW allows switching between connecting and disconnecting the load R and the heat-generating power element 3. The operation of the switch SW is controlled by a control device (not shown).

[0011] <Heat-utilizing power generation element> Figure 2 is a schematic diagram illustrating the configuration of the heat-utilizing power generation element 3 and the mechanism of power generation. Figure 2 shows an example of a heat-utilizing power generation element 3, specifically a heat-utilizing power generation element 3 (STC) using a thermoelectric conversion material such as a semiconductor. A "thermoelectric conversion material" refers to a material that can convert thermal energy into electrical energy regardless of the temperature gradient of the installation environment. For example, if the "thermoelectric conversion material" is a semiconductor, it means a semiconductor that can generate thermally excited charges by being placed in a predetermined temperature environment, even without a temperature difference. Conventional heat-based power generation methods include steam turbine power generation and power generation utilizing the Seebeck effect. However, steam turbines require the use of water resources as well as heat, necessitating large-scale facilities. Power generation utilizing the Seebeck effect requires the application of a temperature gradient to the power generation element, thus necessitating the installation of cooling equipment in addition to a heat source. On the other hand, STC can generate electricity using various types of heat, such as geothermal energy, solar heat, waste heat from factories and data centers, body heat, and room temperature, making it applicable to both small-scale and large-scale power generation. Furthermore, STC is not limited to being installed on a fixed heat source; it can also be installed on a heat flow of liquid or gas to generate electricity. In addition, since STC does not require a cooling device, circuits equipped with STC can be easily miniaturized.

[0012] As shown in Figure 2, the heat-utilizing power generation element 3 has a first part 31, a second part 34 in contact with the first part 31, and an electrode 35 in contact with the second part 34. The first part 31 is heated by electrons (e - The second part 34 includes a semiconductor that generates ) and holes (h). The first part 31, the second part 34, and the electrode 35 can be formed, for example, in layers. When heat is applied to the heat-utilizing power generation element 3, the semiconductor of the first part 31 generates thermally excited electrons (e - This creates a state where ) and holes (h) are generated, creating an energy level difference between the first part 31 and the electrode 35, which generates a voltage. This causes discharge to occur to the load R.

[0013] The first part 31 may specifically consist of two layers: a layer containing a semiconductor (hereinafter simply referred to as the "semiconductor layer 32") and a layer containing an electron transport material (hereinafter simply referred to as the "electron transport layer 33"). In this case, the semiconductor layer 32 is arranged to be in contact with the second part 34. In the configuration example shown in Figure 2, the electron transport layer 33 of the first part 31 functions as the paired electrode to electrode 35. Electrode 35 and the electron transport layer 33 of the first part 31 are connected to connecting lines L1, L2, and load R via tab leads 7 (see Figure 1). Alternatively, a paired electrode to electrode 35 may be provided separately from the first part 31.

[0014] <<Part 1>> As shown in Figure 2, the first part 31 is a thermally excited electron (e - The semiconductor includes a semiconductor that generates ions () and holes (h), and functions substantially as a thermally excited charge generation layer; however, it is not limited to any particular configuration. The valence band level of the semiconductor is positive compared to the redox level of the charge transport ion pair. Therefore, at the interface between the first part 31 and the second part 34 of the present invention, one of the charge transport ion pairs, which is more easily oxidized, is oxidized to become the other ion. The level difference between the valence band level of the semiconductor in the first part 31 and the redox level of the charge transport ion pair in the second part 34 is not limited, but is preferably 0 to 1.0 V, more preferably 0.05 to 0.5 V, and even more preferably 0.05 to 0.3 V. For example, the level difference between the redox level of CuZr2(PO4)3 (Cusicon, a copper ion conductor) and the valence band level of β-FeSi2 is about 0.05 V.

[0015] <<Semiconductor>> The semiconductor in the first part 31 may be any material that can generate thermally excited electrons (e - ) and holes (h), and is not limited. The semiconductor can be, for example, a metal semiconductor, a telluride compound semiconductor, a silicon germanium (Si-Ge) compound semiconductor, a silicide compound semiconductor, a skutterudite compound semiconductor, a clathrate compound semiconductor, a Heusler compound semiconductor, a half-Heusler compound semiconductor, a metal oxide semiconductor, an organic semiconductor, a sulfide semiconductor, and other semiconductors.

[0016] Examples of the metal semiconductor include Si semiconductors and Ge semiconductors. Examples of the telluride compound semiconductor include Bi-Te compounds (e.g., 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 (e.g., PbTe, or Pb 1-x Sn x Te), SnTe, Ge-Te, AgSbTe2, Ag-Sb-Ge-Te compounds (e.g., GeTe-AgSbTe2 (TAGS)), Ga2Te3, (Ga 1-x In x)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 cited as an example. As for silicon germanium (Si-Ge) compound semiconductors, Si x Ge 1-x Examples include, or SiGe-GaP. 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. 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 (CeFe3CoSb12 ) 1-x (WO2) x One could list these: 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) 30 Examples 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 One could list these: 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. 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). 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 kaNax CoO2, NaCo2O4, CaPd3O4, formula Ca a M 1 b Co c M 2 d Ag e O f (In the formula, M 1 M is one or more elements selected from the group consisting of Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and rare earth elements. 2 (where is one or two elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Mo, W, Nb, Ta, and Bi, and the values ​​are 2.2≦a≦3.6, 0≦b≦0.8, 2≦c≦4.5, 0≦d≦2, 0≦e≦0.8, 8≦f≦10), compounds represented by ZnO, Na(Co,Cu)2O4, ZnAlO, Zn 1-x Al x O, or La 1.98 Sr 0.02 CuO4 can be mentioned. Examples of organic semiconductors include organic perovskites, polyaniline, polyacetylene, polythiophene, polyalkylthiophene, or polypyrrole. Examples of sulfide semiconductors include Ag2S, ZnS, and CdS. Other thermoelectric compounds 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 S 12 ), CeInCu2, (Cu,Ag)2Se, Gd2Se3, CeRhAs, or CeFe4Sb 12 Li 7.9 B 105 BaB6, SrB6, CaB6, AlPdRe compounds (e.g., Al 71 Pd 20 (Re 1-x Fe x)9), AlCuFe quasicrystal, Al 82.6-x Re 17.4 Si x 1 / 1 - cubic approximate crystal, YbAl3, YbMn x Al3, β - CuAgSe, B4C / Ba3C, (Ce 1-x La x )Ni2, or (Ce 1-x La x )In3 can be mentioned.

[0017] <<Electron transport material>> The electron transport material contained in the electron transport layer 33 can be a semiconductor or a metal. The electron conduction band level of the electron transport material is the same as or positive with respect to the conduction band level (the energy level of the electron conductor) of the semiconductor that generates thermal excitation electrons (e - ) and holes (h). The electron transport material only needs to have an electron conduction band level (the energy level of the electron conduction band) that is the same as or positive with respect to the conduction band level of the semiconductor, and is not limited. Specific electron transport materials can be, for example, an N - type semiconductor containing at least one selected from the group consisting of silicon, niobium, titanium, zinc, tin, vanadium, indium, tungsten, tantalum, zirconium, molybdenum, and manganese, an N - type metal oxide, an N - type metal sulfide, an alkali metal halide, an alkali metal, or an electron - transporting organic substance, various metals (such as copper).

[0018] More specifically, the electron transport material can be, for example, titanium oxide, tungsten oxide, zinc oxide, niobium oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, or SrTiO3. Furthermore, electron-transporting organic materials can include, for example, N-type conductive polymers, N-type low-molecular-weight organic semiconductors, π-electron conjugated compounds, surfactants, carbon materials, specifically, oxadiazole derivatives, triazole derivatives, perylene derivatives, or quinolinol metal complexes, cyano-group-containing polyphenylene vinylenes, boron-containing polymers, vasocuproin, vasophenanthrene, hydroxyquinolinatoaluminum, oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, phosphine oxide compounds, phosphine sulfide compounds, fluoro-group-containing phthalocyanines, fullerenes and their derivatives, phenylene vinylene polymers, perylenetetracarboxylic acid imide derivatives, and graphite.

[0019] The difference in energy levels between the electron conduction band level of an electron transport material and the conduction band level of a semiconductor is not limited, but is preferably 0.01 to 1 V, more preferably 0.01 to 0.5 V, even more preferably 0.01 to 0.3 V, and most preferably 0.05 to 0.2 V. For example, the difference in energy levels between the conduction band level of β-FeSi2 and the conduction band level of n-type silicon, i.e., the electron conduction band level, is approximately 0.01 V.

[0020] The semiconductor in the first part 31 can be manufactured by, for example, the squeegee method, screen printing method, discharge plasma sintering method, compression molding method, sputtering method, vacuum deposition method, roll-to-roll method, inkjet printing method, dip coating method, powder coating method, CVD method, Czochralski method, or spin coating method. When using the spin coating method, the semiconductor can be manufactured by dispersing β-FeSi2 in a polar solvent such as acetone and spin coating the solution onto an electron transport material or the second part 34 described below. Alternatively, β-FeSi2 may be manufactured by the discharge plasma sintering method, and the resulting β-FeSi2 powder and a conductive binder (e.g., a high-temperature conductive coating agent) may be squeegeeed onto the electron transport material or the second part 34.

[0021] Electron transport materials can be fabricated by methods such as squeegeeing, screen printing, sputtering, vacuum deposition, single crystal growth, roll-to-roll, inkjet printing, dip coating, powder coating, CVD, Czochralski method, or spin coating. 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 semiconductor to produce the electron transport material. The n-type silicon described later can be obtained by single crystal growth. Semiconductors may also be laminated using n-type silicon as a substrate. The first part 31 may contain other components to the extent that the semiconductor can generate a sufficient number of thermally excited electrons and holes for power generation by applying heat. These other components are not limited to, but may include, for example, binders (such as polyvinyl alcohol, methylcellulose, acrylic resin, or agar) and sintering aids that help in the formation of the semiconductor (such as magnesium oxide, yttrium oxide, or calcium oxide). Furthermore, the first part 31 may contain residual solvents used in the manufacturing process.

[0022] <<Part 2>> Part 2, section 34, should contain an electrolyte that allows the two ions of the charge-transporting ion pair to move. For example, electrolytes can be solid electrolytes or electrolyte solutions. In other words, the electrolyte included in the second part 34 should have an appropriate redox energy level relative to the valence band position (valence band energy level) of the semiconductor in the first part 31, and should be such that charge transport ion pairs can move freely within the electrolyte. Furthermore, the electrolyte should have a sufficient number of thermally excited electrons (e) for the semiconductor in the first part 31 to generate electricity. - Preferably, the material is physically and chemically stable at the temperature at which it generates ) and holes (h) (hereinafter also referred to as the "power generation temperature").

[0023] Depending on the temperature, electrolytes can exist as either an electrolyte solution (liquid electrolyte) or a solid electrolyte. In this specification, the electrolyte solution is such that the semiconductor of the first part 31 generates a sufficient number of thermally excited electrons (e - This refers to a solution (liquid) at the temperature at which it generates ) and holes (h). In addition, a solid electrolyte is defined as a semiconductor in the first part 31 that has a sufficient number of thermally excited electrons (e) for power generation. - This refers to a solid state in which charge-transporting ion pairs can move within the body at the temperature at which ) and holes (h) are produced. Furthermore, the electrolyte may include 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. An ionic liquid is a type of molten salt that has a relatively low melting point (for example, below 100°C or below 150°C). In this specification, molten salts in a solid state are referred to as "solid electrolytes," while those in solution form are referred to as "electrolyte solutions (liquid electrolytes)." Specific examples of electrolyte solutions (liquid electrolytes), solid electrolytes, and molten salts are shown below, although there may be some overlap between them.

[0024] The electrolyte solution used is in a liquid state at the aforementioned power generation temperature. As an example, a solution containing compounds (electrolytes) that generate ionic species such as methoxy 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 can be used as an electrolyte solution.

[0025] As a solid electrolyte, for example, an electrolyte that becomes solid at high temperatures can be used. Using an electrolyte that exists in a solid state at high temperatures allows for power generation in high-temperature environments. Solid electrolytes also include solid polymer electrolytes and gel electrolytes. As an example, 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 can be used as solid electrolytes. More specifically, solid electrolytes include, for example, RbAg4I5, Li3N, Na2O·11Al2O3, Sr-β-alumina, Al2(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 Ta x O 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 12 Li3PO4 (LiPON), Li4SiO4-Li3PO4, Li4SiO4, Li3BO3, etc., can be used as solid electrolytes. In addition, as solid polymer electrolytes or gel electrolytes, those obtained by dissolving the aforementioned ions in a polymer such as polyethylene glycol can be used.

[0026] Furthermore, molten salts can be used as solid electrolytes or electrolyte solutions. When used in relatively low-temperature environments, ionic liquids can also be used. Deep eutectic solvents (DES) can be used as ionic liquids. As an example, the molten salt can include (a) 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 (b) 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.

[0027] In the thermal power generation element 3, the electrolyte functions as both a hole-transfer material and an electron-transfer material. A charge-transporting ion pair consists of two stable ions with different valencies. In an ion pair, one ion is oxidized or reduced to become the other ion (Ox / Red), and electrons (e - It can carry charge-transporting ions (H) and holes (H). The charge-transporting ion pair may be ions of the same element but with different valencies. For example, 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.

[0028] At the interface between the first part 31 and the second part 34, an oxidation reaction occurs between the two ions, with the ion being more easily oxidized. At the interface between the electrode 35 and the second part 34, a reduction reaction occurs between the two ions, with the ion being more easily reduced. As described above, the valence band level of the semiconductor in the first part 31 is more positive than the redox level of the charge transport ion pair in the second part 34. As a result, at the interface between the first part 31 and the second part 34, of the two ions (Ox / Red), the ion that is more easily oxidized is oxidized to become the other ion. As a result, electrons (e - ) and holes (h) are carried.

[0029] The second part 34 may preferably contain alkali metal ions as additives. These alkali metal ions may be, for example, lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, or francium ions. Preferably, the alkali metal ions are lithium ions, sodium ions, or potassium ions. The inclusion of alkali metal ions in the second part 34 can extend the lifespan of the heat-utilizing power generation element 3. Furthermore, the discharge characteristics can be restored by applying heat to the heat-utilizing power generation element 3 and leaving it to stand. The alkali metal ions may be added to the electrolyte in the form of, but are not limited to, halides, perchloric acid (e.g., LiClO4), sulfates, or strong acid salts. For example, alkali metal compounds can be used in various forms as long as they do not degrade the solvent.

[0030] The halogens that form halides with alkali metal ions can be, for example, fluorine, chlorine, bromine, iodine, and astatine. Examples of compounds formed by alkali metal ions and chlorine include LiCl, NaCl, KCl, RbCl, CsCl, or FrCl. The amount of alkali metal compound added is not limited, but for example, adding 0.001 to 100 parts by weight, preferably 0.01 to 10 parts by weight, and more preferably 0.03 to 0.1 parts by weight per 100 parts by weight of electrolyte can contribute to extending the battery life of the thermal power generation element 3.

[0031] The second part 34 may include components other than solid electrolytes or electrolyte solutions. For example, the second part 34 may include polar solvents for dissolving or dispersing the electrolyte (such as water, methanol, toluene, or tetrahydrofuran), binders for binding the electrolytes (such as polyvinyl alcohol, methylcellulose, acrylic resin, or agar), and sintering aids for shaping hole-transfer materials (such as magnesium oxide, yttrium oxide, or calcium oxide).

[0032] The second part 34 can be fabricated 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 is fabricated by the sol-gel method. The resulting sol can be prepared as the second part 34 by the squeegee method. Also, if the electrolyte is an electrolyte solution (liquid electrolyte), the second part 34 will be in the liquid phase. When the second part 34 is in the liquid phase, it is preferable to prepare the second part 34 in the heat-utilizing power generation element 3 when fabricating the power generation module 10. That is, the second part 34 can be fabricated by providing a tank for holding the electrolyte solution (liquid electrolyte).

[0033] <<Electrode>> The material that makes up electrode 35 is electron (e - Any transportable material is acceptable and not limited to the specified material. The material constituting the electrode 35 can be, for example, fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), antimond-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), zinc oxide (ZnO), indium oxide (In2O3), tin oxide (SnO2), IZO (In-Zn-O), or IGZO (In-Ga-Zn-O). Furthermore, the material constituting the electrode 35 may be a metal that does not react with charge transport ion pairs, such as 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 electrode 35 may be laminated on the first part 31 and the second part 34, or it may be provided in the form of a wire. When the electrode 35 is laminated on the first part 31 and the second part 34, it can be manufactured by a vacuum deposition method or a spin coating method, etc.

[0034] By applying heat to the heat-utilizing power generation element 3, the following (i) to (vi) occur. (i) electrons of the semiconductor layer 32 of the first part 31 (e - Energy is transferred when heat is applied to it (=thermal excitation). (ii) Thermally excited electrons (e - ) moves to the more stable electron transport layer 33. (iii) When the first part 31 and electrode 35 are connected to the load R via the tab lead 7 (see Figure 1) and connecting wires L1 and L2, electrons (e - ) moves the connecting wire L1, load R, and connecting wire L2 through the first part 31 to the side of the counter electrode 35. (iv) Electrons that moved to electrode 35 (e - ) is formed on the electrode 35 surface in contact with the second part 34, by oxide ions (Cu) of the electrolyte contained in the second part 34. 2+ (Ox)) reduces ions (Cu + Reduce to (Red) (v) The semiconductor holes (h) in semiconductor layer 32 replace the electrons lost in the movement in (ii) by reducing ions (Cu) of the electrolyte in the second part 34. + (Red)) and oxide ions (Cu 2+ It oxidizes to (Ox). (vi) The oxidized and reduced ions of part 34 move within the electrolyte, respectively. This causes electrons (e - ) and holes (h) are carried.

[0035] Figure 3 illustrates the ion distribution within the electrolyte of the second part 34. Figure 3(a) schematically shows a state where the ion distribution within the electrolyte is uniform and the heat-generating power element 3 is able to discharge. Figure 3(b) schematically shows a state where the ion distribution within the electrolyte is non-uniform and the discharge of the heat-generating power element 3 has stopped. Figure 4 is a schematic diagram showing an example of the output voltage waveform of the heat-utilizing power generation element 3. Figure 4 shows the change in output voltage when the switch SW is repeatedly opened and closed according to the characteristics of the heat-utilizing power generation element 3.

[0036] The thermal power generation element 3 generates electricity by combining thermally excited charges of a semiconductor with oxidation-reduction reactions of an electrolyte to convert thermal energy into electrical energy. As oxidation-reduction reactions are repeated in the heat-utilizing power generation element 3, the Fermi level of the semiconductor layer 32 and the oxidation-reduction level of the electrolyte in the second part 34 reach a state of chemical equilibrium. As a result, the discharge of the heat-utilizing power generation element 3 ends.

[0037] In this state, an uneven distribution of ions occurs within the electrolyte of the second part 34. As shown in Figure 3(b), at the end of the discharge, oxide ions (Cu 2+ The concentration of (Ox) decreases as it moves from the semiconductor layer 32 towards the electrode 35, and the reducing ions (Cu + The concentration of (Red) decreases as you move from electrode 35 towards semiconductor layer 32. That is, the concentration of oxide ions (Cu) near semiconductor layer 32 decreases. 2+ The concentration of (Ox) is highest, while the concentration of reducing ions (Cu) is highest near electrode 35. + The concentration of (Red) will be the highest.

[0038] After the discharge of the heat-utilizing power generation element 3 is completed, if the switch SW is opened while heat is still being applied to the heat-utilizing power generation element 3, thereby disconnecting the heat-utilizing power generation element 3 from the load R, the electrons that have been thermally excited in the semiconductor layer 32 have nowhere to go, resulting in a change in the equilibrium state of the electrolyte in the second part 34. Specifically, the ions in the electrolyte of the second part 34 diffuse in an attempt to eliminate the uneven distribution. As a result, within the electrolyte of the second part 34, oxide ions (Cu 2+ The uneven distribution of (Ox) concentration and the reduction ion (Cu + As the concentration imbalance of (Red) gradually disappears, the thermal power generation element 3 recovers toward its initial state where discharge is possible (see Figure 3(a)). As shown in Figure 4, after the time the switch SW is turned off, the voltage that the thermal power generation element 3 can output recovers (Figure 4: Voltage recovery).

[0039] When the ions in the electrolyte have diffused and the ion distribution is no longer uneven (see Figure 3(a)), the switch SW is closed and the thermal power generation element 3 is connected to the load R, causing the thermal power generation element 3 to start discharging again (Figure 4: Discharge).

[0040] Thus, when the heat-utilizing power generation element 3 continues to discharge and reaches a chemical equilibrium state (see Figure 3(b)), power generation ceases. Even after power generation has ceased, by transitioning to a state where no power is extracted, it recovers towards a state where power generation can resume (see Figure 3(a)).

[0041] The heat-utilizing power generation element 3 generates a large open-circuit voltage (OCV) when heat is applied. As shown in Figure 4, when the switch SW is closed (ON), the heat-utilizing power generation element 3 starts discharging. For example, if the load R is a battery, the power from the heat-generating element 3 is supplied to the battery, and the battery is charged.

[0042] The voltage of the heat-generating power generation element 3 drops rapidly due to discharge, then gradually decays until it reaches a voltage value indicating the end of discharge. When the switch SW is opened (OFF) at this timing, the connection between the heat-generating power generation element 3 and the load R is interrupted, and the voltage of the heat-generating power generation element 3 recovers. Then, when the ion distribution bias in the heat-generating power generation element 3 is resolved (recovered) to a degree that discharge is possible (see Figure 3(a)), the switch SW is closed again (ON), and the heat-generating power generation element 3 starts discharging again.

[0043] <Example of laminated battery configuration> The following describes a specific example of the configuration of a thermal power generation element 3 used in the laminate-type battery 1 shown in Figure 1. As an example, the thermal power generation element 3 can be composed of a laminated electrode in which three electrodes are stacked with a separator (a spacer that can be impregnated with an electrolyte solution) in between. Figure 5 is an exploded perspective view of the multilayer electrode 4 that constitutes the heat-utilizing power generation element 3. Figure 6 is a schematic diagram showing a cross-section of the laminate-type battery 1 along line AA in Figure 1. In Figure 5, the coating layers 43 and 47 are shown with hatching. In Figure 6, the cross-section of the separator 48 is shown without hatching for clarity. Also, Figure 6 is a schematic diagram, and the thickness (length in the Z direction) of the laminated electrode 4 is exaggerated. Furthermore, although Figure 6 shows a gap between the laminated electrode 4 and the packaging 5, in the actual laminated battery 1, the laminated electrode 4 and the packaging 5 are in close contact. Furthermore, in the following explanation, the stacking direction of the first electrode 41 and the second electrode 45 will be referred to as the Z direction, and of the two directions orthogonal to the Z direction, the left-right direction in Figure 6 will be referred to as the X direction, and the direction orthogonal to both the Z and X directions will be referred to as the Y direction.

[0044] As shown in Figure 5, the laminated electrode 4 comprises a first electrode 41 including a thermoelectric conversion material (semiconductor) and a current collector which serves as an electron transport material, and a second electrode 45 including a current collector. In the laminated electrode 4, the second electrode 45 is laminated on both sides of the first electrode 41 in the stacking direction (thickness direction), with a separator 48 in between. The first electrode 41 and the second electrode 45 can be, for example, rectangles of the same shape and size. The first electrode 41 and the second electrode 45 are stacked so that they overlap each other when viewed from the Z direction.

[0045] As shown in Figure 6, the first electrode 41 is composed of, for example, a Cu foil 42 which is an electron transport material, and a coating layer 43 formed on both sides of the Cu foil 42. The coating layer 43 can be formed, for example, by kneading Ge powder (semiconductor) and a conductive binder (for example, a high-temperature conductive coating agent) and applying it to the surface of the Cu foil 42. The second electrode 45 is composed of, for example, a Cu foil 46 which is a current collector and a coating layer 47 formed on both sides of the Cu foil 46. The coating layer 47 can be formed, for example, by applying carbon paste to the surface of the Cu foil 46. Furthermore, the second electrode 45 may be composed solely of a current collector, without the formation of the coating layer 47.

[0046] The separator 48 can be made of, for example, a porous membrane formed from a resin film, paper, or nonwoven fabric. Although not shown in the figures, the separator 48 has pores through which the electrolyte solution can pass. To ensure insulation between the first electrode 41 and the second electrode 45, the separator 48 can be the same size as the first electrode 41 and the second electrode 45, or larger than the first electrode 41 and the second electrode 45. The spacer interposed between the first electrode 41 and the second electrode 45 is not limited to the separator 48, as long as it ensures insulation between the first electrode 41 and the second electrode 45 and is impregnable with the electrolyte solution. For example, it may be a spacer made of fine glass particles. For example, a spacer can be formed by coating or fusing fine glass particles to at least one of the opposing surfaces of the first electrode 41 and the second electrode 45.

[0047] As shown in Figure 6, in the laminated battery 1, the electrolyte solution EL is sealed inside the packaging 5 along with the stacked electrodes 4. The electrolyte solution EL impregnates the separator 48 of the stacked electrodes 4 inside the packaging 5. The first electrode 41 functions as the first part 31 of the thermal power generation element 3 (see Figure 2), the separator 48 impregnated with the electrolyte solution EL functions as the second part 34, and the second electrode 45 functions as electrode 35.

[0048] As shown in Figure 5, each of the stacked electrodes 4 is connected to a tab lead 7. The tab lead 7 comprises a first lead 71 connected to the first electrode 41 and a second lead 72 connected to the second electrode 45. The first lead 71 is connected, for example, to one edge 41a of the first electrode 41 in the Y direction. The first lead 71 extends along the Y direction away from the first electrode 41. The second lead 72 is connected, for example, to one edge 45a of the second electrode 45 in the Y direction. The second lead 72 extends along the Y direction away from the second electrode 45. The first lead 71 and the second lead 72 extend substantially parallel to each other along the Y direction.

[0049] The first lead 71 and the second lead 72 are positioned so as not to overlap when viewed from the Z direction, which is the stacking direction. For example, the first lead 71 is provided at one end in the X direction of the edge 41a of the first electrode 41, and the second lead 72 is provided at the other end in the X direction of the edge 45a of the second electrode 45. Note that the first lead 71 and the second lead 72 only need to be spaced apart from each other, and the configuration is not limited to this. For example, the first lead 71 may be provided on one edge 41a in the Y direction of the first electrode 41, and the second lead 72 may be provided on the other edge 45b in the Y direction of the second electrode 45. In this case, the first lead 71 and the second lead 72 extend away from each other from the stacked first electrode 41 and second electrode 45. Furthermore, the second leads 72 of the two second electrodes 45 are positioned to overlap each other when viewed from the Z direction. In other words, the two second leads 72 are positioned opposite each other in the Z direction. The two second leads 72 are integrated by bonding their opposing surfaces with an adhesive, and function as a single terminal, as shown in Figure 1.

[0050] The first lead 71 and the second lead 72 can be made of current collectors such as Cu foil 42, 46 (see Figure 6), similar to the first electrode 41 and the second electrode 45. The first lead 71 and the second lead 72 may be formed integrally with the first electrode 41 and the second electrode 45, or they may be formed separately from the first electrode 41 and the second electrode 45 and connected to the first electrode 41 and the second electrode 45 by welding or the like. The base end 71a of the first lead 71, which connects to the first electrode 41, is located inside the packaging 5 (see Figure 6) in the laminated battery 1, while the tip end 71b is located outside the packaging 5. The base end 72a of the second lead 72, which connects to the second electrode 45, is located inside the packaging 5 (see Figure 6) in the laminated battery 1, while the tip end 72b is located outside the packaging 5. As shown in Figure 5, the base end 71a of the first lead 71, like the first electrode 41, has coating layers of Ge powder (semiconductor) and a conductive binder (e.g., high-temperature conductive coating agent) formed on both sides of the Cu foil. The base end 72a of the second lead 72, like the second electrode 45, has a carbon paste coating layer formed on both sides of the Cu foil. The tip ends 71b and 72b of the first lead 71 and the second lead 72 have the surface of the Cu foil exposed.

[0051] The packaging body 5 (see Figure 6) in which the laminated electrode 4 is enclosed can be made from, for example, a laminate sheet made of aluminum foil coated with an insulating resin. The packaging body 5 can be formed, for example, by overlapping two rectangular laminate sheets (first sheet 51, second sheet 52) ​​with the laminated electrode 4 in between, and welding the four opposing edges of the first sheet 51 and second sheet 52 together. Furthermore, the packaging material 5 can be made from various materials as long as it has high thermal conductivity and insulating properties.

[0052] The following describes an example of a manufacturing method for laminate-type battery 1. Figure 7 is a flowchart showing the manufacturing method of the laminated battery 1. Figure 8 is a diagram illustrating the placement steps. Figure 9 illustrates the application of the tab film 75 during the placement step. Figure 10 illustrates the welding step and the injection step. Figure 11 illustrates the sealing step. As shown in Figure 7, the manufacturing process of the laminate-type battery 1 includes steps S01: placement step, step S02: welding step, step S03: injection step, and step S04: sealing step.

[0053] As shown in Figure 8, in the arrangement step, each element constituting the laminated electrode 4 is placed on the first sheet 51 that makes up the packaging 5. Specifically, the first second electrode 45, separator 48, first electrode 41, separator 48, and second second electrode 45 are placed on the first sheet 51 in that order. Alternatively, these elements may be stacked in advance to form the laminated electrode 4 before being placed on the first sheet 51. In the illustrated example, the first lead 71 and the second lead 72 are integrally formed with the first electrode 41 and the second electrode 45. As shown in Figure 9, when the laminated electrode 4 is placed on the first sheet 51, when viewed from the Z direction, the edges 51a to 51d of the first sheet 51 surround the laminated electrode 4 with some space between them. The first lead 71 and the second lead 72 extend from the laminated electrode 4 placed on the first sheet 51 to one side in the Y direction (upper side in the figure). The first lead 71 and the second lead 72 traverse one edge 51a of the first sheet 51 in the Y direction and extend outward from the first sheet 51.

[0054] As shown in Figure 9, a tab film 75 (film) is attached so as to cover the portions (transverse portions 71c, 72c) of the first lead 71 and the second lead 72 that cross the edge 51a of the first sheet 51. The tab film 75 enhances the adhesion between the tab lead 7 and the first sheet 51. The tab film 75 is attached to the first sheet 51 so as to sandwich the transverse portions 71c and 72c of the tab lead 7. The length L75 of the tab film 75 in the X direction is longer than the lengths L71 and L72 of the first lead 71 and second lead 72 in the X direction, respectively. In other words, when viewed from the Z direction, the tab film 75 covers the entire transverse portions 71c and 72c. The tab film 75 is positioned such that its lower portion in the Y direction is below the edge 51a of the first sheet 51, and its upper portion in the Y direction is above the edge 51a of the first sheet 51. Note that attaching the tab film 75 can be omitted.

[0055] As shown in Figure 10(a), in the welding step, the second sheet 52 is placed on top of the first sheet 51 on which the laminated electrode 4 is positioned, and the three edges are welded together. In Figure 10, the areas to be welded are indicated by dashed hatching. Specifically, first, the two sheets are overlapped so that the four edges 51a to 51d of the first sheet 51 face the four edges 52a to 52d of the second sheet 52 in the Z direction. Then, the three opposing edges of the overlapped first sheet 51 and second sheet 52 are welded together to form a bag 50 with an opening OP, as shown in Figure 10(b). In the illustrated example, one edge 51a of the first sheet 51 in the Y direction (upper side in the figure) and the edges 51c and 51d that connect to one and the other ends of the edge 51a in the X direction are welded to the opposing edges 52a, 52c, and 52d of the second sheet 52. In this case, the edges 51b and 52b on the other side (lower side in the figure) of the first lead 71 and the second lead 72 in the Y direction remain unwelded, and the opening OP of the bag body 50 is formed between these edges 51b and 52b. The proximal ends 71a and 72a of the first lead 71 and the second lead 72 are located inside the bag 50, while the tip ends 71b and 72b are located outside the bag 50. Furthermore, the portion of the tab film 75 below the edge 51a is located inside the bag 50, while the portion above it is located outside the bag 50. In addition, the edges that remain unwelded in the welding step are not limited to edges 51b and 52b, but may be other edges.

[0056] As shown in Figure 10(b), in the injection step, the electrolyte solution EL is injected into the bag 50 through the opening OP. This impregnates the separator 48 of the stacked electrode 4 placed inside the bag 50 with the electrolyte solution EL, thereby forming the heat-generating power generation element 3.

[0057] As shown in Figure 11, the sealing step seals the opening OP of the bag 50. This completes the formation of a laminated battery 1 in which the heat-generating element 3 is enclosed inside the packaging 5 (see Figure 1). In the sealing step, it is desirable to weld the opening OP of the bag 50 in a vacuum. By welding in a vacuum, the air inside the bag 50 is removed, which prevents deterioration of the laminated battery 1. Furthermore, when the laminated battery 1 is returned to atmospheric pressure after welding, the pressure difference between the inside of the packaging 5 and the atmosphere applies pressure in the stacking direction, which is the thickness direction of the packaging 5. This causes each element of the heat-utilizing power generation element 3 (first electrode 41, second electrode 45, and separator 48) sealed inside the packaging 5 to adhere closely to each other, fixing the position of the heat-utilizing power generation element 3 inside the packaging 5.

[0058] The above-mentioned example configuration and manufacturing method for laminate-type battery 1 are merely examples, and various variations are available. Several variations are described below.

[0059] For example, in the configuration example described above (see Figure 5), a tab lead 7 (first lead 71, second lead 72) formed integrally with the first electrode 41 and the second electrode 45 is shown extending from the inside to the outside of the packaging body 5. However, the invention is not limited to this example. For example, another tab lead may be connected to the tab lead 7 formed integrally with the first electrode 41 and the second electrode 45 located inside the packaging body 5, and extended to the outside of the packaging body 5.

[0060] Figure 12 is a flowchart showing another example of a manufacturing method for laminate-type battery 1. For example, Figure 7 shows an example where the welding step (step S02) and injection step (step S03) are performed after the placement step (step S01). However, as shown in Figure 12, the placement step (step S13) may be performed after the welding step (step S11) and injection step (step S12).

[0061] For example, first, the second sheet 52 is placed on top of the first sheet 51, and the three edges are welded together to form a bag 50 (welding step). Next, the electrolyte solution EL is injected into the bag 50 (injection step). Then, the laminated electrodes 4 are placed inside the bag 50 into which the electrolyte solution EL has been injected (placement step). After that, the opening OP of the bag 50 is sealed (sealing step: step S14), and a laminate-type battery 1 can be constructed in which the heat-utilizing power generation element 3 is enclosed inside the packaging 5.

[0062] Figure 13 is a schematic diagram showing another configuration example of the separator 48A used in the multilayer electrode 4. Note that in Figure 13, the thickness in the Z direction of the separator 48A, the first electrode 41, and the second electrode 45 is omitted from the illustration. As shown in Figure 13, the separator 48A has a plurality of housing sections 49a to 49c capable of accommodating the first electrode 41 and the second electrode 45. The number of housing sections is formed in proportion to the total number of first electrodes 41 and second electrodes 45 that constitute the stacked electrode 4. In the illustrated example, an example is shown in which three housing sections 49a, 49b, and 49c are formed. The housing sections 49a, 49b, and 49c are each formed in a bag shape and are arranged in the Z direction, which is the stacking direction of the first electrode 41 and the second electrode 45. When viewed from the Z direction, the housing sections 49a, 49b, and 49c overlap each other. Housing sections 49b and 49c are arranged on one side (upper side in the figure) and the other side (lower side in the figure) of housing section 49a in the Z direction. Both ends of housing sections 49a, 49b, and 49c in the X direction and one end in the Y direction (rear side in the figure) are closed, and an opening K is formed at the other end in the Y direction (front side in the figure) into which the first electrode 41 or the second electrode 45 can be inserted.

[0063] Figure 14 illustrates an example of a method for forming the housing portions 49a, 49b, and 49c of the separator 48A. Figure 14(a) shows multiple regions A1 to A4 that partition the separator 48A, and Figure 14(b) shows the state in which the multiple regions A1 to A4 are folded over. As shown in Figure 14(a), the separator 48A can be made from, for example, a single rectangular sheet. By folding the separator 48A, the housing portions 49a, 49b, and 49c for the first electrode 41 and the second electrode 45 can be formed. For example, when forming three housing sections 49a, 49b, and 49c in the separator 48A, the separator 48A is divided equally into four rectangular regions A1, A2, A3, and A4 aligned in the X direction. Regions A1 to A4 are larger in size than the first electrode 41 and the second electrode 45.

[0064] As shown in Figure 14(b), the separator 48A is folded along the boundaries La, Lb, and Lc of each region (dashed lines in Figure 14(a)). In doing so, the folding direction (mountain fold and valley fold) of each boundary La, Lb, and Lc is set to the opposite direction from the adjacent boundary, so that regions A1, A2, A3, and A4 are folded in the Z direction relative to the adjacent regions. For example, fold separator 48A in a mountain fold along the boundary line La between region A1 and region A2, and fold region A2 onto region A1 in the Z direction. Next, fold separator 48A in a valley fold along the boundary line Lb between region A2 and region A3, and fold region A3 onto region A2. Finally, fold separator 48A in a mountain fold along the boundary line Lc between region A3 and region A4, and fold region A4 onto region A3.

[0065] By folding the separator 48A in this way, regions A1, A2, A3, and A4 each face and overlap with their adjacent regions in the Z direction. The edges of the overlapping regions of the folded separator 48A (hatched areas in the diagram) are glued together. Specifically, the ends of the overlapping regions in the X direction and one end in the Y direction (the far side of the paper) are glued together, while the other end in the Y direction (the near side of the paper) is left unglued. The bonding method may be, for example, welding, or an adhesive may be used. The housing portions 49a, 49b, and 49c of the separator 48A only need to be able to hold the first electrode 41 or the second electrode 45 inside, and the airtightness required for the packaging 5 that encloses the electrolyte solution EL is not necessary. Therefore, each end may be bonded together completely, or partially bonded in several places.

[0066] As shown in Figure 13, by bonding the ends of opposing regions of the folded separator 48A together, bag-shaped housing portions 49a, 49b, and 49c capable of accommodating the first electrode 41 or the second electrode 45 are formed. Specifically, regions A1 and A2 form a housing portion 49c for housing the second electrode 45. Regions A2 and A3 form a housing portion 49a for housing the first electrode 41. Regions A3 and A4 form a housing portion 49b for housing the second electrode 45. Furthermore, an opening K is formed on the other side (front side in the figure) in the Y direction of each housing section 49a, 49b, and 49c for inserting the first electrode 41 or the second electrode 45.

[0067] In the illustrated example, three storage compartments 49a, 49b, and 49c are shown, but any number of storage compartments can be formed by increasing or decreasing the number of regions that partition a single sheet (see Figure 14(a)).

[0068] When the first electrode 41 is inserted into the housing portion 49a of the separator 48A, and the second electrodes 45 are inserted into the housing portions 49b and 49c respectively, the first electrode 41 and the two second electrodes 45 are stacked with the separator 48A in between, forming a stacked electrode 4 that can be applied to the thermal power generation element 3. When inserting the first electrode 41 and the second electrode 45, the edges 41a and 45a of the tab lead 7 to which the first lead 71 and the second lead 72 are connected should be oriented toward the opening K. As a result, with the first electrode 41 and the second electrode 45 housed in the housing portions 49a, 49b, and 49c, the first lead 71 and the second lead 72 extend outside the housing portions 49a, 49b, and 49c.

[0069] Furthermore, the method for forming the housing portions 49a, 49b, and 49c of the separator 48A is not limited to the method of folding a single sheet. Figure 15 illustrates another example of a method for forming the housing portions 49a, 49b, and 49c of the separator 48A. Figure 15(a) shows multiple regions A5 to A8 that partition the separator 48A, and Figure 15(b) shows the multiple regions A5 to A8 superimposed. As shown in Figure 15(a), the four rectangular regions A5, A6, A7, and A8 corresponding to the three housing portions 49a, 49b, and 49c of the separator 48A may be formed separately from each other. Regions A5, A6, A7, and A8 may be formed by cutting a sheet of one separator, or they may be formed from sheets of different separators. Regions A5 to A8 are larger in size than the first electrode 41 and the second electrode 45.

[0070] As shown in Figure 15(b), regions A5, A6, A7, and A8 of the separator 48A are stacked in the Z direction with an electrode (first electrode 41 or second electrode 45) in between. For example, the second electrode 45, region A6, and first electrode 41 are stacked on top of region A5 of the separator 48A in that order. Although not shown in the diagram, region A7, the second electrode 45, and region 8 of the separator 48A are further stacked on top of the first electrode 41. The first electrode 41 or the second electrode 45 is smaller in size than regions A5 to A8. In the stacked state, the edges of each region A5 to A8 face the edges of other overlapping regions in the Z direction. By bonding the edges of the overlapping regions together, bag-shaped housing portions 49a, 49b, and 49c (see Figure 13) for housing the first electrode 41 or the second electrode 45 are formed in the separator 48A, and the laminated electrode 4 is constructed.

[0071] The stacked electrode 4 using the bag-shaped separator 48A can be applied to either of the manufacturing methods shown in Figures 7 and 12. By housing the first electrode 41 and the second electrode 45 together in the bag-shaped separator 48A, the laminated electrode 4 becomes easier to handle, and an improvement in the manufacturing efficiency of the laminated battery 1 is expected. In addition, since the first electrode 41 and the second electrode 45 are held within the housing sections 49a, 49b, and 49c, misalignment of the laminated positions of the first electrode 41 and the second electrode 45 is reduced, making it easier to ensure mutual insulation.

[0072] As described above, the laminate-type battery 1 according to this embodiment has, for example, the following configuration. (1) The laminated battery 1 includes a heat-generating element 3 that is independent of the temperature gradient, The system comprises a package 5 in which a heat-generating element 3 is enclosed.

[0073] According to the present invention, by applying a thermal power generation element 3 that is independent of temperature gradients to a laminate-type battery 1 that is easy to manufacture and has a compact configuration, it can be used in a variety of situations. Furthermore, the laminated battery 1 has a larger surface area compared to the cylindrical battery. In other words, by applying the heat-utilizing power generation element 3 to the laminated battery 1, it is possible to secure a larger contact area with heat and improve power generation efficiency.

[0074] (2) In the laminated battery 1 of (1) above, The heat-utilizing power generation element 3 is The device comprises a first part 31 containing a thermoelectric conversion material and an electron transport material, a second part 34 in contact with the first part 31 and containing an electrolyte, and an electrode 35 in contact with the second part 34.

[0075] In this way, the heat-utilizing power generation element 3, which is independent of the temperature gradient, can have a simple structure of at least three layers. Tab leads 7, which serve as terminals, can be connected to the electrodes 35 and the first portion 31. By connecting the heat-utilizing power generation element 3 to the load R via the tab leads 7 and connecting wires L1 and L2, stable power generation and heat absorption can be achieved. In particular, unlike power generation elements that utilize the Seebeck effect, the heat-utilizing power generation element 3 of this embodiment can generate electricity using heat without requiring a temperature gradient in the installation environment. Therefore, since it does not require a mechanism to create a temperature gradient, the heat-utilizing power generation element 3 can be made smaller.

[0076] (3) In the laminated battery 1 of (1) or (2) above, The heat-generating power generation element 3 is equipped with a tab lead 7 that extends from the inside to the outside of the packaging 5.

[0077] Since the tab lead 7, which is a terminal, extends from the outside of the packaging 5, the heat-generating power generation element 3 enclosed inside the packaging 5 can be easily connected to an external load R, etc.

[0078] (4) In the laminated battery 1 of (3) above, The heat-utilizing power generation element 3 is A laminated electrode 4 is formed by stacking a first electrode 41 containing a current collector and semiconductor material, and a second electrode 45 containing a current collector, with separators 48 and 48A (spacers) interposed between them. The packaging 5 contains an electrolyte solution EL which is sealed inside the packaging body together with the stacked electrode 4 and impregnated into the separator.

[0079] In the stacked electrode 4, the first electrode 41 functions as a pair of electrodes for the first part 31 and electrode 35 of the heat-utilizing power generation element 3. Separators 48 and 48A impregnated with electrolyte solution EL function as the second part 34. The second electrode 45 functions as an electrode 35 in contact with the second part 34. The multilayer electrode 4 is lightweight and easy to make thin. Furthermore, the multilayer electrode 4 can be easily manufactured by stacking multiple electrodes (first electrode 41, second electrode 45) with separators 48, 48A in between. Also, the first electrode 41 and second electrode 45 can be easily formed integrally with the tab lead 7. In this way, by configuring the heat-utilizing power generation element 3 with a stacked electrode 4, a laminate-type battery 1 that can be used in various situations can be easily manufactured. Furthermore, the "spacer" is not limited to a separator; it can be anything that ensures insulation between the first electrode 41 and the second electrode 45 and is capable of being impregnated with the electrolyte solution. For example, it may be a spacer made of fine glass particles.

[0080] (5) In the laminated battery 1 of (4) above, The second electrode 45 is laminated on one side and the other side of the first electrode 41 in the Z direction (thickness direction), with separators 48 and 48A interposed between them.

[0081] Thus, in the stacked electrode 4, when the second electrode 45 is stacked on both sides of the first electrode 41, a structure can be formed in which the second part 34 containing the electrolyte and the electrode 35 are formed on both sides of the first part 31 of the heat-utilizing power generation element 3 shown in Figure 2. This makes it possible to increase the surface area of ​​the heat-utilizing power generation element 3 that is in contact with heat. As mentioned above, since the laminated battery 1 makes it easy to secure a surface area in contact with heat, the heat-utilizing power generation element 3 can generate power that makes better use of the advantages of the laminated battery 1.

[0082] (6) In the laminated battery 1 of (5) above, The tab lead 7 comprises a first lead 71 connected to the first electrode 41 and a second lead 72 connected to the second electrode 45.

[0083] For example, the first lead 71 and the second lead 72 can be formed integrally with the first electrode 41 and the second electrode 45, respectively. In this case, since there is no need to connect separate tab leads 7 to the first electrode 41 and the second electrode 45, the manufacturing of the laminated battery 1 can be made easier.

[0084] (7) Any of the laminate-type batteries 1 described in (4) to (6) above may have a separator 48A that constitutes the stacked electrode 4. The separator 48A has a housing section 49a (first housing section) that houses the first electrode 41, The device has housing sections 49b and 49c (second housing sections) which are provided on top of the housing section 49a and house the second electrode 45.

[0085] By housing the first electrode 41 and the second electrode 45 together in the separator 48A, the laminated electrode 4 becomes easier to handle, and an improvement in the manufacturing efficiency of the laminated battery 1 is expected. In addition, since the first electrode 41 and the second electrode 45 are held within the housing sections 49a, 49b, and 49c, misalignment of the laminated positions of the first electrode 41 and the second electrode 45 is reduced, making it easier to ensure mutual insulation.

[0086] The manufacturing method of this embodiment is a method for manufacturing a laminate-type battery 1 in which a heat-utilizing power generation element 3 that is independent of the temperature gradient is enclosed in a package 5, and comprises, for example, the following steps. (8) An example of a manufacturing method (see Figure 7) is: The arrangement step (step S01) involves placing a laminated electrode 4 on a first sheet 51, which is formed by laminating a first electrode 41 containing a current collector and semiconductor material, and a second electrode 45 containing a current collector, with separators 48 and 48A (spacers that can be impregnated with an electrolyte solution) in between. A welding step (step S02) is performed in which a second sheet 52 is placed on a first sheet 51 on which a stacked electrode 4 is arranged, and the edges of the first sheet 51 and the second sheet 52 are welded together to form a bag 50 having an opening OP. The injection step (step S03) involves injecting the electrolyte solution EL into the bag body 50 through the opening OP, The process includes a sealing step (step S04) to seal the opening OP and form the package 5. (9) Another example of a manufacturing method (see Figure 12) is: A welding step (step S11) is performed by placing the second sheet 52 on the first sheet 51 and welding the edges 51a, 51c, 51d, 52a, 52c, and 52d of the first sheet 51 and the second sheet 52 to form a bag body 50 having an opening OP. The injection step (step S12) involves injecting the electrolyte solution EL into the bag 50 through the opening OP, The arrangement step (step S13) involves placing a stacked electrode 4 inside the bag 50, which is formed by stacking a first electrode 41 containing a current collector and a semiconductor material, and a second electrode 45 containing a current collector, with separators 48 and 48A (spacers that can be impregnated with an electrolyte solution) in between. The process includes a sealing step (step S14) to seal the opening OP and form the package 5.

[0087] In this embodiment, the packaging 5 and the heat-utilizing power generation element 3 to be sealed inside the packaging 5 can be formed simultaneously, allowing for the production of a laminate-type battery 1 with the heat-utilizing power generation element 3 sealed inside in a simple process. This improves the production efficiency of the laminate-type battery 1, which can utilize the heat-utilizing power generation element 3 in various situations.

[0088] (10) In the method for manufacturing the laminated battery 1 described in (8) or (9) above, The first sheet 51 and the second sheet 52 are rectangular laminate sheets (sheets) having four edges 51a to 51d and 52a to 52d, respectively. In the welding step, three opposing edges of the first sheet 51 and the second sheet 52 (edges 51a, 51c, 51d and edges 52a, 52c, 52d) are welded together, and an opening OP is formed between the remaining edge 51b, 52b.

[0089] In this way, in the welding step, a bag 50 with an opening OP can be formed by welding only the three edges of the first sheet 51 and the second sheet 52 together. In the next injection step, the electrolyte solution EL can be injected into the bag 50 through the opening OP. Thus, this embodiment allows for the manufacture of a laminate-type battery 1 using an easy manufacturing method and in a manner that prevents leakage of the electrolyte solution EL.

[0090] (11) In any of the methods for manufacturing the laminated battery 1 described in (8) to (10) above, The separator 48A (see Figures 13 to 15) can be configured to have a plurality of housing sections 49a, 49b, and 49c that house the first electrode 41 and the second electrode 45, respectively. The separator 48A can be divided into multiple regions corresponding to the multiple housing sections 49a, 49b, and 49c (regions A1 to A4 in Figure 14(a) or regions A5 to A8 in Figure 15(a)), and the multiple regions A1 to A4 or A5 to A8 can be overlapped and the overlapping ends can be bonded together to form the housing sections 49a, 49b, and 49c.

[0091] In this way, by forming the housing portions 49a, 49b, and 49c for the first electrode 41 or the second electrode 45 in the separator 48A, the misalignment of the stacking positions of the first electrode 41 and the second electrode 45 is reduced, making it easier to ensure mutual insulation. As a method for forming the housing portion in separator 48A, for example, multiple regions A1 to A4 may be divided into a single separator sheet, each region may be folded along the boundary lines La, Lb, and Lc (see Figure 14(a)), and the overlapping ends of each region may be bonded together (see Figure 14(b)). Alternatively, for example, the multiple regions A5 to A8 of separator 48A may be separate from each other (see Figure 15(a)). Then, the multiple regions A5 to A8 may be overlapped and the overlapping ends of each region may be bonded together (see Figure 15(b)).

[0092] (i) In the method for manufacturing the laminated battery 1 described in (8) above, Tab leads 7 are connected to the stacked electrode 4. In the arrangement step (step S01), the stacked electrode 4 can be placed on the first sheet 51, and the tab lead 7 can be positioned so as to extend across the edge 51a of the first sheet 51 and outwards from the first sheet 51. (ii) In the method for manufacturing the laminated battery 1 described in (9) above, Tab leads 7 (first lead 71, second lead 72) are connected to the multilayer electrode 4. In the placement step (step S13), the laminated electrode 4 can be placed inside the bag 50, and the tab lead 7 can be positioned to extend to the outside of the bag 50, traversing the edge 51a of the first sheet 51 that forms the opening OP of the bag 50.

[0093] For example, the tab lead 7 can be formed integrally with the first electrode 41 and the second electrode 45 that constitute the multilayer electrode 4. In this case, during the placement step, the tab lead 7 can be placed when the multilayer electrode 4 is placed on the first sheet 51.

[0094] (iii) In the method for manufacturing the laminated battery 1 described in (8) or (9) above, In the placement step, the edge 51a of the first sheet 51 and the transverse portions 71c and 72c of the first lead 71 and second lead 72 (tab lead), which are the portions that cross the edge 51a of the first sheet 51, can be covered with the tab film 75 (film).

[0095] By covering the transverse portions 71c and 72c, which form the boundary where the tab lead 7 extends from the inside to the outside of the packaging body 5, with the tab film 75, the adhesion of the tab lead 7 can be improved, and the possibility of leakage of the electrolyte solution EL can be reduced.

[0096] The present invention is not limited to the embodiments and modifications described above, and can be modified as appropriate within the scope of the technical spirit of the invention. Furthermore, the modifications may not only be applied to the embodiments, but at least a part of the content of each may be applied to other modifications. [Explanation of Symbols]

[0097] 1: Laminated battery 3: Heat-generating power generation element 4: Multilayer electrodes 5: Packaging 7: Tabread 31: Part 1 34:Second part 35: Electrode 32: Semiconductor layer 33: Electron transport layer 41: 1st electrode 42: Cu foil 43: Coating layer 45:Second electrode 46: Cu foil 47: Coating layer 48, 48A: Separator 49a, 49b, 49c: Containment section 51: First sheet 51a, 51b, 51c, 51d: Edge 52: Second seat 52a, 52b, 52c, 52d: Edge 71: First lead 71a: proximal end 71b:Tip 71c: Cross section 72: Second lead 72a: proximal end 72b: Tip 72c: Cross section 75: Tab film (film) R: Load L1, L2: Connecting wires SW: Switch La, Lb, Lc: Boundary line OP: Opening K: Opening

Claims

1. A heat-utilizing power generation element that is independent of the temperature gradient, The package comprises the aforementioned heat-generating power generation element and, The aforementioned heat-utilizing power generation device is A laminated electrode is formed by stacking a first electrode, which is formed by contact between a current collector that serves as an electron transport layer and a semiconductor layer that serves as a thermoelectric conversion material, and a second electrode that includes a current collector, with a spacer in between. The packaging comprises an electrolyte solution sealed inside the stacked electrodes and impregnated into the spacer, The electron conduction band level of the electron transport material in the electron transport layer is the same as or positive to the conduction band level of the thermoelectric conversion material. The spacer is in contact with the semiconductor layer of the first electrode and the second electrode. The electrolyte solution impregnated in the spacer is an electrolyte that allows two ions of a charge-transporting ion pair to move, The valence band level of the thermoelectric conversion material is more positive than the redox level of the charge transport ion pair. Laminated batteries.

2. In the laminated battery of claim 1, The heat-generating power generation element is equipped with a tab lead extending from the inside to the outside of the packaging. The tab lead comprises a first lead connected to the first electrode and a second lead connected to the second electrode, in a laminated battery.

3. In the laminated battery of claim 1, A laminate-type battery in which the second electrode is laminated on one side and the other side in the thickness direction of the first electrode, with the spacer interposed between them.

4. In a laminated battery according to any one of claims 1 to 3, The spacer has a first housing portion for housing the first electrode, A laminate-type battery having a second housing section that is placed on top of the first housing section and houses the second electrode.

5. A method for manufacturing a laminate-type battery in which a heat-utilizing power generation element that does not depend on a temperature gradient is enclosed in a package, The arrangement step involves arranging a laminated electrode on a first sheet, which is formed by stacking a first electrode, in which a current collector that serves as an electron transport layer and a semiconductor layer that serves as a thermoelectric conversion material are in contact, and a second electrode including a current collector, with an electrolyte solution impregnable spacer in between. A welding step involves placing a second sheet on the first sheet on which the stacked electrodes are arranged, welding the edges of the first and second sheets together to form a bag having an opening, An injection step of injecting the electrolyte solution into the inside of the bag through the opening, The process includes a sealing step of sealing the opening to form the package, The electron conduction band level of the electron transport material in the electron transport layer is the same as or positive to the conduction band level of the thermoelectric conversion material. The spacer is in contact with the semiconductor layer of the first electrode and the second electrode. The electrolyte solution impregnated in the spacer is an electrolyte that allows two ions of a charge-transporting ion pair to move, The valence band level of the thermoelectric conversion material is more positive than the redox level of the charge transport ion pair. Manufacturing method for laminated batteries.

6. A method for manufacturing a laminate-type battery in which a heat-utilizing power generation element that does not depend on a temperature gradient is enclosed in a package, A welding step involves placing a second sheet on top of a first sheet and welding the edges of the first and second sheets together to form a bag with an opening. An injection step in which an electrolyte solution is injected into the inside of the bag through the opening, The arrangement step involves placing a stacked electrode inside the bag, which is formed by stacking a first electrode, in which a current collector that serves as an electron transport layer and a semiconductor layer that serves as a thermoelectric conversion material are in contact, and a second electrode, which includes a current collector, with a spacer that can be impregnated with the electrolyte solution interposed between them. The process includes a sealing step of sealing the opening to form the package, The electron conduction band level of the electron transport material in the electron transport layer is the same as or positive to the conduction band level of the thermoelectric conversion material. The spacer is in contact with the semiconductor layer of the first electrode and the second electrode. The electrolyte solution impregnated in the spacer is an electrolyte that allows two ions of a charge-transporting ion pair to move, A method for manufacturing a laminate-type battery, wherein the valence band level of the thermoelectric conversion material is more positive than the redox level of the charge transport ion pair.

7. In the method for manufacturing a laminated battery according to claim 5 or claim 6, The first sheet and the second sheet are rectangular sheets, each having four edges. A method for manufacturing a laminate-type battery, comprising the welding step of welding together the three edges of the first sheet and the second sheet and forming the opening between the remaining edge.

8. In the method for manufacturing a laminated battery according to claim 5 or claim 6, The spacer is a separator having a plurality of housing sections that accommodate the first electrode and the second electrode, respectively. The method for manufacturing a laminate-type battery involves dividing the separator into multiple regions corresponding to the multiple storage regions, overlapping the multiple regions, and bonding the overlapping ends together.

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