Heating structure and heating device

Abstract

The invention provides a heating structural body and a heating device which can improve the heating stability and controllability of a heating body. The heat-generating structure (2) is provided with a silicon substrate (13) and a heat-generating body (14) that generates heat by storage and release of hydrogen, the heat-generating body (14) having a support body (61) provided on the silicon substrate (13) and a multilayer film (62) provided on the support body (61), the support body (61) being formed from at least one of a porous body, a hydrogen-permeable film, and a proton conductor. The multilayer film (62) has a first layer (71) that is formed of a hydrogen storage metal or a hydrogen storage alloy and has a thickness of less than 1000 nm, and a second layer (72) that is formed of a hydrogen storage metal, a hydrogen storage alloy, or a ceramic that is different from the first layer (71) and has a thickness of less than 1000 nm.

Description

TECHNICAL FIELD

[0001] The present application relates to a heat generating structure and a heat generating device. BACKGROUND

[0002] In recent years, a heat generating phenomenon in which heat is generated by hydrogen storage and release of hydrogen using a nanostructure formed of a hydrogen storage metal has been reported (see Non-Patent Literature 1). This heat generating phenomenon can generate larger heat energy than chemical reactions, and is expected to be used as an effective heat source or power source.

[0003] The present inventors have previously proposed a heat generating device provided with a heat generating body, wherein the heat generating body is provided with a pedestal formed of a hydrogen storage metal, a hydrogen storage alloy, or a proton conductor, and a multilayer film formed on the surface of the pedestal (see Patent Literature 1). The heat generating body is disposed inside a container into which a hydrogen-based gas that contributes to heat generation is introduced. The multilayer film has a configuration in which a first layer formed of a hydrogen storage metal or a hydrogen storage alloy and having a thickness of less than 1000 nm is laminated, and a second layer formed of a hydrogen storage metal, a hydrogen storage alloy, or a ceramic that is different from the first layer and having a thickness of less than 1000 nm, and a heterogeneous substance interface is present between the first layer and the second layer. In the heat generating device of Patent Literature 1, after hydrogen gas is stored in the heat generating body, the heat generating body is heated using a heater, and the inside of the container is evacuated, whereby hydrogen is made to penetrate the heterogeneous substance interface by quantum diffusion, or hydrogen is made to diffuse to the heterogeneous substance interface by quantum diffusion, and heat is generated in the heat generating body.

[0004] Prior Art Documents Patent Literature Non-Patent Literature 1: 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. Patent Literature 1: WO2018 / 230447 SUMMARY Technical problem to be solved by the invention However, when the surface of the pedestal has a slight unevenness, it is difficult to form a smooth heterogeneous substance interface, thereby causing a problem of a decrease in the heat generation stability and controllability of the heat generating body.

[0005] The object of the present invention is to provide a heat generating structure and a heat generating device capable of improving the heat generation stability and controllability of a heat generating body.

[0006] Technical solution for solving the technical problem The heat generating structure of the present invention has a silicon substrate and a heat generating body that generates heat by storage and release of hydrogen, wherein the heat generating body has a support provided on the silicon substrate and a multilayer film provided on the support, wherein the support is formed of at least one of a porous body, a hydrogen permeation film, and a proton conductor, and the multilayer film has a first layer formed of a hydrogen storage metal or a hydrogen storage alloy and having a thickness of less than 1000 nm, and a second layer formed of a hydrogen storage metal, a hydrogen storage alloy, or a ceramic different from the first layer and having a thickness of less than 1000 nm.

[0007] The heat generating device of the present invention has the above-mentioned heat generating structure, a closed container that accommodates the heat generating structure, a supply portion that supplies a hydrogen-based gas containing the hydrogen to the inside of the closed container, and a discharge portion that discharges the hydrogen-based gas from the inside of the closed container.

[0008] Effects of the invention The present invention can provide a heat generating structure and a heat generating device capable of forming a smooth heterogeneous substance interface and improving the heat generation stability and controllability of a heat generating body by providing a support on a silicon substrate and a multilayer film on the support. BRIEF DESCRIPTION OF DRAWINGS

[0009] Figure 1 is a schematic view showing the structure of a heat generating device of the present embodiment.

[0010] Figure 2 is a schematic view showing the structure of a heat generating structure of the present embodiment.

[0011] Figure 3 is a schematic view showing the structure of a heat generating body.

[0012] Figure 4 is a schematic view showing a laminate having a first layer and a second layer.

[0013] Figure 5 is a schematic view for showing generation of excess heat.

[0014] Figure 6is a schematic diagram for showing a heat generating body of a first modification having a first layer, a second layer, and a third layer.

[0015] Figure 7 is a schematic diagram for showing a heat generating body of a second modification having a first layer, a second layer, a third layer, and a fourth layer.

[0016] Figure 8 is a schematic diagram showing a heat generating method.

[0017] Figure 9 is a schematic diagram showing a microcrystalline state in which a ternary alloy is formed.

[0018] Figure 10 is a schematic diagram showing modification and reduction of a heterogeneous substance interface.

[0019] Figure 11 is a schematic diagram showing a structure of a heat generating device of another embodiment. DETAILED DESCRIPTION

[0020] Hereinafter, embodiments for carrying out the present application will be described with reference to the accompanying drawings. In the following description and drawings, the same element symbols are used for the same structures. The description will be appropriately omitted for the structures using the same element symbols.

[0021] (Heat generating device) Figure 1 is a schematic diagram showing a structure of a heat generating device 1 of the present embodiment. In Figure 1 , the heat generating device 1 is provided with a heat generating body 2, a sealed container 3, a supply portion 4, a discharge portion 5, a vacuum exhaust portion 6, a control portion 7, and a support mechanism 8.

[0022] The sealed container 3 is a hollow container composed of an upper portion 3a, a bottom portion 3b, and a side portion 3c. The sealed container 3 is configured so that at least one of the upper portion 3a and the bottom portion 3b is freely attachable and detachable with respect to the side portion 3c, and is sealed by attaching the upper portion 3a and the bottom portion 3b to the side portion 3c. A pressure sensor (not shown) that detects a pressure inside the sealed container 3 is provided in the sealed container 3. The sealed container 3 is formed of a material having heat resistance and pressure resistance such as carbon steel, austenitic stainless steel, heat-resistant non-ferrous alloy steel, or a material that reflects radiant heat such as nickel (Ni), copper (Cu), and molybdenum (Mo). The shape of the sealed container 3 is not particularly limited, and can be a cylindrical shape, an elliptical cylindrical shape, a square cylindrical shape, or the like.

[0023] A hydrogen-based gas is introduced into the closed container 3. The hydrogen-based gas is a gas containing isotopes of hydrogen. As the hydrogen-based gas, deuterium gas, protium gas, or a mixed gas of an inert gas and deuterium gas, an inert gas and protium gas can be used. The protium gas is a mixture of naturally occurring protium and deuterium, that is, a mixture containing protium at a ratio of 99.985% and deuterium at a ratio of 0.015%. In the following description, when protium and deuterium are not distinguished, they are described as "hydrogen" or "H2". As the inert gas, for example, argon (Ar) gas, nitrogen (N2) gas, helium (He) gas, neon (Ne) gas, or the like can be used.

[0024] The supply section 4 has a pipe 4a connected to the closed container 3 and a switching valve 4b provided on the pipe 4a. Although not shown, the supply section 4 also has a tank for storing the hydrogen-based gas, a pump for delivering the hydrogen-based gas in the tank to the closed container 3, a pressure sensor for detecting the pressure inside the pipe 4a, and the like. The switching valve 4b is a pressure adjustment valve configured to be switched in accordance with the pressure inside the pipe 4a.

[0025] The discharge section 5 has a pipe 5a connected to the closed container 3 and a switching valve 5b provided on the pipe 5a. The discharge section 5 has a function as a safety mechanism for preventing the closed container 3 from being damaged when the pressure inside the closed container 3 excessively rises due to excessive heating. Although not shown, the discharge section 5 also has a pump for discharging the hydrogen-based gas inside the closed container 3, a pressure sensor for detecting the pressure inside the pipe 5a, and the like. The switching valve 5b is a pressure adjustment valve configured to be switched in accordance with the pressure inside the pipe 5a.

[0026] The vacuum exhaust section 6 has a pipe 6a connected to the closed container 3 and a switching valve 6b provided on the pipe 6a. Although not shown, the vacuum exhaust section 6 also has a pump for performing vacuum exhaust on the inside of the closed container 3, a pressure sensor for detecting the pressure inside the pipe 6a, and the like. The switching valve 6b is a pressure adjustment valve configured to be switched in accordance with the pressure inside the pipe 6a.

[0027] The control section 7 mainly has a storage section and the like, for example, a central processing unit, a read only memory, a random access memory, and the like. In the central processing unit, various arithmetic processing is performed using, for example, a program, data, and the like stored in the storage section.

[0028] The control unit 7 controls the operation of the supply portion 4, the discharge portion 5, and the vacuum exhaust portion 6 of the heat generating apparatus 1. The control unit 7 is electrically connected to a pressure sensor and an on-off valve 4b provided on a pipe 4a of the supply portion 4, and performs on-off control of the on-off valve 4b based on the pressure detected by the pressure sensor. The control unit 7 is electrically connected to a pressure sensor and an on-off valve 5b provided on a pipe 5a of the discharge portion 5, and performs on-off control of the on-off valve 5b based on the pressure detected by the pressure sensor. The control unit 7 is electrically connected to a pressure sensor and an on-off valve 6b provided on a pipe 6a of the vacuum exhaust portion 6, and performs on-off control of the on-off valve 6b based on the pressure detected by the pressure sensor.

[0029] The control unit 7 is electrically connected to the heater 15 and the temperature sensor 16 described later, and controls the output of the heater 15 based on the temperature detected by the temperature sensor 16. The control unit 7 adjusts the temperature of the heat generating body 14 by controlling the output of the heater 15, so as to maintain the heat generating body 14 at a temperature most suitable for heat generation (for example, 300°C to 1000°C).

[0030] The support mechanism 8 is provided inside the closed container 3, and supports the heat generating structure 2. The support mechanism 8 has a placement portion 8a in which the heat generating structure 2 is placed, and a support portion 8b that fixes the placement portion 8a to the closed container 3. In the support mechanism 8, for example, four support portions 8b protrude from the bottom of the placement portion 8a, and the four support portions 8b are fixed to the bottom 3b of the closed container 3.

[0031] (Heat generating structure) Figure 2 is a schematic view showing the structure of the heat generating structure 2 of the present embodiment. As shown in Figure 2 , the heat generating structure 2 includes a silicon substrate 13, a heat generating body 14, a heater 15, and a temperature sensor 16. In the present embodiment, the heat generating structure 2 has a structure in which the silicon substrate 13, the heat generating body 14, the heater 15, and the temperature sensor 16 are unitized. The heat generating structure 2 is configured to be mounted in a manner that can be freely attached and detached with respect to the placement portion 8a of the support mechanism 8.

[0032] The silicon substrate 13 serves as a pedestal for the heat generating body 14. The silicon substrate 13 has a flat surface, and the heat generating body 14 is provided on the flat surface. The surface roughness of the flat surface of the silicon substrate 13 is preferably 10 nm or less, and further preferably 1 nm or less. The surface roughness can be calculated based on, for example, the arithmetic mean roughness Ra defined in Japanese Industrial Standards JIS B 0601:2013. The thickness of the silicon substrate 13 is not particularly limited, and is, for example, 1 mm or less.

[0033] The silicon substrate 13 is a single-crystal silicon wafer having a silicon oxide film 13a. Commercially available wafers, such as those in a disk shape, can be used as the single-crystal silicon wafer having the silicon oxide film 13a. The thickness of the silicon substrate 13 is not particularly limited, for example, it is 1 mm or less. The thickness of the silicon oxide film 13a is not particularly limited, for example, it is 3 nm to 100 nm. It should be noted that the silicon substrate 13 is not limited to a single-crystal silicon wafer having a silicon oxide film 13a; it can be, for example, a single-crystal silicon wafer without a silicon oxide film.

[0034] The purity of the silicon substrate 13 is preferably 99.99999% or higher, and more preferably 99.999999999% or higher.

[0035] The heating element 14 generates heat through the storage and release of hydrogen. The heating element 14 has a support 61 disposed on the silicon substrate 13 and a multilayer film 62 disposed on the support 61. The detailed structure of the heating element 14 will be described below using another accompanying drawing.

[0036] Heater 15 heats heating element 14. Heater 15 heats up according to the supplied power. Power supply for supplying power to heater 15 is provided, for example, in control unit 7. In this embodiment, heater 15 is a plate-shaped ceramic heater having a structure in which conductors are provided inside a substrate formed of ceramic.

[0037] Temperature sensor 16 detects the temperature of heating element 14. In this embodiment, temperature sensor 16 is a thermocouple built into heater 15 and is configured to detect the temperature of heating element 14 through heater 15.

[0038] (Heating element) Next, refer to Figure 3 and Figure 4 The detailed structure of the heating element 14 is described below. For example... Figure 3 As shown, the heating element 14 has a laminate 14a, which has a support 61 and a multilayer film 62.

[0039] The support 61 can be of any structure, as long as it allows hydrogen gas to be stored in and released from the heating element 14, and the support 61 can be formed from at least one of a porous body, a hydrogen permeation membrane, and a proton conductor. In this example, the support 61 is formed as a plate having a surface and a back surface. The porous body has pores of a size through which hydrogen gas can pass. The porous body can be formed from, for example, metals, non-metals, ceramics, etc. The porous body is preferably formed from a material that does not impede the reaction (hereinafter referred to as the heating reaction) between hydrogen gas and the multilayer membrane 62. The hydrogen permeation membrane can be formed from, for example, a hydrogen storage metal or a hydrogen storage alloy. Nickel (Ni), palladium (Pd), vanadium (V), niobium (Nb), tantalum (Ta), titanium (Ti), etc., can be used as hydrogen storage metals. LaNi5, Ca5Cu, Mg2Zn, ZrNi2, ZrCr2, TiFe, TiCo, Mg2Ni, Mg2Cu, etc., can be used as hydrogen storage alloys. The hydrogen permeation membrane comprises a sheet with a mesh structure. BaCeO3 series can be used (e.g., Ba(Ce) 0.95 Y 0.05 )O 3-δ SrCeO3 series (e.g., Sr(Ce) 0.95 Y 0.05 )O 3-δ ), CaZrO3 series (e.g., CaZr) 0.95 Y 0.05 O 3-α ), SrZrO3 series (e.g., SrZr) 0.9 Y 0.1 O 3-α βAl2O3, βGa2O3, etc. are used as proton conductors.

[0040] like Figure 4 As shown, a multilayer film 62 is disposed on a support 61. The multilayer film 62 includes a first layer 71 formed of a hydrogen storage metal or hydrogen storage alloy, and a second layer 72 formed of a hydrogen storage metal, hydrogen storage alloy, or ceramic different from the first layer 71. A heterogeneous material interface 73, described later, is formed between the first layer 71 and the second layer 72. Figure 4 In this configuration, the first layer 71 and the second layer 72 of the multilayer film 62 are alternately stacked on one side (e.g., the surface) of the support 61 in this order. The first layer 71 and the second layer 72 each have five layers. It should be noted that the number of layers in each of the first layer 71 and the second layer 72 can be appropriately varied. The second layer 72 and the first layer 71 of the multilayer film 62 can also be alternately stacked on the surface of the support 61 in this order. This is as long as the first layer 71 and the second layer 72 of the multilayer film 62 each have more than one layer and form more than one heterogeneous material interface 73. Figure 2As shown, when the first layer 71 and the second layer 72 are alternately stacked on the surface of the support 61 in this order, a dissimilar material interface 73 is also formed between the first layer 71 and the support 61. Although not shown, when the second layer 72 and the first layer 71 are alternately stacked on the surface of the support 61 in this order, a dissimilar material interface 73 is also formed between the second layer 72 and the support 61.

[0041] The first layer 71 can be formed from any of the following: titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), tantalum (Ta), and their alloys. The alloy forming the first layer 71 is preferably an alloy formed from two or more of the following: titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), and tantalum (Ta). Alloys in which additive elements have been added to titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), and tantalum (Ta) can be used as the alloy forming the first layer 71.

[0042] The second layer 72 can be formed from any of the following: titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), tantalum (Ta), and their alloys, as well as silicon carbide (SiC). The alloy forming the second layer 72 is preferably an alloy formed from two or more of the following: titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), and tantalum (Ta). Alloys containing additive elements in titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), and tantalum (Ta) can be used as alloys to form the second layer 72.

[0043] As a combination of the first layer 71 and the second layer 72, if the types of elements are represented as "first layer 71-second layer 72 (second layer 72-first layer 71)", then Pd-Ni, Ni-Cu, Ni-Cr, Ni-Fe, Ni-Mg, Ni-Co, and Ni-Ca are preferred. When the second layer 72 is formed of ceramic, "first layer 71-second layer 72" is preferably Ni-SiC.

[0044] like Figure 5 As shown, the heterogeneous material interface 73 allows hydrogen atoms to pass through. Figure 5 This diagram illustrates the state in which hydrogen atoms in the metal lattice of the first layer 71, formed by a face-centered cubic hydrogen storage metal, penetrate the dissimilar material interface 73 and move into the metal lattice of the second layer 72. Hydrogen is known to be light and can hop to sites (octahedral sites, tetrahedral sites, etc.) occupied by hydrogen in substances A and B, while simultaneously undergoing quantum diffusion. Therefore, the hydrogen stored in the heating element 14 undergoes both hopping and quantum diffusion within the multilayer film 62. In the heating element 14, hydrogen penetrates the first layer 71, the dissimilar material interface 73, and the second layer 72 through quantum diffusion.

[0045] The thicknesses of the first layer 71 and the second layer 72 are preferably less than 1000 nm each. When the thicknesses of the first layer 71 and the second layer 72 are each 1000 nm or more, hydrogen becomes difficult to penetrate the multilayer film 62. Furthermore, by making the thicknesses of the first layer 71 and the second layer 72 less than 1000 nm, a nanostructure that does not exhibit bulk properties can be maintained. It is more preferable that the thicknesses of the first layer 71 and the second layer 72 are each less than 500 nm. By making the thicknesses of the first layer 71 and the second layer 72 less than 500 nm, a nanostructure that does not exhibit bulk properties at all can be maintained.

[0046] Next, an example of the manufacturing method of the heating element 14 will be described. A plate-shaped support 61 is prepared, and the hydrogen storage metal or hydrogen storage alloy constituting the first layer 71 and the second layer 72 is deposited in a gaseous state using a vapor deposition apparatus. The first layer 71 and the second layer 72 are alternately deposited on the surface of the support 61 by condensation or adsorption. Thus, a laminate 14a with multiple layers 62 is formed on the surface of the support 61. It should be noted that the first layer 71 and the second layer 72 are preferably deposited continuously under vacuum. Therefore, no natural oxide film is formed between the first layer 71 and the second layer 72, but only a dissimilar material interface 73 is formed. A physical vapor deposition apparatus that vapor-deposits the hydrogen storage metal or hydrogen storage alloy using physical means can be used as the vapor deposition apparatus. Sputtering apparatus, vacuum vapor deposition apparatus, and chemical vapor deposition (CVD) apparatus are preferred as physical vapor deposition apparatuses. Alternatively, hydrogen storage metal or hydrogen storage alloy can be deposited on the surface of the support 61 by electroplating, forming alternating first layer 71 and second layer 72.

[0047] As described above, the heating element 14 is disposed on the smooth surface of the silicon substrate 13, which serves as a pedestal. Therefore, by forming a support 61 on the smooth surface of the silicon substrate 13 and forming a multilayer film 62 on the support 61, a smooth heterogeneous material interface 73 can be formed.

[0048] The support 61 functions as a hydrogen storage layer for storing hydrogen. The thickness of the support 61 can be preset according to the thickness of the multilayer film 62. The thickness of the support 61 is approximately the same as or slightly greater than the thickness of the multilayer film 62. Specifically, when the thickness of the support 61 is T1 and the thickness of the multilayer film 62 is T2, T1 / T2 is preferably 0.1 or more and 2.0 or less, more preferably 0.2 or more and 1.0 or less.

[0049] In this embodiment, the support 61 is formed of Pd. The thickness of the support 61 is 20 nm. The multilayer film 62 includes a first layer 71 formed of Cu and a second layer 72 formed of Ni. The first layer 71 and the second layer 72 are each six layers. The thickness of the first layer 71 is 2 nm. The thickness of the second layer 72 is 14 nm.

[0050] Although the heating device 1 includes a heating element 14 in this embodiment, it may also include a heating element with a different structure from the heating element 14. (Refer to...) Figure 6 The first variation will be explained, and reference will be made to... Figure 7 The second variation will be explained.

[0051] [First Variation] Heating device 1 has the following features: Figure 6 The heating element 75 shown is used in place of the heating element 14.Figure 6 The multilayer film 62 of the stacked structure of the heating element 75 shown has a third layer 77 in addition to the first layer 71 and the second layer 72. The third layer 77 is formed of a hydrogen storage metal, hydrogen storage alloy, or ceramic, which is different from the first layer 71 and the second layer 72. The thickness of the third layer 77 is preferably less than 1000 nm. Figure 6 In this structure, the first layer 71, the second layer 72, and the third layer 77 are stacked on the surface of the support 61 in the order of first layer 71, second layer 72, first layer 71, and third layer 77. It should be noted that the first layer 71, second layer 72, and third layer 77 can be stacked on the surface of the support 61 in the order of first layer 71, third layer 77, first layer 71, and second layer 72. That is, the multilayer film 62 has a stacked structure in which the first layer 71 is disposed between the second layer 72 and the third layer 77. The multilayer film 62 only needs to have one or more third layers 77. Similar to the dissimilar material interface 73, the dissimilar material interface 78 formed between the first layer 71 and the third layer 77 allows hydrogen atoms to permeate.

[0052] The third layer 77 can be formed from any of the following: titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), tantalum (Ta) and their alloys, silicon carbide (SiC), calcium oxide (CaO), yttrium oxide (Y₂O₃), titanium carbide (TiC), lanthanum hexaboride (LaB₆), strontium oxide (SrO), and barium oxide (BaO). The alloy forming the third layer 77 is preferably an alloy formed from two or more of the following: titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), and tantalum (Ta). Alloys containing additive elements in titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), and tantalum (Ta) can be used as alloys to form the third layer 77.

[0053] Specifically, the third layer 77 is preferably formed from any one of calcium oxide (CaO), yttrium trioxide (Y2O3), titanium carbide (TiC), lanthanum hexaboride (LaB6), strontium oxide (SrO), and barium oxide (BaO). The heating element 75 having a third layer 77 formed from any one of these materials increases its hydrogen storage capacity and the amount of hydrogen penetrating the dissimilar material interfaces 73 and 78, thereby enabling high output of excess heat. The third layer 77 formed from any one of these materials preferably has a thickness of 10 nm or less. Therefore, the multilayer film 62 allows hydrogen atoms to easily penetrate. The third layer 77, formed from any of the following: calcium oxide (CaO), yttrium trioxide (Y₂O₃), titanium carbide (TiC), lanthanum hexaboride (LaB₆), strontium oxide (SrO), and barium oxide (BaO), may not be a complete film but rather an island-like structure. Furthermore, the first layer 71 and the third layer 77 are preferably formed continuously under vacuum. Thus, no natural oxide film forms between the first layer 71 and the third layer 77; only a heterogeneous material interface 78 is formed.

[0054] As a combination of the first layer 71, the second layer 72, and the third layer 77, if the types of elements are represented as "first layer 71-third layer 77-second layer 72", then the preferred choices are 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, and Ni-La. B6-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, Ni-La B6-Mg, Ni-CaO-Co, Ni-Y2O3-Co, Ni-TiC-Co, Ni-LaB6-Co, Ni-CaO-SiC, Ni-Y2O3-SiC, Ni-TiC-SiC, Ni-LaB6-SiC.

[0055] Similar to the heating element 14, the heating element 75 is disposed on the smooth surface of the silicon substrate 13, which serves as a pedestal. Therefore, by forming a support 61 on the smooth surface of the silicon substrate 13 and forming a multilayer film 62 on the support 61, a smooth heterogeneous interface 73 and heterogeneous interface 78 can be formed.

[0056] [Second variation] Heating device 1 has the following features: Figure 7 The heating element 80 shown is used in place of the heating element 14. Figure 7 The multilayer film 62 of the stacked structure of the heating element 80 shown has a fourth layer 82 in addition to the first layer 71, the second layer 72, and the third layer 77. The fourth layer 82 is formed of a hydrogen storage metal, hydrogen storage alloy, or ceramic, which is different from the first layer 71, the second layer 72, and the third layer 77. The thickness of the fourth layer 82 is preferably less than 1000 nm. Figure 7 In this structure, the first layer 71, the second layer 72, the third layer 77, and the fourth layer 82 are stacked on the surface of the support 61 in the following order: first layer 71, second layer 72, first layer 71, third layer 77, first layer 71, fourth layer 82. It should be noted that the first layer 71, second layer 72, third layer 77, and fourth layer 82 can be stacked on the surface of the support 61 in the following order: first layer 71, fourth layer 82, first layer 71, third layer 77, first layer 71, second layer 72. That is, the multilayer film 62 has a stacked structure in which the second layer 72, third layer 77, and fourth layer 82 are stacked in any order, and the first layer 71 is disposed between the second layer 72, third layer 77, and fourth layer 82. The multilayer film 62 only needs to have one or more fourth layers 82. Similar to the heterogeneous interface 73 and heterogeneous interface 78, the heterogeneous interface 83 formed between the first layer 71 and the fourth layer 82 allows hydrogen atoms to permeate.

[0057] The fourth layer 82 can be formed from any of the following: titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), tantalum (Ta) and their alloys, silicon carbide (SiC), calcium oxide (CaO), yttrium oxide (Y₂O₃), titanium carbide (TiC), lanthanum hexaboride (LaB₆), strontium oxide (SrO), and barium oxide (BaO). The alloy forming the fourth layer 82 is preferably an alloy formed from two or more of the following: titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), and tantalum (Ta). Alloys containing additive elements in titanium (Ti), vanadium (V), nickel (Ni), palladium (Pd), copper (Cu), chromium (Cr), iron (Fe), magnesium (Mg), cobalt (Co), calcium (Ca), zirconium (Zr), niobium (Nb), molybdenum (Mo), and tantalum (Ta) can be used as alloys to form the fourth layer 82.

[0058] Specifically, the fourth layer 82 is preferably formed from any one of calcium oxide (CaO), yttrium trioxide (Y2O3), titanium carbide (TiC), lanthanum hexaboride (LaB6), strontium oxide (SrO), and barium oxide (BaO). The heating element 80 having a fourth layer 82 formed from any one of calcium oxide (CaO), yttrium trioxide (Y2O3), titanium carbide (TiC), lanthanum hexaboride (LaB6), strontium oxide (SrO), and barium oxide (BaO) increases its hydrogen storage capacity and the amount of hydrogen penetrating the heterogeneous interface 73, heterogeneous interface 78, and heterogeneous interface 83, thereby enabling high output of excess heat. The fourth layer 82, formed from any one of calcium oxide (CaO), yttrium trioxide (Y₂O₃), titanium carbide (TiC), lanthanum hexaboride (LaB₆), strontium oxide (SrO), and barium oxide (BaO), is preferably 10 nm or less in thickness. This allows hydrogen atoms to easily penetrate the multilayer film 62. The fourth layer 82, formed from any one of calcium oxide (CaO), yttrium trioxide (Y₂O₃), titanium carbide (TiC), lanthanum hexaboride (LaB₆), strontium oxide (SrO), and barium oxide (BaO), may not be formed as a complete film, but rather as an island. Furthermore, the first layer 71 and the fourth layer 82 are preferably formed continuously under vacuum. This prevents the formation of a natural oxide film between the first layer 71 and the fourth layer 82, instead creating only a heterogeneous material interface 83.

[0059] As a combination of the first layer 71, the second layer 72, the third layer 77 and the fourth layer 82, if the types of elements are represented as "first layer 71-fourth layer 82-third layer 77-second layer 72", then Ni-CaO-Cr-Fe, Ni-Y2O3-Cr-Fe, Ni-TiC-Cr-Fe, and Ni-LaB6-Cr-Fe are preferred.

[0060] Similar to the heating element 14, the heating element 80 is disposed on the smooth surface of the silicon substrate 13, which serves as a pedestal. Therefore, by forming a support 61 on the smooth surface of the silicon substrate 13 and forming a multilayer film 62 on the support 61, smooth heterogeneous material interfaces 73, 78, and 83 can be formed.

[0061] It should be noted that, as a multi-layered heating element, it can be used in combination with other materials, such as... Figure 4 The heating element 14 shown is as follows: Figure 6 The heating element 75 shown is as follows: Figure 7 Two or more of the heating elements 80 shown can be used. A multilayer heating element structure can be adopted with multiple layers arranged in any order. Furthermore, the structure of the multilayer film 62, for example, the thickness ratio of each layer, the number of layers, and the material, can be appropriately changed according to the temperature to be used.

[0062] (Functions and Effects) In the heating device 1 constructed as described above, the sealed container 3 is opened, and the heating element 2 is placed in the mounting portion 8a of the support mechanism 8 located inside the sealed container 3. The sealed container 3 is then sealed, and the pump of the vacuum exhaust unit 6 is driven to exhaust a vacuum from the inside of the sealed container 3. The heater 15 is then driven to heat the heating element 14. For example, the temperature of the heating element 14 is adjusted to approximately 200°C by the heater 15 to remove moisture from the heating element 14.

[0063] The output of heater 15 is increased, and the heating element 14 is further heated. For example, the temperature of the heating element 14 is adjusted to about 300°C by heater 15. The pump of supply unit 4 is driven to introduce hydrogen gas stored in tank (not shown) into the sealed container 3 through pipe 4a. As a result, hydrogen is stored in the support 61 and multilayer film 62 of heating element 14. A mixed gas containing, for example, H2 and Ar (3% H2 / Ar gas) can be used as the hydrogen gas. After the hydrogen is stored in heating element 14, the drive of supply unit 4 is stopped. The output of heater 15 is controlled to set the temperature of heating element 14 to any temperature within the temperature range most suitable for heating (for example, about 700°C), thereby heating heating element 14. While heating heating element 14, the pump of vacuum exhaust unit 6 is driven to exhaust the hydrogen gas inside sealed container 3 through pipe 6a. As a result, heating element 14 is in a heated state (hereinafter referred to as the heated state). That is, hydrogen stored in the support 61 and multilayer film 62 of the heating element 14 penetrates the heterogeneous material interface 73 through quantum diffusion, or hydrogen diffuses to the heterogeneous material interface 73 through quantum diffusion, thereby generating excess heat in the heating element 14.

[0064] While the vacuum exhaust unit 6 continues to operate, the hydrogen stored in the heating element 14 is slowly released (exhausted). Therefore, when the heating element 14 continues to heat for an extended period, the operation of the vacuum exhaust unit 6 is stopped, and the supply unit 4 is activated to introduce hydrogen gas into the sealed container 3, thus storing (replenishing) hydrogen in the heating element 14. For example, hydrogen gas is slowly introduced until the pressure inside the sealed container 3 reaches one atmosphere. At this time, the temperature of the heating element 14 is maintained within the optimal temperature range for heating by controlling the output of the heater 15. After hydrogen is stored in the heating element 14, the operation of the supply unit 4 is stopped, and the vacuum exhaust unit 6 is activated, thereby enabling the heating element 14 to continue heating.

[0065] Figure 8 This is a schematic diagram illustrating a heating method. Figure 8 The heater 15 and temperature sensor 16 of the heating structure 2 are omitted in the original text. Hydrogen-based gas is introduced into the sealed container 3, causing hydrogen molecules to adsorb onto the surface of the multilayer film 62 of the heating element 14 (the side opposite to the support 61), and these hydrogen molecules dissociate into two hydrogen atoms. The dissociated hydrogen atoms then enter (store) inside the multilayer film 62 and the support 61. At this time, the hydrogen atoms entering the multilayer film 62 and the support 61 do not enter the silicon substrate 13. By expelling the hydrogen-based gas from the sealed container 3, the hydrogen atoms that entered the multilayer film 62 and the support 61 return to the surface of the multilayer film 62 and recombine to form hydrogen molecules, thus releasing them. In this way, hydrogen atoms penetrate the heterogeneous material interface 73 (see reference 73) through quantum diffusion. Figure 5Alternatively, hydrogen atoms can diffuse to the interface 73 of a different substance through quantum diffusion, thereby raising the temperature in the heating element 14 to a temperature above the heating temperature of the heater 15, thus generating excess heat.

[0066] According to the heating structure 2 of this embodiment, by placing the heating element 14 on the silicon substrate 13, which serves as a pedestal, a smooth heterogeneous material interface 73 can be formed, and the heating stability and controllability of the heating element 14 can be improved.

[0067] Since the heating structure 2 can be manufactured easily and inexpensively using a commercially available single-crystal silicon wafer with a silicon oxide film 13a as the silicon substrate 13, it can be manufactured readily and cheaply. Furthermore, by using a large-diameter single-crystal silicon wafer as the silicon substrate 13 and providing a large-diameter heating element 14 on its surface, high output can be achieved.

[0068] Since the purity of the silicon substrate 13 is above 99.99999%, the heating structure 2 suppresses the contamination and deterioration of the foreign substance interface 73 caused by impurities contained in the silicon substrate 13, thereby further improving the heating stability and controllability of the heating element 14.

[0069] The heating structure 2 has a unitized structure that integrates the silicon substrate 13, the heating element 14, the heater 15, and the temperature sensor 16. Therefore, it is easy to add or remove the heating structure 2 provided on the heating device 1, thereby increasing the design freedom of the heating device 1.

[0070] According to the heating device 1 of this embodiment, by having the heating structure 2 described above, the stability and controllability of the heating of the heating element 14 can be improved.

[0071] Furthermore, in the heating device 1, when the temperature T of the heating element 14 reaches the critical temperature Tc, a chemical reaction or alloying reaction occurs between the metals constituting the first layer 71, the second layer 72, and the support 61, forming microcrystals of a ternary alloy with different alloy concentrations (alloy compositions). The critical temperature Tc is the temperature at which the metals constituting the support 61, the first layer 71, and the second layer 72 alloy, and is also called the alloying reaction initiation temperature. For example, when the first layer 71 is composed of Cu, the second layer 72 is composed of Ni, and the support 61 is composed of Pd, the critical temperature Tc is 500°C, and when the temperature T of the heating element 14 reaches the critical temperature Tc (500°C), microcrystals of a ternary alloy (Pd-Ni-Cu alloy) will be formed.

[0072] Figure 9 This is a schematic diagram illustrating the microcrystalline state of a ternary alloy. For example... Figure 9As shown, when the condition T = Tc is met, in the heating element 14, the metal constituting the first layer 71, the metal constituting the second layer 72, and the metal constituting the support 61 are alloyed to form microcrystals 90 of a ternary alloy with different alloy concentrations. Figure 9 In the diagram, the difference in alloy concentration among the microcrystals 90 is represented by different types of hatching. Between the microcrystals 90 of the ternary alloy with different alloy concentrations, a dissimilar interface 91, different from the dissimilar interface 73, will form. For convenience, the formation of this dissimilar interface 91, different from the dissimilar interface 73, is referred to as "deterioration of the dissimilar interface." It is important to note that silicon atoms constituting the silicon substrate 13 will not diffuse into the interior of the support 61 or the multilayer films 62 (first layer 71 and second layer 72). Furthermore, because the silicon substrate 13 is of high purity, impurity elements in the silicon substrate 13 will not segregate into the interior of the support 61 or the multilayer films 62.

[0073] When the thickness of the support 61 is approximately the same as or slightly greater than the thickness of the multilayer film 62, the metal constituting the support 61 will not further diffuse into the ternary alloy microcrystals 90 after the formation of the ternary alloy microcrystals 90. Although the alloying reaction causes the dissimilar material interface to deteriorate, the reduction of the dissimilar material interface (also known as thinning) is suppressed. In the heating device 1, although the dissimilar material interface deteriorates, because the dissimilar material interface 91 is formed, hydrogen atoms can penetrate the dissimilar material interface 91 through quantum diffusion, or hydrogen atoms can diffuse into the dissimilar material interface 91 through quantum diffusion, thereby generating excess heat above the heating temperature in the heating element 14.

[0074] It should be noted that, although in this embodiment, the thickness of the support 61 is approximately the same as or slightly greater than the thickness of the multilayer film 62, when the thickness of the support relative to the thickness of the multilayer film 62 is, for example, three orders of magnitude or more, the degradation and reduction of the heterogeneous material interface may be exacerbated when the temperature T of the heating element exceeds the critical temperature Tc. In the following description, as a comparative example of the heating element, the case where the thickness of the support is, for example, three orders of magnitude or more than the thickness of the multilayer film will be used.

[0075] use Figure 10 This explains the deterioration and reduction at the interface of different substances. Figure 10 (a) indicates the state where the temperature T of the heating element is less than the critical temperature Tc. Figure 10 (b) indicates that the temperature T of the heating element has reached the critical temperature Tc. Figure 10 (c) indicates the state where the temperature T of the heating element is greater than the critical temperature Tc.

[0076] like Figure 10As shown in (a), the heating element 214 has a support 261 and a multilayer film 262 disposed on the support 261. The multilayer film 262 has a first layer 271 and a second layer 272. A heterogeneous material interface 273 is formed between the first layer 271 and the second layer 272. The thickness of the support 261 is, for example, three orders of magnitude or more relative to the thickness of the multilayer film 262. Figure 10 In the state shown in (a), the interface 273 of the different substances has not deteriorated. Therefore, the heating element 214 can generate heat as designed.

[0077] like Figure 10 As shown in (b), when the temperature T of the heating element 214 reaches the critical temperature Tc, the metals constituting the support 261, the first layer 271, and the second layer 272 are alloyed to form microcrystals 290 of ternary alloys with different alloy concentrations. Between these microcrystals 290 of ternary alloys with different alloy concentrations, a dissimilar interface 291, different from the dissimilar interface 273, is formed. That is, the dissimilar interface undergoes degradation. Figure 10 In the state shown in (b), the heating element 214 can generate heat as designed, since a heterogeneous material interface 291 is eventually formed.

[0078] like Figure 10 As shown in (c), when the temperature T of the heating element 214 is greater than the critical temperature Tc, the metal constituting the support 261 diffuses into the microcrystals 290 of the ternary alloy. In this way, the number of microcrystals constituting the support 261 with a metal content approaching 100% increases, and the heterogeneous material interface 291 decreases. Figure 11 In the state shown in (c), the heating in the heating element 214 is suppressed due to the reduction of the heterogeneous material interface 291.

[0079] (Other implementation methods) In the above embodiments, a heating device 1 having a heating structure 2 is described, but the present invention is not limited thereto.

[0080] Figure 11 This is a schematic diagram illustrating the structure of the heating device 100 in other embodiments. Components that are the same as or equivalent to those in the embodiments described above are given the same component symbols. Descriptions that are repeated in the embodiments described above will be appropriately omitted, and structures that differ from the embodiments described above will be described in detail.

[0081] exist Figure 5The heating device 100 includes three heating structures 2, a sealed container 3, a supply unit 4, a discharge unit 5, a vacuum exhaust unit 6, a control unit 7, and a support mechanism 108. The heater 15 and temperature sensor 16 of each heating structure 2 are electrically connected to the control unit 7. Based on the temperature detected by the temperature sensor 16, the control unit 7 controls the output of the heater 15 of each heating structure 2. Although the heating device 100 has three heating structures 2 in this embodiment, it is not limited to this; the heating device 100 may include two or more heating structures 2.

[0082] A support mechanism 108 is disposed inside the sealed container 3 to support each heating structure 2. The support mechanism 108 has three mounting portions 108a and three support portions 108b. The three mounting portions 108a are used to respectively mount the three heating structures 2, and the three support portions 108b are used to fix the three mounting portions 108a to the sealed container 3. The three mounting portions 108a are arranged at different heights and fixed to the support portions 108b. The support portions 108b are fixed to the upper part 3a and the bottom part 3b of the sealed container 3.

[0083] Similar to the embodiments described above, the heating device 100, by providing heating structures 2, can improve the stability and controllability of the heating of the heating element 14. Furthermore, by providing multiple heating structures 2, the heating device 100 can achieve high output.

[0084] This invention is not limited to the above-described embodiments, and appropriate modifications can be made without departing from the spirit of this invention.

[0085] In the above embodiment, the heating structure 2 has a unitized structure comprising the silicon substrate 13, the heating element 14, the heater 15, and the temperature sensor 16, but is not limited thereto. The heating structure 2 only needs to include the silicon substrate 13 and the heating element 14. For example, in the heating device 1, the heater 15 and the temperature sensor 16 can be mounted on the mounting portion 8a of the support mechanism 8, and the heating structure 2, which includes the silicon substrate 13 and the heating element 14, can be configured to be freely mounted and detached relative to the heater 15. In this case, for example, when the heating structure 2 is replaced with another heating structure, the heater 15 and the temperature sensor 16 can remain on the mounting portion 8a of the support mechanism 8, and only the heating structure 2 can be replaced.

[0086] exist ​ In this paper, the crystal structure of hydrogen storage metals is described as face-centered cubic, but the crystal structure is not limited to face-centered cubic and can also be body-centered cubic, etc.

[0087] When the thickness of the support 61 is T1 and the thickness of the multilayer film 62 is T2, T1 / T2 is preferably 0.1 or more and 5.0 or less, and more preferably 0.2 or more and 3.0 or less.

[0088] Explanation of reference numerals in the attached figures 1: Heating device 2: Heating structure 3: Sealed container 4: Supply Department 4a: Piping 4b: Switch valve 5: Discharge section 5a: Piping 5b: Switch valve 6: Vacuum Exhaust Section 6a: Piping 6b: Switch valve 7: Control Department 8: Supporting institutions 8a: Setting Department 8b: Support column 13: Silicon substrate 13a: Silicon oxide film 14: Fever-generating body 14a: Laminated body 15: Heater 16: Temperature sensor 61: Support 62: Multilayer film 71: First Floor 72: Second layer 73: Interface of different substances 75: Fever element 77: Third Floor 78: Interface of different substances 80: Heating element 82: Fourth Floor 83: Interface of different substances 100: Heating device 108: Supporting Institutions 108a: Setup Department 108b: Support column

Claims

1. A heating structure, characterized in that, have: Silicon substrate; and A heating element that generates heat through the storage and release of hydrogen. The heating element has a support disposed on the silicon substrate and a multilayer film disposed on the support. The support is formed of at least one of a porous body, a hydrogen-permeable membrane, and a proton conductor. The multilayer film has a first layer formed of a hydrogen storage metal or hydrogen storage alloy with a thickness of less than 1000 nm, and a second layer formed of a hydrogen storage metal, hydrogen storage alloy or ceramic different from the first layer with a thickness of less than 1000 nm.

2. The heating structure as described in claim 1, characterized in that, The silicon substrate is a single-crystal silicon wafer with a silicon oxide film.

3. The heating structure as described in claim 1, characterized in that, The purity of the silicon substrate is above 99.99999%.

4. The heating structure as described in claim 1, characterized in that, have: A heater for heating the heating element; and A temperature sensor that detects the temperature of the heating element.

5. A heating device, characterized in that, have: The heating structure as described in any one of claims 1 to 4; A sealed container that houses the heating structure; A supply unit for supplying hydrogen-based gas containing the hydrogen to the interior of the sealed container; and The exhaust section for discharging the hydrogen-based gas from inside the sealed container.

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