Potential difference generating device

Abstract

A potential difference generating device capable of generating power directly is provided. A potential difference generating device (10) comprises a base (24) made of a hydrogen-absorbing metal, etc., a nanostructure (16A) having a multilayer film (25A) provided on the base (24), a first electrode (17) provided on the nanostructure (16A), and a second electrode (18) provided opposite to the multilayer film (25A). The multilayer film (25A) has a configuration in which a first layer made of a hydrogen-absorbing metal, etc., and has a thickness of less than 1000 nm, and a second layer made of a hydrogen-absorbing metal, etc., different from the first layer, and has a thickness of less than 1000 nm, are stacked, and a heterogeneous material interface is formed between the first layer and the second layer. When the nanostructure (16A) is heated, hydrogen permeates or diffuses through the heterogeneous material interface by quantum diffusion, releasing charged particles from the multilayer film (25A) and capturing the charged particles on the second electrode (18), thereby the first A potential difference is generated between the electrode (17) and the second electrode (18).

Description

Technology Field

[0001] The present invention relates to a potential difference generating device having a nanostructure comprising a first layer and a second layer stacked on top of each other, the first layer being composed of different hydrogen-absorbing metals, and having a thickness of nano-size (less than 1000 nm). Background Technology

[0002] In recent years, an exothermic phenomenon has been reported in which nanostructures formed by hydrogen-absorbing metals, etc., generate heat by absorbing and releasing hydrogen (see Non-Patent Literature 1). Since this exothermic phenomenon can obtain more thermal energy than chemical reactions, it is expected to be utilized as an effective heat source or power source.

[0003] The inventors of the present invention have previously proposed a heating device comprising a base made of a hydrogen-absorbing metal, etc., and a heating element having a multilayer film formed on the surface of the base (see Patent Document 1). The multilayer film has a configuration in which a first layer made of a hydrogen-absorbing metal, etc., with a thickness of less than 1000 nm, and a second layer made of a hydrogen-absorbing metal, etc., different from the first layer, with a thickness of less than 1000 nm, are stacked, and a heterogeneous material interface is formed between the first layer and the second layer. When the heating element formed by the hydrogen-absorbing metal, etc., as described above is heated by a heater, hydrogen permeates or diffuses through the heterogeneous material interface by quantum diffusion, thereby generating heat. Prior art literature

[0004] International Publication No. 2018 / 230447

[0005] A. Kitamura, A. Takahashi, K. Takahashi, R. Seto, T. Hatano, Y. Iwamura, T. Itoh, J. Kasagi, M. Nakamura, M. Uchimura, H. Takahashi, S. Sumitomo, T. Hioki, T. Motohiro, Y. Furuyama, M. Kishida, H. Matsune, "Excess heat evolution from nanocomposite samples under exposure to hydrogen isotope gases", International Journal of Hydrogen Energy 43 (2018) 16187-16200. The problem to be solved

[0006] The heat generated by the heating element of Patent Document 1 can be converted into electricity and utilized, for example, by using a turbine. However, there is a problem that heat loss occurs when converting heat into electricity. For this reason, there is a desire to develop a new power generation device that can generate electricity directly without passing heat.

[0007] As a result of various studies, the inventors of the present invention have obtained a new finding that charged particles are emitted from the surface of a nanostructure by absorbing hydrogen in a nanostructure formed by a hydrogen-absorbing metal or the like and then causing the hydrogen to protonate. The present invention is based on this new finding and aims to provide a potential difference generating device capable of direct power generation. means of solving the problem

[0008] The potential difference generating device of the present invention comprises a base made of a hydrogen-absorbing metal, a hydrogen-absorbing alloy, or a proton conductor, a nanostructure having a multilayer film provided on the base, a first electrode provided on the nanostructure, and a second electrode provided opposite to the multilayer film, wherein the multilayer film is composed of a hydrogen-absorbing metal or a hydrogen-absorbing alloy and has a thickness of less than 1000 nm, and a second layer is formed of a hydrogen-absorbing metal, a hydrogen-absorbing alloy, or a ceramic that is different from the first layer and has a thickness of less than 1000 nm, and a heterogeneous material interface is formed between the first layer and the second layer, and when the nanostructure is heated, hydrogen permeates or diffuses through the heterogeneous material interface by quantum diffusion, thereby releasing charged particles from the multilayer film and capturing the charged particles on the second electrode, thereby generating a potential difference between the first electrode and the second electrode. Effects of the invention

[0009] According to the present invention, a potential difference generating device capable of generating electricity directly by absorbing hydrogen in a nanostructure formed by a hydrogen-absorbing metal, etc., and then diffusing the hydrogen into the quantum diffusion. Brief explanation of the drawing

[0010] Figure 1 is a schematic diagram illustrating a schematic of a potential difference generating device. Figure 2 is a cross-sectional view illustrating the composition of a nanostructure. Figure 3 is an explanatory diagram illustrating the mechanism by which a nanostructure emits charged particles. Figure 4 is a cross-sectional view illustrating the composition of another nanostructure. Figure 5 is a cross-sectional view illustrating the configuration of another nanostructure. Figure 6 is a schematic diagram illustrating the experimental apparatus used to perform the verification test. Figure 7 is an explanatory diagram illustrating the configuration of the nanostructure and heater of the experimental apparatus. Specific details for implementing the invention

[0011] Hereinafter, embodiments for implementing the present invention will be described with reference to the drawings. In the following description and drawings, common components are denoted by common reference numerals. Descriptions of components denoted by common reference numerals will be appropriately omitted.

[0012] [Potential difference generating device]

[0013] In FIG. 1, the potential difference generating device (10) comprises a container (11), a heater (12), a power source (13), a temperature sensor (14), a control unit (15), a nanostructure (16A), a first electrode (17), and a second electrode (18). The potential difference generating device (10) is configured to generate a potential difference between the first electrode (17) and the second electrode (18) by capturing charged particles emitted during the process of hydrogen quantum diffusion when heating is performed by the heater (12) while the nanostructure (16A) has absorbed hydrogen. By connecting a load, such as various electrical devices driven by power, between the first electrode (17) and the second electrode (18), current resulting from the potential difference flows to the load. The “potential difference generating device” is a novel power generation device capable of generating power directly by absorbing hydrogen in a nanostructure in which a first layer and a second layer are stacked, with a thickness of nano-size (less than 1000 nm) and composed of different hydrogen-absorbing metals, and by quantum diffusing hydrogen into a heterogeneous material interface formed between the first layer and the second layer. It is also called a “quantum hydrogen battery.” The detailed configuration of the potential difference generating device (10) is described below.

[0014] The container (11) is a hollow container composed of an upper part (11a), a lower part (11b), and a side part (11c). At least one of the upper part (11a) and the lower part (11b) is configured to be detachably connected to the side part (11c), and the container (11) is sealed by the upper part (11a) and the lower part (11b) being installed on the side part (11c). In this embodiment, a heater (12), a power source (13), a temperature sensor (14), a control unit (15), a nanostructure (16A), a first electrode (17), and a second electrode (18) are housed inside the container (11), but the power source (13) and the control unit (15) may be provided outside the container (11). A pressure sensor (not shown) for detecting the pressure inside the container (11) is provided inside the container (11). By using a vacuum generating device (not shown), such as a vacuum pump, the interior of the container (11) becomes a vacuum state. By using a hydrogen introduction device (not shown), such as a hydrogen tank that stores hydrogen-based gas, hydrogen-based gas is introduced into the interior of the container (11). Hydrogen-based gas is a gas containing isotopes of hydrogen. As hydrogen-based gas, at least one of deuterium gas and light hydrogen gas is used. Light hydrogen gas includes a mixture of naturally occurring light hydrogen and deuterium, that is, a mixture in which the abundance of light hydrogen is 99.985% and the abundance of deuterium is 0.015%. In the following description, if light hydrogen and deuterium are not distinguished, they are referred to as "hydrogen."

[0015] The container (11) has a positive terminal (21) and a negative terminal (22). In FIG. 1, the negative terminal (22) is provided at the top (11a) and the positive terminal (21) is provided at the bottom (11b), but the positions of the positive terminal (21) and the negative terminal (22) are not particularly limited and can be designed appropriately. The container (11) is formed from a material having heat resistance and pressure resistance, such as carbon steel, austenitic stainless steel, or heat-resistant non-ferrous alloy steel, or a material that reflects radiant heat, such as Ni, Cu, or Mo. The shape of the container (11) is not particularly limited and may be cylindrical, elliptical, rectangular, etc.

[0016] The heater (12) heats the nanostructure (16A) by increasing the temperature according to the supplied power. In this embodiment, the heater (12) is a plate-shaped ceramic heater having a configuration in which a conductor is provided inside a ceramic body formed of ceramic. The power supply (13) is electrically connected to the heater (12) and supplies power to the heater (12). The temperature sensor (14) detects the temperature of the nanostructure (16A). In this embodiment, the temperature sensor (14) is a thermocouple embedded in the heater (12) and is configured to detect the temperature of the nanostructure (16A) through the heater (12). The control unit (15) is electrically connected to the power supply (13) and the temperature sensor (14) and controls the output of the power supply (13) based on the detection result of the temperature sensor (14) to bring the nanostructure (16A) to a desired temperature.

[0017] The nanostructure (16A) has a base (24) made of a hydrogen-absorbing metal, a hydrogen-absorbing alloy, or a proton conductor, and a multilayer film (also called a nanostructure film) (25A) provided on the base (24). In FIG. 1, the multilayer film (25A) is provided on one side of the base (24), but the multilayer film (25A) may be provided on both sides of the base (24).

[0018] In this embodiment, the nanostructure (16A) is a plate-shaped member. The nanostructure (16A) is provided on both sides of the heater (12) via a shielding plate (27). One side of the shielding plate (27) is in contact with the base (24) of the nanostructure (16A), and the other side is in contact with the heater (12). For example, an SiO2 plate is used for the shielding plate (27). The nanostructure (16A) is integrated with the heater (12) and the shielding plate (27) by a holder (28). The holder (28) holds and supports the nanostructure (16A) so that the surface of the multilayer film (25A) of the nanostructure (16A) (the side opposite to the base (24) in FIG. 1) is exposed. The holder (28) is formed, for example, by ceramics.

[0019] The first electrode (17) is provided in the nanostructure (16A). In FIG. 1, the first electrode (17) is provided on the base (24) of the nanostructure (16A). The first electrode (17) is electrically connected to the negative electrode terminal (22). The first electrode (17) is formed by a material having conductivity, heat resistance, and pressure resistance. Examples of materials for the first electrode (17) include nickel (Ni), palladium (Pd), vanadium (V), titanium (Ti), niobium (Nb), iron (Fe), molybdenum (Mo), platinum (Pt), zirconium (Zr), tantalum (Ta), tungsten (W), and alloys based on these metals.

[0020] The second electrode (18) is provided facing the multilayer film (25A). The second electrode (18) is positioned with a predetermined gap in a direction orthogonal to the surface of the multilayer film (25A) (left-right direction of the ground in FIG. 1). In this embodiment, the second electrode (18) is supported by a support member not shown that is fixed to the inner wall of the container (11). The second electrode (18) is electrically connected to the positive electrode terminal (21). The second electrode (18) is formed by a material that has conductivity, heat resistance, and pressure resistance, and is also capable of capturing charged particles emitted from the surface of the multilayer film (25A) described later. As materials for the second electrode (18), examples include nickel (Ni), palladium (Pd), gold (Au), silver (Ag), copper (Cu), aluminum (Al), iron (Fe), molybdenum (Mo), platinum (Pt), tantalum (Ta), tungsten (W), and alloys based on these metals.

[0021] [Nanostructure]

[0022] Using FIG. 2, the composition of the nanostructure (16A) is described in detail.

[0023] An example of a material constituting the base (24) is described below. As a hydrogen-absorbing metal, for example, Ni, Pd, V, Nb, Ta, Ti, etc. are used. As a hydrogen-absorbing alloy, for example, LaNi5, CaCu5, MgZn2, ZrNi2, ZrCr2, TiFe, TiCo, Mg2Ni, Mg2Cu, etc. are used. As a proton conductor, for example, a BaCeO3-based (for example, Ba(Ce 0.95 Y 0.05 )O3 -6 ), SrCeO3 system (e.g., Sr(Ce 0.95 Y 0.05 )O3 -6 ), CaZrO3 system (e.g., CaZrO . 95 Y0 . 05 O3 -α), SrZrO3 system (e.g., SrZrO . 9Y0 . 103 -α Materials such as ), βAl2O3, βGa2O3, etc. are used. The base (24) may be composed of a porous body or a hydrogen permeable membrane. The porous body has holes of a size that allow the passage of hydrogen-based gas. The porous body is formed, for example, by a metal, a non-metal, ceramics, etc. It is preferable that the porous body be formed by a material that does not inhibit the reaction between the hydrogen-based gas and the multilayer membrane (25A). The hydrogen permeable membrane is formed, for example, by a hydrogen-absorbing metal or a hydrogen-absorbing alloy. The hydrogen permeable membrane includes having a mesh-like sheet.

[0024] The multilayer film (25A) is composed of a hydrogen-absorbing metal or a hydrogen-absorbing alloy and has a thickness of less than 1000 nm, and has a configuration in which a first layer (31) is made of a hydrogen-absorbing metal, a hydrogen-absorbing alloy, or a ceramic that is different from the first layer (31) and has a thickness of less than 1000 nm, and a second layer (32) is laminated and a heterogeneous material interface (36) is formed between the first layer (31) and the second layer (32).

[0025] In FIG. 2, the multilayer film (25A) has a configuration in which a first layer (31) and a second layer (32) are alternately stacked on the surface of the base (24), but it is not limited to this configuration and may have a configuration in which a second layer (32) and a first layer (31) are alternately stacked on the surface of the base (24). The number of each of the first layer (31) and the second layer (32) may be appropriately changed. As for the multilayer film (25A), it is sufficient to have at least one layer of the first layer (31) and at least one layer of the second layer (32), and to have at least one heterogeneous material interface (36) formed.

[0026] The first layer (31) is formed by, for example, any of Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, or alloys thereof. The alloy forming the first layer (31) is preferably an alloy composed of two or more of Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co. As the alloy forming the first layer (31), an alloy in which an additive element is added to Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co may be used.

[0027] The second layer (32) is formed by any of, for example, Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, alloys thereof, or SiC. The alloy forming the second layer (32) is preferably an alloy composed of two or more of Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co. As the alloy forming the second layer (32), an alloy in which an additive element is added to Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co may be used.

[0028] As for the combination of the first layer (31) and the second layer (32), if the types of elements are represented as “first layer (31) - second layer (32),” it is preferable that they be Pd-Ni, Ni-Cu, Ni-Cr, Ni-Fe, Ni-Mg, or Ni-Co. If the second layer (32) is made of ceramic, it is preferable that “first layer (31) - second layer (32)” be Ni-SiC.

[0029] It is preferable that the thickness of the first layer (31) and the thickness of the second layer (32) are each less than 1000 nm. If the thickness of each of the first layer (31) and the second layer (32) is 1000 nm or more, it becomes difficult for hydrogen to penetrate the multilayer film (25A). In addition, by having the thickness of each of the first layer (31) and the second layer (32) less than 1000 nm, a nano structure that does not exhibit bulk characteristics can be maintained. It is more preferable that the thickness of each of the first layer (31) and the second layer (32) is less than 500 nm. By having the thickness of each of the first layer (31) and the second layer (32) less than 500 nm, a nano structure that does not exhibit bulk characteristics can be maintained.

[0030] When a hydrogen-based gas is supplied to the nanostructure (16A), hydrogen is absorbed at high density in the base (24) and multilayer film (25A) of the nanostructure (16A). The nanostructure (16A) can maintain the state of having absorbed hydrogen in the base (24) and multilayer film (25A) even when the supply of the hydrogen-based gas is stopped. When the nanostructure (16A) is heated, the hydrogen absorbed in the base (24) and multilayer film (25A) undergoes quantum diffusion while hopping. Since hydrogen is light, it is known to undergo quantum diffusion while hopping to sites (octahedral or tetrahedral sites) occupied by hydrogen in some material A and material B.

[0031] FIG. 3 illustrates a nanostructure (16A) having a first layer (31) and a second layer (32) formed by a hydrogen-absorbing metal with a face-centered legislative structure, wherein hydrogen atoms in the metal lattice of the first layer (31) pass through a heterogeneous material interface (36) and move into the metal lattice of the second layer (32).

[0032] As illustrated in FIG. 3, when the nanostructure (16A) is heated, hydrogen permeates or diffuses through the heterogeneous material interface (36) formed between the first layer (31) and the second layer (32) by quantum diffusion, and charged particles CP are emitted from the multilayer film (25A). In this embodiment, the charged particles CP are ions carrying a positive charge. The charged particles CP are thought to be atomic nuclei of elements (Ni, Cu, etc.) constituting the nanostructure (16A) that have been ejected. The charged particles CP emitted from the multilayer film (25A) are captured by a second electrode (18) (see FIG. 1) provided facing the multilayer film (25A). As a result, the second electrode (18) that captures the charged particle CP becomes a positive potential, and the first electrode (17) provided on the base (24) of the nanostructure (16A) becomes a negative potential, so that a potential difference occurs between the first electrode (17) and the second electrode (18).

[0033] Additionally, as the nanostructure (16A) is heated, hydrogen permeates or diffuses through the heterogeneous material interface (36) by quantum diffusion, and heat (hereinafter referred to as excess heat) greater than the temperature at which the nanostructure (16A) is heated is generated.

[0034] An example of a method for manufacturing a nanostructure (16A) is described. First, a plate-shaped base (24) is prepared, and then a multilayer film (25A) is formed on the base (24) using a sputtering method. By doing so, a plate-shaped nanostructure (16A) can be manufactured. When forming the base (24), it is preferable to form it thicker than each of the first layer (31) and the second layer (32). Ni is preferred as the material for the base (24). It is preferable to form the first layer (31) and the second layer (32) continuously in a vacuum state. As a result, a natural oxide film is not formed between the first layer (31) and the second layer (32), and only a heterogeneous material interface (36) is formed. The method for manufacturing the nanostructure (16A) is not limited to the sputtering method, and deposition, wet method, thermal spraying, electroplating, etc., can be used.

[0035] In this embodiment, the nanostructure (16A) is formed in a plate shape, but is not limited thereto. The nanostructure may be formed, for example, in a tubular shape or in a tubular shape with a bottom. An example of a method for manufacturing a tubular nanostructure with a bottom is described. First, a base formed in a tubular shape with a bottom is prepared, and then a multilayer film is formed on the outer surface of the base using a wet film deposition method. By doing so, a tubular nanostructure with a bottom can be manufactured. As a wet film deposition method, spin coating, spray coating, dipping, etc., are used. In addition, the multilayer film may be formed using an Atomic Layer Deposition (ALD) method, or a multilayer film may be formed on the base while rotating the base using a sputtering device equipped with a rotation mechanism for rotating the base. In addition, the multilayer film is not limited to being formed on the outer surface of the base, but may be formed on the inner surface of the base or on both sides of the base. A tubular nanostructure can also be manufactured by the same manufacturing method.

[0036] In this embodiment, the nanostructure (16A) is composed of a base (24) and a multilayer film (25A), but is not limited thereto.

[0037] FIG. 4 is a cross-sectional view illustrating the configuration of another nanostructure (16B). As shown in FIG. 4, the nanostructure (16B) has a base (24) and a multilayer film (25B) provided on the base (24). In FIG. 4, the multilayer film (25B) is provided on one side of the base (24), but the multilayer film (25B) may be provided on both sides of the base (24).

[0038] The multilayer film (25B) is composed of a first layer (31), a second layer (32), a hydrogen-absorbing metal, a hydrogen-absorbing alloy, or a ceramic that is different from the first layer (31) and the second layer (32), and a third layer (33) with a thickness of less than 1000 nm is laminated, and a heterogeneous material interface (37) is formed between the first layer (31) and the third layer (33).

[0039] In FIG. 4, the multilayer film (25B) has a configuration in which a first layer (31), a second layer (32), a first layer (31), and a third layer (33) are stacked in order on the surface of the base (24), but it is not limited to this configuration. It may have a configuration in which the second layer (32) and the third layer (33) are arranged in any order on the surface of the base (24), and the first layer (31) is provided between the second layer (32) and the third layer (33). For example, the multilayer film (25B) may have a configuration in which a first layer (31), a third layer (33), a first layer (31), and a second layer (32) are stacked in order on the surface of the base (24). The number of each of the first layer (31), the second layer (32), and the third layer (33) may be appropriately changed. As for the multilayer film (25B), it is sufficient to have one or more third layers (33) and one or more heterogeneous material interfaces (37) formed.

[0040] The third layer (33) is formed by any one of, for example, Ni, Pd, Cu, Cr, Fe, Mg, Co, alloys thereof, SiC, CaO, Y2O3, TiC, LaB6, SrO, and BaO. The alloy forming the third layer (33) is preferably an alloy composed of two or more of Ni, Pd, Cu, Cr, Fe, Mg, and Co. As the alloy forming the third layer (33), an alloy in which an additive element is added to Ni, Pd, Cu, Cr, Fe, Mg, and Co may be used.

[0041] In particular, the third layer (33) is preferably formed from any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO. A nanostructure (16B) having a third layer (33) formed from any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO can increase the hydrogen absorption amount and increase the amount of hydrogen permeating through the heterogeneous material interface (36) and the heterogeneous material interface (37), thereby increasing the amount of charged particle CP emitted and enabling high output of excess heat. The third layer (33) formed from any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO is preferably formed with a thickness of 10 nm or less. By having a thickness of 10 nm or less of the third layer (33), hydrogen can be easily permeated, and the amount of hydrogen permeated can be further increased. The third layer (33), formed by any one of CaO, Y2O3, TiC, LaB6, SrO, or BaO, may not be formed as a complete film but as an island. Additionally, it is preferable that the first layer (31) and the third layer (33) be formed continuously in a vacuum. As a result, a natural oxide film is not formed between the first layer (31) and the third layer (33), and only a heterogeneous material interface (37) is formed.

[0042] As a combination of the first layer (31), the second layer (32), and the third layer (33), if the types of elements are represented as “first layer (31)-third layer (33)-second layer (32)”, then Pd-CaO-Ni, Pd-Y2O3-Ni, Pd-TiC-Ni, Pd-LaB6-Ni, Ni-CaO-Cu, Ni-Y2O3-Cu, Ni-TiC-Cu, Ni-LaB6-Cu, Ni-Co-Cu, Ni-CaO-Cr, Ni-Y2O3-Cr, Ni-TiC-Cr, Ni-LaB6-Cr, Ni-CaO-Fe, Ni-Y2O3-Fe, Ni-TiC-Fe, Ni-LaB6-Fe, Ni-Cr-Fe, Ni-CaO-Mg, Ni-Y2O3-Mg, Ni-TiC-Mg, It is preferable that it be Ni-LaB6-Mg, Ni-CaO-Co, Ni-Y2O3-Co, Ni-TiC-Co, Ni-LaB6-Co, Ni-CaO-SiC, Ni-Y2O3-SiC, Ni-TiC-SiC, and Ni-LaB6-SiC.

[0043] As the nanostructure (16B) is heated, hydrogen permeates or diffuses through the heterogeneous material interface (36) and the heterogeneous material interface (37) by quantum diffusion, and excess heat is generated as charged particles CP are emitted from the multilayer film (25B). The nanostructure (16B) can be manufactured by the same manufacturing method as the nanostructure (16A). The potential difference generating device (10) may be equipped with the nanostructure (16B) instead of the nanostructure (16A).

[0044] FIG. 5 is a cross-sectional view illustrating the configuration of another nanostructure (16C). As shown in FIG. 5, the nanostructure (16C) has a base (24) and a multilayer film (25C) provided on the base (24). In FIG. 5, the multilayer film (25C) is provided on one side of the base (24), but the multilayer film (25C) may be provided on both sides of the base (24).

[0045] The multilayer film (25C) has a configuration in which a first layer (31), a second layer (32), a third layer (33), a hydrogen-absorbing metal, a hydrogen-absorbing alloy, or a ceramic is different from the first layer (31), the second layer (32), and the third layer (33), and a fourth layer (34) with a thickness of less than 1000 nm is laminated, and a heterogeneous material interface (38) is formed between the first layer (31) and the fourth layer (34).

[0046] In FIG. 5, the multilayer film (25C) has a configuration in which a first layer (31), a second layer (32), a first layer (31), a third layer (33), a first layer (31), and a fourth layer (34) are stacked in order on the surface of the base (24), but is not limited to this. It may have a configuration in which the second layer (32), the third layer (33), and the fourth layer (34) are arranged in any order on the surface of the base (24), and a first layer (31) is provided between the second layer (32), the third layer (33), and the fourth layer (34). For example, the multilayer film (25C) may have a configuration in which a first layer (31), a fourth layer (34), a first layer (31), a third layer (33), a first layer (31), and a second layer (32) are stacked in order on the surface of the base (24). The number of each of the first layer (31), second layer (32), third layer (33), and fourth layer (34) may be appropriately changed. As for the multilayer film (25C), it is sufficient to have one or more layers of the fourth layer (34) and one or more heterogeneous material interfaces (38) formed.

[0047] The fourth layer (34) is formed by any one of, for example, Ni, Pd, Cu, Cr, Fe, Mg, Co, alloys thereof, SiC, CaO, Y2O3, TiC, LaB6, SrO, and BaO. The alloy forming the fourth layer (34) is preferably an alloy composed of two or more of Ni, Pd, Cu, Cr, Fe, Mg, and Co. As the alloy forming the fourth layer (34), an alloy in which an additive element is added to Ni, Pd, Cu, Cr, Fe, Mg, and Co may be used.

[0048] In particular, the fourth layer (34) is preferably formed from any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO. A nanostructure (16C) having a fourth layer (34) formed from any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO can increase the hydrogen absorption amount and increase the amount of hydrogen permeating through the heterogeneous material interface (36), heterogeneous material interface (37), and heterogeneous material interface (38), thereby increasing the amount of charged particle CP emitted and enabling high output of excess heat. The fourth layer (34) formed from any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO is preferably 10 nm or less in thickness. By having a thickness of 10 nm or less of the fourth layer (34), hydrogen can be easily permeated, and the amount of hydrogen permeated can be further increased. The fourth layer (34), formed by any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO, may not be formed as a complete film but as an island. Additionally, it is preferable that the first layer (31) and the fourth layer (34) be formed continuously in a vacuum. As a result, a natural oxide film is not formed between the first layer (31) and the fourth layer (34), and only a heterogeneous material interface (38) is formed.

[0049] As for the combination of the first layer (31), the second layer (32), the third layer (33), and the fourth layer (34), if the types of elements are represented as “first layer (31)-fourth layer (34)-third layer (33)-second layer (32)”, it is preferable that they be Ni-CaO-Cr-Fe, Ni-Y2O3-Cr-Fe, Ni-TiC-Cr-Fe, and Ni-LaB6-Cr-Fe.

[0050] As the nanostructure (16C) is heated, hydrogen permeates or diffuses through the heterogeneous material interface (36), heterogeneous material interface (37), and heterogeneous material interface (38) by quantum diffusion, and excess heat is generated as charged particles CP are emitted from the multilayer film (25C). The nanostructure (16C) can be manufactured by the same manufacturing method as the nanostructure (16A). The potential difference generating device (10) may be equipped with the nanostructure (16C) instead of the nanostructure (16A).

[0051] [Mechanisms and Effects]

[0052] The potential difference generating device (10) is formed by a hydrogen-absorbing metal, etc. and has a nanostructure (16A) in which a first layer (31) and a second layer (32) are stacked, with a thickness of nano-size (less than 1000 nm). A first electrode (17) is provided on a base (24) of the nanostructure (16A), and a second electrode (18) is provided to face the multilayer film (25A) of the nanostructure (16A). When the nanostructure (16A) is heated, hydrogen permeates or diffuses through the heterogeneous material interface (36) formed between the first layer (31) and the second layer (32) by quantum diffusion, and charged particles CP are emitted from the multilayer film (25A). As the emitted charged particles CP are captured by the second electrode (18), a potential difference is generated between the first electrode (17) and the second electrode (18). By connecting a load between the first electrode (17) and the second electrode (18), current resulting from the potential difference flows to the load. As described above, the potential difference generating device (10) can directly generate power by absorbing hydrogen in the nanostructure (16A) and then diffusing the hydrogen.

[0053] [Verification Test]

[0054] An experimental apparatus (50) as shown in Fig. 6 was fabricated, and a verification test was performed to determine whether charged particles CP were emitted from the multilayer film (25A).

[0055] The experimental device (50) is equipped with a container (11), a heater (12), a power source (13), a temperature sensor (14), a control unit (15), a nanostructure (16A), a gas inlet (51), a gas outlet (52), a pressure sensor (53), and a temperature sensor (54). In the experimental device (50), two nanostructures (16A) were used. Each nanostructure (16A) is a plate-shaped member and is formed as a square with a side length of 25 mm when viewed from a plane. In FIG. 6, only one of the two nanostructures (16A) is shown, and the other nanostructure (16A) is hidden on the inside of the ground.

[0056] The container (11) has a viewport (11d) formed of an infrared-transmitting material such as Kovar glass. The heater (12) is a plate-shaped ceramic heater with a thickness of 2.2 mm and is formed as a square with a side length of 25 mm when viewed from a flat surface. The heater (12) has a temperature sensor (14) built in. The heater (12) is connected to a power source (13) through a current-voltage meter (56) provided on the outside of the container (11). The current-voltage meter (56) detects the input power applied to the heater (12) from the power source (13).

[0057] The gas introduction section (51) has a gas storage section (57) for storing hydrogen-based gas, a gas introduction pipe (58) connecting the gas storage section (57) and the container (11), and an adjustment valve (59, 60) provided in the gas introduction pipe (58) for adjusting the flow rate and pressure of the hydrogen-based gas.

[0058] The gas discharge section (52) has a vacuum generating device (61), such as a dry pump, a gas discharge pipe (62) connecting the vacuum generating device (61) and the container (11), and a control valve (63) for adjusting the flow rate and pressure of the hydrogen gas.

[0059] The pressure sensor (53) detects the pressure inside the container (11). The pressure sensor (53) is electrically connected to a control unit (15), although not shown. The control unit (15) is electrically connected to a vacuum generator (61), although not shown, and controls the vacuum generator (61) based on the detection result of the pressure sensor (53) to perform vacuum evacuation inside the container (11). By doing so, the pressure inside the container (11) is controlled.

[0060] The temperature sensor (54) is an infrared radiation thermometer provided on the outside of the container (11) and detects the temperature of the surface of the nanostructure (16A) through the viewport (11d) of the container (11). Two temperature sensors (54) are provided to detect the temperature of each of the two nanostructures (16A). In FIG. 6, the temperature sensor (54) for detecting the temperature of one of the two nanostructures (16A) is illustrated. The temperature sensor (54) for detecting the temperature of the other of the two nanostructures (16A) is omitted from illustration.

[0061] FIG. 7 is an explanatory diagram for explaining the configuration of the nanostructure (16A) and heater (12) of the experimental apparatus (50) shown in FIG. 6. As shown in FIG. 7, one nanostructure (16A) is placed on each side of the heater (12). A shielding plate (27) is provided between the heater (12) and each nanostructure (16A). The shielding plate (27) uses a SiO2 plate with a thickness of 0.3 mm. The nanostructure (16A) is integrated with the heater (12) using a holder (28) while the base (24) is oriented toward the heater (12) and in contact with the shielding plate (27). The base (24) is made of Ni and uses a Ni substrate with a thickness of 0.1 mm. The holder (28) uses a photoveil (registered trademark) manufactured by Ferrotec Ceramics. The holder (28) has a circular opening that exposes the surface of the multilayer film (25A) constituting the nanostructure (16A). The thickness t of the holder (28) is 1.5 mm, and the radius r of the opening is 10 mm.

[0062] The method of the verification test is described. First, a nanostructure (16A) was introduced into a container (11), and vacuum evacuation was performed inside the container (11). Next, the nanostructure (16A) was baked with a heater (12) to remove water and other substances attached to the surface of the nanostructure (16A). Next, a hydrogen-based gas was introduced into the container (11) to absorb hydrogen into the nanostructure (16A). The conditions for introducing the hydrogen-based gas were set to 80°C to 500°C and 100 Pa or higher. Next, while vacuum evacuation was performed inside the container (11), the heater (12) was heated to raise the surface temperature of the nanostructure (16A) to 600°C.

[0063] In the verification test, experiments 1 to 4 were performed by changing the purity of the hydrogen-based gas or the composition of the nanostructure (16A). The nanostructure (16A) used in experiment 1 was formed by stacking six layers each of a first layer (31) made of Cu with a thickness of 2 nm and a second layer (32) made of Ni with a thickness of 14 nm on the surface of a base (24) to form a multilayer film (25A). The purity of the hydrogen-based gas used in experiment 1 was set to 7N (99.99999% or higher). Experiment 2 was performed under the same conditions as experiment 1. Experiment 3 was performed under the same conditions as experiments 1 and 2, except that the purity of the hydrogen-based gas was set to 5N (99.999% or higher). Experiment 4 was conducted under the same conditions as Experiment 1 and Experiment 2, except that the thickness of the first layer (31) made of Cu was 3 nm and the thickness of the second layer (32) made of Ni was 13 nm.

[0064] In the verification test, hydrogen was protonated by heating the nanostructure (16A) using the heater (12) as described above, thereby releasing charged particles CP. The release time of the charged particles CP was set to 10 days. It was assumed that the charged particles CP are released in a hemispherical shape from the center of the surface of the multilayer film (25A). Since the thickness t of the holder (28) was set to 1.5 mm and the radius r of the opening was set to 10 mm, the solid angle Ω is 2πrt / (4πr 2 / 2)=t / r=0.15. The attachment rate η (also called detection efficiency) of the charged particle CP attaching to the holder (28) is set to 0.1. Therefore, Ωη, which is obtained by multiplying the solid angle Ω by the attachment rate η, is 0.015.

[0065] The charged particles CP emitted from the nanostructure (16A) and attached to the holder (28) were analyzed by the ICP-MS (Inductively Coupled Plasma Mass Spectrometry) method. In the ICP-MS method, 20 mL of an aqueous nitric acid solution, prepared by diluting TAMAPURE AA-10 nitric acid manufactured by Tama Kagaku Kogyo Co., Ltd. with pure water five times, was used to elute the charged particles CP attached (captured) to the holder (28), and the concentration of metal in the eluent was measured. As a result of this measurement, it was found that a large amount of Cu and Ni were emitted as charged particles CP.

[0066] (1) Measurement results of Experiment 1

[0067] Table 1 summarizes the measurement results of Experiment 1.

[0068]

[0069] In Table 1, “Cu(A)” and “Ni(A)” represent the measurement results for Cu and Ni in one nanostructure (16A), and “Cu(B)” and “Ni(B)” represent the measurement results for Cu and Ni in the other nanostructure (16A). The concentration (ppb) is the concentration detected by the ICP-MS method. The concentration (mg / L) was calculated from the concentration (ppb). The amount of solution is the amount of aqueous nitric acid solution used in the ICP-MS method. The detected element was calculated as concentration × amount of solution. The number of moles of the detected element is 6.02 × 10⁻⁶ 23 It was calculated as × (detected element / atomic weight). The number of moles of emitted element was calculated as (number of moles of detected element / solid angle / adhesion rate).

[0070] In the evaluation test, an evaluation of the average electrical output based on current (current evaluation) and an evaluation of the average electrical output based on total power (energy evaluation) were performed.

[0071] Table 2 summarizes the conditions and results of the current and energy evaluations in Experiment 1. The average energy was assumed to be 5 MeV, and the conversion efficiency to power was set to 10%.

[0072]

[0073] In the current evaluation, the current was calculated as 1.6 × 10⁻¹⁹ × number of moles of emitted element × average ion valence / total emitted time. The average electric output in the current evaluation was calculated as assumed energy × power conversion efficiency × current. In the energy evaluation, the total electric energy (J) was calculated as the electric energy (1.6 × 10⁻¹⁹) × number of moles of emitted element × average ion valence × assumed energy. The average electric output (W) in the energy evaluation was calculated as total electric energy × power conversion efficiency / total emitted time. In Experiment 1, the total electric output obtained by summing the average electric outputs of "Cu(A)", "Ni(A)", "Cu(B)", and "Ni(B)" in both the current evaluation and the energy evaluation was found to be 15.4 (W).

[0074] From the results of Experiment 1, it was confirmed that charged particles CP are emitted from the nanostructure (16A). By configuring the potential difference generating device (10) using the nanostructure (16A), the emitted charged particles CP are captured by the second electrode (18), thereby generating a potential difference between the first electrode (17) and the second electrode (18).

[0075] (2) Measurement results of Experiment 2

[0076] Table 3 summarizes the measurement results of Experiment 2.

[0077]

[0078] Table 4 summarizes the conditions and results of the current evaluation and energy evaluation in Experiment 2.

[0079]

[0080] As in Experiment 1, the average electric output in the current evaluation and the average electric output in the energy evaluation were calculated. In Experiment 2, the total electric output obtained by summing the average electric outputs of "Cu(A)", "Ni(A)", "Cu(B)", and "Ni(B)" in both the current evaluation and the energy evaluation was found to be 8.0 (W).

[0081] From the results of Experiment 2, it was confirmed that charged particles CP were emitted from the nanostructure (16A), just as in Experiment 1. By configuring the potential difference generating device (10) using the nanostructure (16A), the emitted charged particles CP are captured by the second electrode (18), thereby generating a potential difference between the first electrode (17) and the second electrode (18).

[0082] (3) Measurement results of Experiment 3

[0083] Table 5 summarizes the measurement results of Experiment 3.

[0084]

[0085] Table 6 summarizes the conditions and results of the current and energy evaluations in Experiment 3.

[0086]

[0087] In Experiment 3, the sum of the average electric outputs of "Cu(A)", "Ni(A)", "Cu(B)", and "Ni(B)" for both the current evaluation and the energy evaluation was found to be 0.7 (W).

[0088] From the results of Experiment 3, it was confirmed that charged particles CP were emitted from the nanostructure (16A), just as in Experiments 1 and 2. By configuring the potential difference generating device (10) using the nanostructure (16A), the emitted charged particles CP are captured by the second electrode (18), thereby generating a potential difference between the first electrode (17) and the second electrode (18).

[0089] Experiment 3, in which the purity of the hydrogen-based gas was set to 5N (99.999% or higher), yielded a lower electrical output compared to Experiment 1, in which the purity of the hydrogen-based gas was set to 7N (99.99999% or higher). From this result, it was found that impurities such as H2O, CO2, and N2 contained in the hydrogen-based gas affect the generation of charged particles CP. By changing the concentration of impurities contained in the hydrogen-based gas, the amount of charged particles CP released can be controlled. When designing a potential difference generating device (10), the desired electrical output can be obtained by changing the concentration of impurities contained in the hydrogen-based gas. From the results of Experiments 1 to 3, it was found that the purity of the hydrogen-based gas should be 5N or higher and 7N or lower.

[0090] (4) Measurement results of Experiment 4

[0091] Table 7 summarizes the measurement results of Experiment 4.

[0092]

[0093] Table 8 summarizes the conditions and results of the current and energy evaluations in Experiment 4.

[0094]

[0095] In Experiment 4, the sum of the average electric outputs of "Cu(A)", "Ni(A)", "Cu(B)", and "Ni(B)" for both the current evaluation and the energy evaluation was found to be 1.9 (W).

[0096] From the results of Experiment 4, it was confirmed that charged particles CP were emitted from the nanostructure (16A), just as in Experiments 1 to 3. By configuring the potential difference generating device (10) using the nanostructure (16A), the emitted charged particles CP are captured by the second electrode (18), thereby generating a potential difference between the first electrode (17) and the second electrode (18).

[0097] Experiment 4, in which the thickness of the first layer (31) is 3 nm and the thickness of the second layer (32) is 13 nm, has a lower electrical output compared to Experiment 1, in which the thickness of the first layer (31) is 2 nm and the thickness of the second layer (32) is 14 nm. From this result, it was found that the ratio of the thickness of the first layer (31) to the thickness of the second layer (32) affects the generation of charged particles CP. By changing the ratio of the thickness of the first layer (31) to the thickness of the second layer (32), the amount of charged particles CP emitted can be controlled. When designing a potential difference generating device (10), a desired electrical output can be obtained by changing the ratio of the thickness of the first layer (31) to the thickness of the second layer (32).

[0098] The present invention is not limited to the above embodiments and can be appropriately modified within the scope of not departing from the spirit of the invention.

[0099] In the above embodiment, the potential difference generating device (10) is configured to heat the nanostructure (16A) using a heater (12), but is not limited thereto. Instead of using a heater (12) and a power source (13), the potential difference generating device (10) may be configured to heat the nanostructure (16A) using waste heat from a vehicle or a power plant. For example, the nanostructure (16A) can be heated by the heat medium by providing a flow path through which a heat medium heated by waste heat flows. In this case, the control unit (15) raises the nanostructure (16A) to a desired temperature by controlling the flow rate of the heat medium based on the temperature of the nanostructure (16A) detected by the temperature sensor (14).

[0100] In the above embodiment, the heater (12) is a plate-shaped ceramic heater, but is not limited to this and may be a tubular heater. When the nanostructure (16A) is formed in a tubular shape or a tubular shape with a bottom, the nanostructure (16A) can be efficiently heated by placing a tubular heater inside the nanostructure (16A).

[0101] In the above embodiment, the first electrode (17) is provided on the base (24) of the nanostructure (16A), but is not limited thereto. The first electrode (17) may be provided on the multilayer film (25A). For example, the first electrode (17) may be made by doping impurities into a silicon substrate to impart conductivity. Additionally, the base (24) may be formed from a conductive material so that the base (24) is used as the first electrode.

[0102] In the above embodiment, the second electrode (18) is supported by an unillustrated support member fixed to the inner wall of the container (11), but is not limited thereto. The second electrode (18) may be configured to be supported, for example, by a holder (28). Additionally, an insulator may be separately provided between the surface of the nanostructure multilayer film and the second electrode, and the second electrode may be configured to be supported by this insulator. The second electrode (18) may be, for example, a silicon substrate doped with impurities to impart conductivity.

[0103] The power generated by the potential difference generating device (10) can be used for various purposes. For example, by taking advantage of the features of the potential difference generating device (10), such as being compact and having no moving parts (rotating bodies, etc.), it is thought of to use it for constantly charging devices currently powered by batteries in moving vehicles such as electric vehicles. By appropriately selecting the capacity of the potential difference generating device (10), it is expected that drones, robots, electric vehicles, submarines, airplanes, and spacecraft that do not require charging can be realized. In addition, it is possible to apply it as a power source for communication infrastructure in places that are difficult to access, such as remote islands, jungles, and deep seas.

[0104] The heat (excess heat) generated by the nanostructure (16A) can be used for various purposes. By using a thermoelectric converter that is thermally connected to the nanostructure (16A), the heat of the nanostructure (16A) can be converted into power in the thermoelectric converter. The power converted in the thermoelectric converter may be supplied to the heater (12). By supplying the power converted in the thermoelectric converter to the heater (12), the potential difference generating device (10) achieves power saving. Even if the power supply (13) is turned ON only when the potential difference generating device (10) starts up and the power supply (13) is turned OFF after the charged particle CP is emitted from the nanostructure (16A), it is possible to keep the potential difference generating device (10) running using the power converted in the thermoelectric converter.

[0105] Excess heat generated by the nanostructure (16A) can be recovered using a heat medium. The heat medium is heated by the nanostructure (16A) and becomes high temperature. The high temperature heat medium is used, for example, for household heating, household water heaters, car heaters, agricultural heaters, road heaters, heat sources for seawater desalination, auxiliary heat sources for geothermal power generation, etc. As a heat medium, a gas or liquid may be used, and it is desirable that it has excellent thermal conductivity and is also chemically stable. As a gas, for example, helium gas, argon gas, hydrogen gas, nitrogen gas, water vapor, air, carbon dioxide, etc. are used. As a liquid, for example, water, molten salt (KNO3 (40%)-NaNO3 (60%), etc.), liquid metal (e.g., Pb), etc. are used. In addition, as a heat medium, a mixed heat medium in which solid particles are dispersed in a gas or liquid may be used. The solid particles are metals, metal compounds, alloys, ceramics, etc. As metals, copper, nickel, titanium, cobalt, etc. are used. As metal compounds, oxides, nitrides, silicides, etc. of the above metals are used. As alloys, stainless steel, chrome molybdenum steel, etc. are used. As ceramics, alumina, etc. are used.

[0106] Examples of applications for the excess heat generated by the nanostructure (16A) include heat exchangers and power units. Examples of heat exchangers include devices that perform heat exchange between a heat medium and a gas, devices that perform heat exchange between a heat medium and a liquid, and devices that perform heat exchange between a heat medium and a solid. Devices that perform heat exchange between a heat medium and a gas are used for air conditioning, preheating of air supplied to combustion devices, and the generation of hot air for drying or heating. Examples of combustion devices include boilers, rotary kilns, metal heat treatment furnaces, metal processing furnaces, hot air furnaces, ceramic kilns, petroleum refining towers, carbonization furnaces, drying furnaces, etc. Devices that perform heat exchange between a heat medium and a liquid are used as heat sources for boilers, for oil heating, chemical reaction tanks, etc. Devices that perform heat exchange between a heat medium and a solid are used for double-tube rotary heaters, heating of particulate matter within double tubes, etc. Examples of power units include gas turbines, steam turbines, Stirling engines, and ORCS (Organic Rankine Cycle System). Explanation of the symbols

[0107] 10: Potential difference generating device 11: Courage 12: Heater 13: Power 14: Temperature sensor 15: Control unit 16A, 16B, 16C: Nanostructures 17: First electrode 18: Second electrode 24: Stand 25A, 25B, 25C: Multilayer 31: 1st floor 32: 2nd floor 33: 3rd floor 34: 4th floor 36, 37, 38: Heterogeneous material interface

Claims

Claim 1 A potential difference generating device comprising a base made of a hydrogen-absorbing metal, a hydrogen-absorbing alloy, or a proton conductor, a nanostructure having a multilayer film provided on the base, a first electrode provided on the nanostructure, and a second electrode provided opposite to the multilayer film, wherein the multilayer film is composed of a hydrogen-absorbing metal or a hydrogen-absorbing alloy and has a thickness of less than 1000 nm, and a second layer is composed of a hydrogen-absorbing metal, a hydrogen-absorbing alloy, or a ceramic different from the first layer and has a thickness of less than 1000 nm, and a heterogeneous material interface is formed between the first layer and the second layer, wherein when the nanostructure is heated, hydrogen permeates or diffuses through the heterogeneous material interface by quantum diffusion, thereby releasing charged particles from the multilayer film and capturing the charged particles on the second electrode, thereby generating a potential difference between the first electrode and the second electrode. Claim 2 A potential difference generating device according to claim 1, wherein the purity of the hydrogen-based gas supplied to the nanostructure is 5N or higher and 7N or lower. Claim 3 A potential difference generating device according to claim 1, comprising a temperature sensor for detecting the temperature of the nanostructure, a heater for heating the nanostructure, and a control unit for controlling the heater based on the temperature detected by the temperature sensor.

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