Battery electrode, method and apparatus for manufacturing the battery electrode, and secondary battery using the battery electrode

Abstract

The present invention provides a method for manufacturing electrodes that suppresses the formation of dendrites and also suppresses electrode deformation and a decrease in electrode deposition efficiency. [Solution] A method for manufacturing an electrode for a secondary battery, characterized by comprising a first step of forming a metal film 601 on a base substrate 602, and a second step of generating a temperature gradient between the metal film and the base substrate by thermomigration, thereby alloying the metal film or the base substrate with the metal film.

Description

Technical Field

[0001] The present invention relates to the composition or structure, manufacturing method, and manufacturing apparatus of battery electrodes such as fluoride batteries, zinc secondary batteries, silver zinc oxide secondary batteries, manganese oxide zinc secondary batteries, and zinc air secondary batteries. It also relates to an alloying method and alloying apparatus for metals, battery materials, etc. Further, the present invention relates to a secondary battery using the battery electrode, a battery unit, a control method for the battery unit, and a battery device.

[0002] The present invention relates to an electrolyte solution and a battery structure for improving the efficiency and characteristics of fluoride batteries and zinc secondary batteries. It also relates to a structure, method, usage method, and driving method for preventing short-circuiting between the negative electrode and the positive electrode due to dendrites in zinc (secondary) batteries. The present invention relates to zinc secondary batteries, a motor drive device having a battery unit, an electric vehicle having a zinc secondary battery as a power source, and the like.

Background Art

[0003] There is a demand for a battery with a high amount of electric power per unit weight and capacity, and research and development are underway for secondary batteries. Zinc secondary batteries have a high amount of electric power per unit weight and capacity, but there is a problem of dendrite generation.

[0004] Patent Document 1 describes a method for producing an electrode material for an alkaline secondary battery. Specifically, it is a method for producing a nickel-zinc alloy, in which zinc plating is performed on a base material and then nickel plating is performed. After that, heat treatment is performed to produce an alloy. The pre-heat treatment step involves forming a nickel-zinc alloy film by thermally diffusing nickel and zinc through continuous annealing treatment at a temperature of 400°C or higher and lower than 800°C for 10 seconds to 300 seconds.

[0005] However, since this method is performed with the temperature of the entire system being almost uniform, metal atom movement due to thermal diffusion occurs near the contact surface between the nickel foil and the zinc foil, but there is a problem that the entire system does not form an alloy due to the diffusion of zinc metal atoms and nickel metal atoms.

[0006] Non-Patent Document 1 is a paper regarding a method for suppressing dendrites generated at the negative electrode of a zinc secondary battery. Specifically, a solution in which a small amount of indium or tin, or two types of indium and tin are dissolved in a zincate bath prepared by dissolving ZnO in a 7.5 M (M = mol / L) aqueous NaOH solution was used as an electrolyte, and electrolytic plating was performed on zinc metal. At this time, the electrode reaction and standard potential (E 0 , 25 °C) are as follows. ZnO2 2- + 2H2O + 2e - = Zn + 4OH - -1.215 V HSnO2 - + H2O + 2e - = Sn + 3OH - -0.909 V Sn(OH)6 2- + 2e[[ID=..]] - = HSnO2 - + H2O + 3OH - -0.93 V In(OH)3 + 3e - = In + 3OH - -1.00 V

[0007] From these reduction reaction formulas, since the potential at which zinc is plated and the potential at which tin or indium is plated are almost the same, it is expected that zinc and the above indium or tin are simultaneously plated on the electrode.

[0008] Alloy plating has a dendrite suppression effect rather than zinc plating. However, the solubility of indium or tin that can dissolve in a high-concentration alkaline electrolyte is only several millimoles to several tens of millimoles per liter, and the dendrite suppression effect by alloying has limitations.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

[0010] This disclosure has been made in view of the above circumstances and provides a battery electrode that suppresses the generation of dendrites and a battery electrode that can realize a battery with a high energy storage capacity, and also relates to a method for manufacturing the battery electrode and a manufacturing apparatus for the battery electrode. Furthermore, it relates to a secondary battery, a battery unit and a control method for the battery unit and a battery device using the battery electrode of the present invention.

[0011] Furthermore, this invention relates to a structure, method, method of use, and driving method for preventing short circuits between the negative and positive electrodes caused by dendrites. It also relates to the secondary battery, motor drive device having a battery unit, and electric vehicle having the secondary battery as a power source. [Overview of the project] [Problems that the invention aims to solve]

[0012] Fluoride batteries, zinc secondary batteries, etc., can develop dendrites on their electrodes, leading to short circuits between the electrodes and causing malfunctions. They can also exhibit electrode deformation and reduced electrodeposition efficiency.

[0013] Some rechargeable secondary batteries use zinc as the negative electrode and a strong alkaline aqueous solution as the electrolyte. Zinc electrodes obtained by electrolysis of an additive-free, high-concentration alkaline zincate bath exhibit dendritic crystal growth. Furthermore, repeated dissolution and deposition reactions associated with charging and discharging cause the deposited zinc to become concentrated in the center of the electrode, leading to electrode deformation and a decrease in electrode deposition efficiency.

[0014] Furthermore, some conventional rechargeable batteries have safety issues, such as being flammable. They also suffer from high costs, lack of stability, and high temperature dependence. [Means for solving the problem]

[0015] One or more of the following metals—nickel, zinc, tin, gold, silver, indium, bismuth, or antimony—are formed or constructed on a substrate (film, foil, or plate) using plating, vapor deposition, sputtering, coating, or printing techniques. Furthermore, the material is alloyed using thermomigration or electromigration methods and techniques.

[0016] A metal film 601, such as tin (Sn), is formed on a base metal foil (base metal sheet, base metal foil) 602 made of zinc (Zn) by plating technology. A Peltier element 609a is placed on the metal film 601 side, and a Peltier element 609b is placed on the base metal foil 602 side. Current is supplied to the Peltier element 609a from a current (voltage) source 112a, and current is supplied to the Peltier element 609b from a current (voltage) source 112b. The Peltier element 609a dissipates heat to the metal film 601, heating it. The Peltier element 609b absorbs heat from the base metal foil (metal sheet) 602, cooling it. The Peltier elements 609a and 609b generate a temperature gradient, and a thermomigration effect is implemented on the electrode material 614. The electrode material 614 is heated and alloyed. The electrode material 614 is used as an electrode to constitute a secondary battery.

[0017] One or more of the following metals—nickel, zinc, tin, gold, silver, indium, bismuth, or antimony—are formed or constructed on a substrate (film, foil, or plate) using plating, vapor deposition, sputtering, coating, or printing techniques. Furthermore, the material is alloyed using thermomigration or electromigration methods and techniques.

[0018] Furthermore, in the structure of the battery material (battery electrode) and the manufacturing method of the battery material (battery electrode) of the present invention, a thin metal film (metal layer) of a metal from the 4th period of the periodic table (iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), etc.) and a thin metal film (metal layer) of a metal from the 5th to 6th periods of the periodic table (indium (In), tin (Sn), silver (Ag), gold (Au), antimony (Sb), bismuth (Bi), etc.) are layered on a substrate. By applying thermomigration and electromigration effects to the two layers of metal films, the layered metal films are alloyed. [Effects of the Invention]

[0019] A first metal film 601b is formed on a base metal foil 602, and a second metal film 601a is formed on the first metal film 601b. The second metal film 601a is heated, and the base metal foil 602 is cooled. For heating and cooling, for example, a Peltier element 609 (609a, 609b) is used. The Peltier element generates a temperature gradient between the metal films 601a and 601b, and a thermomigration effect is implemented. Due to the thermomigration effect and electromigration effect, the metals constituting the metal films 601a and 601b move, forming an alloy film 603. By forming an alloy film 603, the generation of dendrites is suppressed. In addition, deformation of the electrodes and a decrease in electrodeposition efficiency can be suppressed.

[0020] By using the battery electrodes of the present invention as electrodes in a secondary battery, dendritic crystal growth can be suppressed. Furthermore, due to the repeated dissolution and deposition reactions associated with charging and discharging, the deposited zinc does not concentrate in the center of the electrode, thereby suppressing electrode deformation and a decrease in electrode deposition efficiency. In addition, cost reduction can be achieved. Moreover, it is non-flammable, safe, and stable. [Brief explanation of the drawing]

[0021] [Figure 1] This is a diagram illustrating the method for manufacturing a battery electrode and the configuration of the battery electrode according to the present invention. [Figure 2] This is a diagram illustrating the method for manufacturing a battery electrode and the configuration of the battery electrode according to the present invention. [Figure 3] This is an explanatory diagram of the method for manufacturing a battery electrode according to the present invention. [Figure 4] This is an explanatory diagram of the method for manufacturing a battery electrode according to the present invention. [Figure 5] This is an explanatory diagram of the method for manufacturing a battery electrode according to the present invention. [Figure 6] This is an explanatory diagram of the method for manufacturing a battery electrode according to the present invention. [Figure 7] This is an explanatory diagram of the method for manufacturing a battery electrode according to the present invention. [Figure 8] This is an explanatory diagram of the method for manufacturing a battery electrode according to the present invention. [Figure 9] These are structural diagrams and explanatory diagrams of the battery of the present invention. [Figure 10] These are structural diagrams and explanatory diagrams of the battery of the present invention. [Figure 11] This is an explanatory diagram of the method for manufacturing the battery of the present invention. [Figure 12] This is an explanatory diagram of the test results for all-solid-state fluoride-ion batteries. [Figure 13] This is the result of EDS (Energy Dispersive X-ray Spectroscopy). [Figure 14] This is the result of EDS (Energy Dispersive X-ray Spectroscopy). [Figure 15] This is the result of EDS (Energy Dispersive X-ray Spectroscopy). [Figure 16] This is an explanatory diagram of a Peltier element. [Figure 17] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 18] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 19] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 20] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 21] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 22] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 23]This is a diagram showing the configuration and explanatory diagram of the heater chip of the present invention. [Figure 24] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 25] This is an explanatory diagram of the method for manufacturing a battery electrode according to the present invention. [Figure 26] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 27] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 28] This is an explanatory diagram of the method for manufacturing battery electrodes and the manufacturing apparatus of the present invention. [Figure 29] This diagram shows the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 30] This diagram shows the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 31] This diagram shows the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 32] This diagram illustrates the relationship between NaOH concentration and the potential window. [Figure 33] This is an explanatory diagram illustrating the relationship between the oxygen evolution potential and the hydrogen evolution potential in 0.0001 mol / L NaOH. [Figure 34] This is a diagram illustrating the relationship between NaOH concentration and oxygen evolution potential. [Figure 35] This is a diagram illustrating the relationship between NaOH concentration and hydrogen evolution potential. [Figure 36] This is a diagram illustrating the relationship between NaOH concentration and the potential window. [Figure 37] This is an explanatory diagram illustrating the relationship between potential and electric current (density). [Figure 38] This is a diagram illustrating the relationship between temperature and electrical conductivity. [Figure 39] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 40] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 41] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 42] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 43] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 44] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 45] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 46] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 47] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 48] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery unit of the present invention. [Figure 49] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery unit of the present invention. [Figure 50] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery unit of the present invention. [Figure 51] This is a configuration diagram and explanatory diagram of the drive control device of the present invention. [Modes for carrying out the invention]

[0022] The technique for forming a metal film or the like on the substrate of the present invention may be any of the following: plating, vapor deposition, sputtering, coating, printing, dropping, or spinner techniques. However, in this specification and in the drawings, the description will primarily assume that the film is formed or constructed using plating techniques.

[0023] Some rechargeable secondary batteries use zinc as the negative electrode and a strong alkaline aqueous solution as the electrolyte. Zinc electrodes obtained by electrolysis of an additive-free, high-concentration alkaline zincate bath exhibit dendritic crystal growth. Furthermore, repeated dissolution and deposition reactions associated with charging and discharging cause the deposited zinc to become concentrated in the center of the electrode, leading to electrode deformation and a decrease in electrode deposition efficiency.

[0024] The present invention makes it possible to suppress the formation of dendrites and prevent deformation of electrodes and a decrease in electrode deposition efficiency by alloying zinc electrodes, fluoride ion batteries, and other battery electrodes with at least one of the following metals: indium (In), tin (Si), bismuth (Bi), zinc (Zn), lead (Pb), copper (Cu), cobalt (Co), and iron (Fe).

[0025] The minimum hydrogen overpotential on indium is 0.533V, which is higher than that of zinc (0.482V), making hydrogen deposition less likely. Therefore, it is preferable to incorporate indium into the metal electrodes of batteries to form an alloy. Tin is an adjacent element to indium in the periodic table, has similar physical properties, and is cheaper than indium. Therefore, tin has a similar effect and is preferable to incorporate into the metal electrodes of batteries to form an alloy. Copper (Cu) also has a similar effect.

[0026] Fluoride-ion batteries are batteries that charge and discharge through the movement of fluoride ions (F-) between the positive and negative electrodes. As F- moves, a defluorination reaction (a reaction in which F- is removed) occurs at the negative electrode during charging, and a fluorination reaction (a reaction in which F- is combined) occurs during discharging. They can achieve more than twice the energy density of current lithium-ion batteries.

[0027] In fluoride-ion batteries, lanthanum fluoride (LaF3), which is expected to achieve a high operating voltage, has a problem in that the pure metallic lanthanum (La) generated during charging causes unintended electrolyte decomposition and internal short circuits (dendrites), hindering repeated charging and discharging.

[0028] By adding indium (In) to the LaF3 negative electrode, an alloy of In and La is reversibly formed instead of pure metallic La. As a result, problems of electrolyte decomposition and internal short circuits are avoided, and repeated charging and discharging becomes possible.

[0029] By implementing the present invention, which involves adding indium (In) to the LaF3 negative electrode of a fluoride-ion battery, electrolyte decomposition and internal short circuits (dendrites) can be suppressed.

[0030] This invention involves sequentially forming metal films on a metal foil (substrate) using electroplating or electroless plating with two or more types of metal, and then forming an alloy film from the metal film layer using thermomigration and electromigration techniques, which is then used as a battery electrode (material).

[0031] In the structure of the battery material (battery electrode) and the method for manufacturing the battery material (battery electrode) of the present invention, a thin metal film (metal layer) 601 of a metal from the 4th period of the periodic table (iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), etc.) and a thin metal film (metal layer) 601 of a metal from the 5th to 6th periods of the periodic table (indium (In), tin (Sn), silver (Ag), gold (Au), antimony (Sb), bismuth (Bi), etc.) are layered on a substrate 602 to form the structure of the battery material (battery electrode) of the present invention.

[0032] Metals in period 4 of the periodic table move from the high-temperature side to the low-temperature side. Metals in periods 5 and 6 of the periodic table move from the low-temperature side to the high-temperature side. Therefore, if a layered structure is formed with metal films 601 representing periods 4 and 5 and 6 of the periodic table, and the metal film side representing period 4 is heated to a high temperature and the metal film side representing periods 5 and 6 is heated to a low temperature, the metals in period 4 will move to the low-temperature side and the metals in periods 5 and 6 will move to the high-temperature side. Due to the movement of the metals, the metals in period 4 and 5 and 6 of the periodic table are mixed, and an alloy film 603 is formed.

[0033] Preferably, a metal layer (indium (In), bismuth (Bi), tin (Sn), zinc (Zn)) made of a metal with a melting point of 500°C (Celsius) or less is formed on the substrate 602, and a metal film 601 of period 4 or period 5 to 6 of the periodic table is formed or constructed on the metal film 601 made of a metal with a melting point of 500°C (Celsius) or less.

[0034] The structure of the metal secondary battery, the method for manufacturing the metal secondary battery, the structure of the battery material, and the method for manufacturing the battery material of the present invention can be applied to lithium-ion batteries, sodium-ion batteries, fluoride-ion batteries, all-solid-state fluoride-ion batteries, all-solid-state batteries, zinc batteries, aluminum batteries, magnesium batteries, calcium batteries, metallic sulfur batteries, and the like.

[0035] Examples of the base material for the battery electrode of the present invention include porous metals (nickel, Ni-Cr alloy, aluminum, copper). Porous metals have a surface area several hundred times larger than that of a metal plate. Using them as the electrode collector of a battery is preferable because it increases the charging speed and improves the charging efficiency.

[0036] Examples of the base substrate and electrode material 602 for the battery electrode of the present invention include perforated metal. Examples of materials for perforated metal include zinc, nickel, aluminum, aluminum alloy, copper, magnesium, magnesium alloy, calcium, and stainless steel (SUS).

[0037] Examples of the base material 602 of the battery electrode of the present invention include zinc, nickel, aluminum, aluminum alloy, copper, magnesium, magnesium alloy, calcium, and SUS, when it is a metal plate or metal foil.

[0038] The base material 602 of the battery electrode may be formed from zinc or the like, but it goes without saying that zinc or the like may be formed on the (base) base material 602 of the battery electrode and used as the base material 602.

[0039] The (base) substrate 602 and the metal substrate (base metal foil, metal sheet, metal plate) 602 are described as being composed or formed solely of metal, such as metal foil, metal plate, or metal sheet, but the present invention is not limited thereto.

[0040] For example, the material may be an inorganic material such as ceramic or glass, a resin material such as polypropylene, polyester, or polyethylene, or a resin film or sheet on which a metal foil or metal film is formed or constructed. Alternatively, the material may be a semiconductor film or semiconductor plate such as SiC or silicon on which a metal foil or metal film is formed or constructed.

[0041] Furthermore, the material may be formed or composed of carbon, graphite, etc., with metal foil, metal film, or conductive material attached. Needless to say, carbon films, metal foils, metal films, metal sheets, etc., may be formed or manufactured using plating technology, vapor deposition technology, sputtering technology, printing technology, coating technology using a spinner, etc.

[0042] Examples of metal films formed or constructed by plating include nickel, zinc, tin, gold, silver, indium, bismuth, antimony, and iron. It is preferable that the thickness of the metal film or layer formed or constructed by plating be 1 nm or more.

[0043] Thermomigration occurs when a temperature gradient in a substance acts as a driving force for atomic diffusion. This effect is called thermotransport or thermomigration. The driving force of thermomigration is expressed by the following equation. F TM = Q * / T(-∂T / ∂x) (1)

[0044] Here, T is the absolute temperature, and ∂T / ∂x represents the temperature gradient. Also, Q * Q represents the heat of transport and shows a value specific to the metal. * Metals in which the value of Q is positive (+) exhibit atomic movement from the high-temperature side to the low-temperature side. * In metals where the value is negative (-), atoms move from the low-temperature side to the high-temperature side.

[0045] In this invention, among the metals used, nickel (Ni), zinc (Zn), tin (Sn), gold (Au), silver (Ag), copper (Cu), indium (In), bismuth (Bi), antimony (Sb), and iron (Fe), Q * The metals that show a positive (+) value are Zn, Cu, In, Sb, and Bi, while the metals that show a negative (-) value are Sn and Au, and Ag is 0. For example, transport heat Q in some pure metals *When expressed in kJ, the values ​​are Ag(0), Au(-25), Al(7), and Pb(9).

[0046] In equation (1), the driving force for the diffusion of atoms is the transport heat Q. * This is determined by the temperature gradient ∂T / ∂x. The larger the temperature difference between the two contacting metals, the more likely thermomigration is to occur. Therefore, in this invention, it is preferable to set the temperature gradient in the range of 1000°C / cm to 4000°C / cm (creating a temperature difference of 1000°C to 4000°C per centimeter between the low-temperature side and the high-temperature side).

[0047] Furthermore, it is preferable to perform thermomigration once, and then reverse the direction of the high-temperature and low-temperature sides. By repeating this several times, a more uniform alloy film can be obtained. For example, in the first step, the base substrate 602 side is the high-temperature side, then in the second step, the base substrate 602 side is the low-temperature side, and in the third step, the base substrate 602 side is the high-temperature side. It can also be combined with electromigration. Furthermore, it is preferable to perform thermomigration with the direction of the heat gradient reversed.

[0048] Electromigration is the phenomenon in which matter moves when a high current density is applied to a thin film of metal or a wire. In a system where two metals are in contact, a high current causes electrons to collide with metal atoms, leading to the transport of those metal atoms. The driving force is shown by the following equation. F EM = Z * eρj (2)

[0049] Here, Z * is the effective charge, and e is the charge of the electron, which is 1.602 × 10⁻⁶. -19 In the coulomb diagram, ρ represents resistivity and j represents current density; the higher the current density, the easier it is for atoms to move.

[0050] However, if the current density is too high, voids may form in the metal film of the plating. After investigation, it was determined that the current density should be set to 1 kA / cm².2 ~50kA / cm 2 It is preferable to carry it out within the specified range. Figure 1 is an explanatory diagram of the manufacturing method of the battery electrode of the present invention. It is also an explanatory diagram of the structure of the battery electrode of the present invention.

[0051] Figure 1(c) is a diagram and explanatory diagram showing the configuration in which a metal film 601 formed or constructed on a metal substrate (base metal foil, metal sheet, metal plate) 602 is alloyed by thermomigration / electromigration to form a metal alloy film (metal alloy foil) 603.

[0052] Although we will be describing this as a metal substrate (base metal foil) 602, it is not limited to metals. For example, it may be a conductive material such as carbon, or a semiconductor material such as SiC.

[0053] Furthermore, a configuration or structure consisting of a metal film 601 formed or constructed on a metal substrate (base metal foil, metal sheet, metal plate) 602 is referred to as an electrode material (electrode foil) 614.

[0054] In the embodiments of the present invention, the metal film 601 is described as a plated metal film formed or constructed by plating technology, but is not limited thereto. Needless to say, the metal film 601 may also be formed or constructed by sputtering technology, vapor deposition technology, spinner coating technology, printing technology, etc.

[0055] Figure 1(a) shows an example in which a single metal film (plating film, metal foil, metal layer) 601 is formed or constructed on a metal substrate (base metal foil, metal sheet, metal plate) 602.

[0056] A Peltier element 609a is placed on the high-temperature side and heated from the metal film 601 side. A Peltier element 609b is placed on the low-temperature side and cooled from the base metal plate 602 side. A temperature gradient is generated between the Peltier elements 609a and 609b, and a metal alloy film 603 is formed or fabricated by the thermomigration effect, as shown in Figure 1(c).

[0057] In the embodiment shown in Figure 1(a), if the base metal plate 602 is formed or composed of a metal that moves from the low temperature side to the high temperature side, for example, a metal from the 5th to 6th period of the periodic table, and the metal film 601 is formed or composed of a metal that moves from the high temperature side to the low temperature side, for example, a metal from the 4th period of the periodic table, then the metal of the metal film 601 moves towards the base metal plate 602, and the metal of the base metal plate 602 moves towards the metal film 601, thereby forming or creating the alloy layer 603.

[0058] In Figure 1(a), when the metal film 601 is the low-temperature side and the base metal plate 602 is the high-temperature side, and the base metal plate 602 is formed or composed of metals from the 4th period of the periodic table and the metal film 601 is formed or composed of metals from the 5th to 6th periods of the periodic table, the metal of the metal film 601 moves towards the base metal plate 602, and the metal of the base metal plate 602 moves towards the metal film 601, forming the alloy layer 603.

[0059] In embodiments of the present invention, metal films 601a and 601b are formed from different materials and metals, and the metal film 601 is subjected to a thermomigration effect to form an alloy layer 603. Even if only a small amount of metal from the metal film 601 penetrates or is contained in the alloy layer 603, the generation of dendrites may be suppressed.

[0060] Figure 1(b) shows an example in which two metal films (plating film, metal foil, metal layer) 601a and metal film (plating film, metal foil, metal layer) 601b are formed or constructed on a metal substrate (base metal foil, metal sheet, metal plate) 602.

[0061] Furthermore, the metal film (plating film, metal foil, metal layer) 601 is not limited to two layers. It goes without saying that three or more layers of metal film (plating film, metal foil, metal layer) 601 may be formed or constituted.

[0062] A Peltier element 609a is placed on the high-temperature side and heated from the metal film 601 side. A Peltier element 609b is placed on the low-temperature side and cooled from the base metal plate 602 side. A temperature gradient is generated between the Peltier elements 609a and 609b, and a metal alloy film 603 is formed or fabricated by the thermomigration effect, as shown in Figure 1(c). Alternatively, a metal alloy film 603 is formed or fabricated by the electromigration effect, as shown in Figure 1(c).

[0063] Alternatively, a metal alloy film 603 can be formed or fabricated by combining the thermomigration effect and the electromigration effect, as shown in Figure 1(c). It goes without saying that the above embodiments can also be applied to other embodiments of the present invention.

[0064] In the embodiment shown in Figure 1(b), a metal film 601a is formed or constructed on a base metal plate (metal foil, metal sheet) 602 using a metal that moves from the high-temperature side to the low-temperature side, for example, a metal of the 4th period of the periodic table, and a metal film 601b is formed or constructed on a metal that moves from the low-temperature side to the high-temperature side, for example, a metal of the 5th or 6th period of the periodic table.

[0065] The metal in metal film 601a moves to the lower temperature side, and the metal in metal film 601b moves to the higher temperature side, so that an alloy layer 603 is formed or composed of the metal in metal film 601a and the metal in metal film 601b, as shown in Figure 1(c).

[0066] In Figure 1(b), when the metal film 601a is on the low-temperature side and the metal film 601b is on the high-temperature side, if the metal film 601a is formed from metals of the 5th to 6th periods (periods 5 and 6) of the periodic table and the metal film 601b is formed from or composed of metals of the 4th period of the periodic table, the metal of metal film 601a moves to the metal film 601b side, and the metal of metal film 601b moves to the metal film 601a side, forming an alloy layer 603 on the base metal plate 602.

[0067] A Peltier element 609a is placed on the high-temperature side and heated from the metal film 601a side. A Peltier element 609b is placed on the low-temperature side and cooled from the base metal plate 602 side. A temperature gradient is generated between the Peltier elements 609a and 609b, and a metal alloy film 603 is formed or fabricated by the thermomigration effect, as shown in Figure 1(c). Alternatively, or in addition, a metal alloy film 603 is formed or fabricated by the electromigration effect, as shown in Figure 1(c).

[0068] Alternatively, a metal alloy film 603 is formed or fabricated by alternately or simultaneously performing thermomigration and electromigration effects, as shown in Figure 1(c). It goes without saying that the above embodiments can also be applied to other embodiments of the present invention.

[0069] Figure 2 is an explanatory diagram of the method for manufacturing a battery electrode and the structure of a battery electrode according to the present invention. Figure 2(a) shows that a metal film 601a is formed on a base substrate 602 (base substrate, base electrode material, base metal foil, base metal electrode, base battery electrode, base metal plate, base metal sheet), a metal film 601b is formed on the metal film 601a, and a metal film 601c is formed on the metal film 601b.

[0070] The metal film 601a is formed or composed of a metal layer 601 (indium (In), bismuth (Bi), tin (Sn), zinc (Zn)) that has a melting point of 500°C (Celsius) or less.

[0071] Metal film 601b is formed or composed of a thin metal film (metal layer) of a metal from the 4th period of the periodic table (iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), etc.), and metal film 601c is formed or composed of a thin metal film (metal layer, metal film, metal foil) 601 of a metal from the 5th to 6th periods of the periodic table (indium (In), tin (Sn), silver (Ag), gold (Au), antimony (Sb), bismuth (Bi), etc.). Metals in period 4 of the periodic table move from the high-temperature side to the low-temperature side. Metals in periods 5 and 6 of the periodic table move from the low-temperature side to the high-temperature side.

[0072] As shown in Figure 2(a), a heat-dissipating Peltier element 609a is placed on the base substrate 602 (upper side of the paper), and a heat-absorbing Peltier element 609b is placed under the metal film 601c (lower side of the paper).

[0073] A temperature gradient is generated between the Peltier elements 609a and 609b, causing a thermomigration effect. The metals in period 4 of the periodic table of metal film 601b move to the lower temperature side, and the metals in periods 5-6 of the periodic table of metal film 601b move to the higher temperature side. Due to the movement of the metals in metal film 601b and metal film 601c, the metals in metal film 601b and metal film 601c are mixed, and an alloy film 603 is formed.

[0074] Since the metal film 601a is a metal with a melting point of 500°C or lower, the base substrate 602 remains unchanged and stable even when subjected to the heat that causes the thermomigration effect.

[0075] Figure 2(a) shows an embodiment in which the base material 602 is positioned on the upper side of the paper, but the present invention is not limited to this. As shown in Figure 2(b), the base material 602 may also be positioned on the lower side of the paper.

[0076] In Figure 2(b), the metal film 601c may be formed or composed of a metal layer containing an element with a melting point of 500°C or lower. The metal film 601a may be formed or composed of a thin metal film (metal layer) containing a metal from the 4th period of the periodic table (iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), etc.), and the metal film 601b may be formed or composed of a thin metal film (metal layer) containing a metal from the 5th to 6th periods of the periodic table (indium (In), tin (Sn), silver (Ag), gold (Au), antimony (Sb), bismuth (Bi), etc.). Metals in period 4 of the periodic table move from the high-temperature side to the low-temperature side. Metals in periods 5 and 6 of the periodic table move from the low-temperature side to the high-temperature side and undergo alloying.

[0077] Figures 2(a) and 2(b) show an embodiment in which the metal film 601 forms or constitutes three layers: metal film 601a, metal film 601b, and metal film 601c. However, the present invention is not limited thereto. As shown in Figure 2(c), two layers of metal film 601 may be formed, and an alloy layer may be formed using the two formed layers of metal film 601.

[0078] In Figure 2(c), a metal film 601b is formed on the base substrate 602 (base substrate, base metal foil, base metal electrode, base battery electrode, base metal plate, base metal sheet), and a metal film 601a is formed on the metal film 601b.

[0079] Metal film 601a is formed or composed of a thin metal film (metal layer) containing metals from period 4 of the periodic table (iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), etc.), and metal film 601b is formed or composed of a thin metal film (metal layer) containing metals from period 5 to 6 of the periodic table (indium (In), tin (Sn), silver (Ag), gold (Au), antimony (Sb), bismuth (Bi), etc.). Metals in period 4 of the periodic table move from the high-temperature side to the low-temperature side. Metals in periods 5 and 6 of the periodic table move from the low-temperature side to the high-temperature side.

[0080] As shown in Figure 2(c), a heat-dissipating Peltier element 609a is placed on the metal film 601a (upper side of the paper), and a heat-absorbing Peltier element 609b is placed under the base substrate 602 (lower side of the paper).

[0081] A temperature gradient is generated between the Peltier elements 609a and 609b, causing a thermomigration effect. The metals in period 4 of the periodic table in metal film 601a move to the lower temperature side. The metals in periods 5-6 of the periodic table in metal film 601b move to the higher temperature side. Due to the movement of the metals in metal film 601a and metal film 601b, the metals in metal film 601a and metal film 601b are mixed, and an alloy film 603 is formed.

[0082] In the method for manufacturing the electrode material of the present invention, a metal film 601a and a metal film 601b are formed by overlapping them. The metal film 601a or the metal film 601b uses a metal whose element moves from the low temperature side to the high temperature side, and the metal film 601b or the metal film 601a uses a metal whose element moves from the high temperature side to the low temperature side.

[0083] In the embodiment shown in Figure 2, if you swap the Peltier elements 609a and 609b and reverse the temperature gradient of the thermomigration effect, you swap the position of the metal film 601 in the 4th period of the periodic table with the position of the metal film 601 in the 5th to 6th periods of the periodic table. Figure 3 is an explanatory diagram of the method for forming or fabricating a metal alloy film 603 by thermomigration.

[0084] In Figure 3(a), metal film 601a is formed of a thin metal film (metal layer) whose main component is or contains copper (Cu), a metal of period 4 in the periodic table. Metal film 601b is formed of a thin metal film (metal layer) whose main component is or contains tin (Sn), a metal of periods 5-6 in the periodic table. Copper (Cu), a metal of period 4 in the periodic table, migrates from the high-temperature side to the low-temperature side.

[0085] Tin (Sn), a metal in periods 5-6 of the periodic table, moves from the low-temperature side to the high-temperature side. The movement of copper (Cu) and tin (Sn) forms an alloy film 603, as shown in Figure 3(b). Thermomigration and electromigration effects are utilized to move the metals.

[0086] As shown in Figure 3(a), in one embodiment, a metal film (plated film, metal foil) 601b made of tin (Sn) is formed on a base metal foil (metal sheet, metal plate) 602. The metal film 601b is formed by plating technology as an example.

[0087] Next, a metal film (plating film, metal foil) 601a made of copper (Cu) is formed on the metal film 601b. In one example embodiment, the metal film 601a is formed by plating technology.

[0088] A Peltier element 609a is placed on the side of a copper (Cu) metal film (plating film, metal foil) 601a. ​​The lower surface of the Peltier element 609a dissipates heat, and the upper surface of the copper (Cu) metal film (plating film, metal foil) 601a dissipates heat (heats).

[0089] On the other hand, the Peltier element 609b is placed on the side of the tin (Sn) metal film (plating film, metal foil) 601b. In the embodiment shown in Figure 3(a), since the metal film (plating film, metal foil) 601b is formed on the base metal foil (metal sheet, metal plate) 602, the Peltier element 609b is placed on the lower side of the base metal foil (metal sheet, metal plate) 602. The upper surface of the Peltier element 609b absorbs heat, and the lower surface of the tin (Sn) metal film (plating film, metal foil) 601b absorbs heat (cools).

[0090] The Peltier elements 609a and 609b create a temperature gradient in the metal film (plating film, metal foil) 601, and tin (Sn) and copper (Cu) move due to the thermomigration effect. Copper (Cu) moves from the high-temperature side to the low-temperature side, and tin (Sn) moves from the low-temperature side to the high-temperature side, and a metal alloy film 603 is formed (fabricated) as shown in Figure 3(b).

[0091] The metal film 601 is formed by containing at least one of the following metals: indium (In), tin (Sn), bismuth (Bi), zinc (Zn), lead (Pb), copper (Cu), cobalt (Co), iron (Fe), nickel (Ni), and silver (Ag). Multiple metal films 601 are alloyed by thermomigration and electromigration effects. By using the metal film 603, which is an alloy of the metal films 601, as a metal electrode, the generation of dendrites can be suppressed, and electrode deformation and a decrease in electrode deposition efficiency can be suppressed. The embodiment shown in Figure 4 is an example in which three layers of metal film 601 are formed or constructed.

[0092] As shown in Figure 4(a), in one embodiment, a metal film 601c made of tin (Sn) is formed on a base metal foil (metal sheet, metal plate) 602. A metal film 601b made of copper (Cu) is formed on the metal film 601c, and a metal film 601a made of silver (Ag) is formed on the metal film 601b.

[0093] A Peltier element 609a is placed on the side of a silver (Ag) metal film (plating film, metal foil) 601a. ​​The lower surface of the Peltier element 609a dissipates heat, while the upper surface of the silver (Ag) metal film 601a dissipates heat (heats).

[0094] On the other hand, a Peltier element 609b is placed on the side of the tin (Sn) metal film 601c. The upper surface of the Peltier element 609b absorbs heat, and the lower surface of the tin (Sn) metal film 601c absorbs heat (cools).

[0095] The Peltier elements 609a and 609b create a temperature gradient across the metal film 601 (metal film 601a, metal film 601b, metal film 601c), causing tin (Sn) and copper (Cu) to migrate due to the thermomigration effect. Copper (Cu) moves from the high-temperature side to the low-temperature side, and tin (Sn) moves from the low-temperature side to the high-temperature side, forming (fabricate) a metal alloy film 603 as shown in Figure 3(b).

[0096] Silver (Ag) is a metal that has the property of moving from the low-temperature side to the high-temperature side. The silver (Ag) metal film 601a is located on the high-temperature side, so it does not move or moves very little and remains in place. Therefore, as shown in Figure 4(b), an alloy film 603 made of copper (Cu) and tin (Sn) is formed on the base substrate 602, and a film made of silver (Ag) remains (forms) on the alloy film 603.

[0097] In the battery material 614 (base substrate 602, alloy film 603, metal film 601a), the surface is formed of silver (Ag), resulting in good conductivity and good matching with the electrolyte. Figure 5 is an explanatory diagram of the manufacturing method and configuration of the battery electrode of the present invention in another embodiment.

[0098] The embodiment shown in Figure 5(a) (Figures 5(a1) and 5(a2)) is an embodiment in which three layers of metal films 601 (metal film 601a, metal film 601b, and metal film 601c) are formed on the base substrate 602, similar to the embodiment shown in Figure 4.

[0099] As shown in Figure 5(a), a metal film 601c made of tin (Sn) is formed on a base metal foil (metal sheet, metal plate) 602. A metal film 601b made of silver (Ag) is formed on the metal film 601c, and a metal film 601a made of copper (Cu) is formed on the metal film 601b.

[0100] A Peltier element 609a is placed on the side of a copper (Cu) metal film (plating film, metal foil) 601a. ​​The lower surface of the Peltier element 609a dissipates heat, while the copper (Cu) metal film 601a is heated from above.

[0101] On the other hand, a Peltier element 609b is placed on the side of the tin (Sn) metal film 601c. The upper surface of the Peltier element 609b absorbs heat and is cooled from the lower surface of the tin (Sn) metal film 601c.

[0102] The Peltier elements 609a and 609b generate a temperature gradient across the metal film 601 (metal film 601a, metal film 601b, metal film 601c), causing silver (Ag), tin (Sn), and copper (Cu) to migrate due to the thermomigration effect. It is also preferable to simultaneously or alternately provide the electromigration effect described in Figure 6, etc.

[0103] Copper (Cu) and silver (Ag) move from the high-temperature side to the low-temperature side, and tin (Sn) moves from the low-temperature side to the high-temperature side, forming (fabricate) a metal alloy film 603 as shown in Figure 5(a2). The metal alloy film 603 is formed in a state where silver (Ag), tin (Sn), and copper (Cu) are alloyed. Figure 5(b) shows an example in which two layers of metal film 601 (metal film 601a, metal film 601b) are formed to create an alloyed metal alloy film 603.

[0104] As shown in Figure 5(b1), a metal film 601b mainly composed of or containing tin (Sn) is formed on a base metal foil (metal sheet, metal plate) 602, and a metal film 601a containing indium (In) is formed on the metal film 601b.

[0105] A Peltier element 609a is placed on the side of a metal film (plating film, metal foil) 601a made of indium (In). The lower surface of the Peltier element 609a dissipates heat, while the metal film 601a made of indium (In) is heated from above.

[0106] On the other hand, a Peltier element 609b is placed on the side of the tin (Sn) metal film 601b. The upper surface of the Peltier element 609b absorbs heat and is cooled from the lower surface of the tin (Sn) metal film 601b.

[0107] The Peltier elements 609a and 609b create a temperature gradient in the metal film 601 (metal film 601a, metal film 601b), causing tin (Sn) and indium (In) to move due to the thermomigration effect. Both indium (In) and tin (Sn) are elements that move from the low temperature side to the high temperature side, but tin (Sn) moves faster, so indium (In) and tin (Sn) are mixed, and a metal alloy film 603 is formed as shown in Figure 5(b2).

[0108] The lower layer of the metal alloy layer 603 has a high concentration of tin (Sn) components, while the slower-moving indium (In) components remain largely in the upper layer. The accumulation of indium (In) components on the surface of the metal alloy film 603 suppresses electrolyte decomposition and internal short circuits (dendrites). To advance the tin (Sn) and indium (In) alloy, it is preferable to induce the electromigration effect, as explained in Figure 6, etc.

[0109] The battery electrode shown in Figure 5(b2) is suitable as a battery electrode for a fluoride-ion battery. Furthermore, by implementing the present invention, which involves adding indium (In) to the LaF3 negative electrode of a fluoride-ion battery, it is possible to suppress electrolyte decomposition and the generation of internal short circuits (dendrites).

[0110] Figure 5(c) shows an example of forming a metal film 601b composed of a mixture of multiple metals. As shown in Figure 5(c1), a metal film 601a made of zinc (Zn) is formed on a base metal foil (metal sheet, metal plate) 602. A metal film 601b, composed of a mixture of indium (In) and tin (Sn), is then formed on the metal film 601a.

[0111] A metal film 601b, which is a mixture of indium (In) and tin (Sn), can be formed in a deposition apparatus by simultaneously depositing multiple metals (indium (In), tin (Sn)).

[0112] A heater, such as a Peltier element 609a, is placed on the metal film 601a side. The lower surface of the heater 609a dissipates heat, and the metal film 601a is heated from above. A cooler, such as a Peltier element 609b, is placed on the metal film 601b side. The upper surface of the cooler absorbs heat, and the metal film 601b is cooled from below.

[0113] The heater and cooler, such as the Peltier elements 609a and 609b, create a temperature gradient in the metal film 601 (metal film 601a, metal film 601b), causing zinc (Zn) to migrate due to the thermomigration effect. Indium (In) and tin (Sn) also migrate and penetrate into metal film 601a.

[0114] Furthermore, it is also preferable to provide both thermomigration and electromigration effects simultaneously, or alternately with the thermomigration effect, as explained in Figure 6, etc.

[0115] Indium (In) and tin (Sn) move to the higher temperature side, while zinc (Zn) moves to the lower temperature side. As shown in Figure 5(c2), a metal alloy film 603 is formed (fabricated). In addition, a portion of the zinc (Zn) metal film 601a is also alloyed. The metal alloy film 603 is formed in a state where indium (In), tin (Sn), and zinc (Zn) are alloyed.

[0116] In the embodiments of the present invention, it is described that a metal film 601a and a metal film 602b are formed on a base substrate 602, and an alloy film 603 is formed or manufactured by alloying the metal films 601a and 601b. However, the present invention is not limited to this. It goes without saying that the electrode material 614 may be constructed by forming a metal film 601b on a metal film 601a without using a base substrate 602, and then forming or manufacturing an alloy film 603 by alloying the metal films 601a and 601b. In other words, the electrode material 614 does not have a base substrate 602.

[0117] Figure 6 is an explanatory diagram of the principle of electromigration in the present invention. For the sake of clarity, the base metal foil (metal sheet, metal plate) 602 is omitted from the illustration in Figures 6, 7, 8, etc.

[0118] As shown in Figure 6, a metal film (plating film, metal foil) 601b made of indium (In) is formed, and a metal film (plating film, metal foil) 601a made of tin (Sn) is formed on the metal film (plating film, metal foil) 601b.

[0119] Electrode 604 is placed on the metal film (plated film, metal foil) 601a side, and electrode 605 is placed on the metal film (plated film, metal foil) 601b side. A variable voltage (current) source 112 is connected between electrode 604 and electrode 605. Electrode 605 becomes positively charged, and electrode 604 becomes negatively charged.

[0120] As shown in Figure 6(a), when current is passed from the (variable) current (voltage) source 112 in the direction of the arrow, the direction of the electrons becomes the direction of the arrow in Figure 6(a). Tin (Sn) moves to the positive potential side. The (variable) current (voltage) source 112 can vary the magnitude of the supplied current and voltage, and can also control the stopping and supply of the supplied current and voltage.

[0121] In the electromigration effect, a metal film 601 that will be positively charged and a metal film 601 that will be negatively charged are formed in a layered structure, and an alloy film 603 is formed or fabricated by applying an electric field.

[0122] By increasing the electric field strength, the time required to form or manufacture the alloy film 603 can be shortened. Furthermore, by heating the metal film 601, the time required to form or manufacture the alloy film 603 can also be shortened. The thermomigration effect allows for a reduction in the time required to form or fabricate the alloy film 603 by increasing the thermal gradient.

[0123] When the thermomigration effect is being implemented, the metal film 601 is in a heated state. Therefore, by simultaneously implementing the electromigration effect, the time required to form or manufacture the alloy film 603 can be shortened.

[0124] As tin (Sn) moves, as shown in Figure 6(b), tin (Sn) is mixed into the metal film (plating film, metal foil) 601b made of indium (In), and the metal film (plating film, metal foil) 601b made of indium (In) becomes an alloy film 603 of indium (In) and tin (Sn).

[0125] Figures 7 and 8 are explanatory diagrams of a manufacturing method for forming or producing a metal film 601 containing tin (Sn) and indium (In) on a base metal foil (metal sheet, metal plate, metal foil) 602 made of zinc using plating technology.

[0126] An electrolytic tin plating film and an electrolytic indium plating film are formed on a porous zinc plate 602. Each plating film is alloyed by the thermomigration effect, the electromigration effect, or both effects to form a metal alloy film 603. By using a porous metal base plate 602, the contact area with the electrolyte and electrolyte solution is increased, which can increase the battery's power output (battery capacity).

[0127] Figure 7 is an explanatory diagram of a method for forming a metal film 601 using plating technology. As an example of forming a metal film 601 by plating, Figure 7 shows the formation of tin (Sn) as the metal film 601.

[0128] A porous zinc plate 602, serving as the base metal plate, is immersed in an electrolyte solution prepared by dissolving 40g of tin sulfate, 100g of sulfuric acid, 40g of potassium cresol sulfonate, 2g of gelatin, and 1g of β-naphthol in 1 liter of deionized water to form the negative electrode. The tin plate is used as the positive electrode, and a current density of 1.5 A / dm² is achieved at 25°C using a current source 112. 2 A current is supplied. By supplying current, tin (Sn) is formed on the zinc plate 602 to a thickness of 3 μm.

[0129] Figure 8 shows a method in which a zinc (Zn) plating film made of tin (Sn) is formed on a base metal plate 602, a zinc (Zn) and tin (Sn) metal alloy film 603 is formed on the base metal plate 602 by the thermomigration effect of the present invention as explained in Figure 1, etc., and then a metal film 601 made of indium (In) is formed by plating technology.

[0130] As shown in Figure 8, a metal film with an alloy film 603 formed on a zinc plate 602 is immersed in an electroplating solution prepared by dissolving 80g of trisodium succinate dihydrate, 40g of nitrilotriacetic acid, 25g of indium chloride tetrahydrate, and 6g of titanium chloride in 1 L (1 liter) of deionized water, and then adjusting the pH to 10 using ammonia water. At 80°C, an indium coating 601 is deposited to a thickness of 3 μm.

[0131] Subsequently, indium (In) is incorporated into the metal alloy film 603 by the thermomigration effect, forming a metal alloy film 603 of zinc (Zn), tin (Sn), and indium (In). Electromigration is also performed.

[0132] As shown in Figures 3(a) and 17, a zinc plate 602 and tin (Sn) are sandwiched between two Peltier elements 609 (Peltier element 609a and Peltier element 609b), and a temperature gradient is generated by heating and cooling to induce a thermomigration effect. As shown in Figure 8, an alloy film 603 made of zinc (Zn) and tin (Sn) is formed by the thermomigration effect.

[0133] As shown in Figures 3(a) and 17, a zinc plate 602 and indium (In) are sandwiched between two Peltier elements 609 (Peltier element 609a and Peltier element 609b), and a temperature gradient is generated by heating and cooling to induce a thermomigration effect.

[0134] Through the thermomigration effect, an alloy film 603 composed of zinc (Zn), tin (Sn), and indium (In) is formed. Furthermore, the electromigration effect, as explained in Figure 6, is combined with this.

[0135] Figure 16 is a diagram illustrating the configuration and operation of the Peltier element 609 as a heating and cooling means. The Peltier element 609 used in electronic cooling has the property that when a direct current is passed through it in a certain direction, it absorbs heat (cools) on its upper surface and generates heat (heats) on its lower surface.

[0136] The Peltier element 609 utilizes the inverse of the Seebeck effect. The Seebeck effect is the phenomenon where an electromotive force is generated between two ends of a material when there is a temperature difference between them. When a material is heated, carriers, which are negatively charged electrons or positively charged holes, are generated. If only one end of the material is heated at this time, no carriers are generated at the other end, so carriers move from the heated side to the cooled side in an attempt to restore internal equilibrium. This is the electromotive force due to the Seebeck effect.

[0137] The Seebeck effect occurs in all materials, but it is particularly strong in some semiconductor materials. In particular, connecting a material with electron carriers and a material with hole carriers in series results in a large amount of cooling or heating power.

[0138] The principle of a Peltier element is the reverse of the Seebeck effect. When an electric current is passed through a material, heat is generated at one end and absorbed at the other to balance the charge carriers. By simply changing the direction of the current, cooling and heating can be switched.

[0139] Therefore, as shown in Figures 1(a), 1(b), and 3(a), when the Peltier element 609 is placed on the high-temperature side, it acts as a heat dissipator, heating the metal film 601. When the Peltier element 609 is placed on the low-temperature side, it acts as an absorbent, cooling the metal film 601.

[0140] As shown in Figure 16(a), the Peltier element 609 is configured by connecting a p-type semiconductor 611 and an n-type semiconductor 612 in series. As shown in Figure 16(b), when obtaining power by the Seebeck effect, the p-type semiconductor and n-type semiconductor are connected alternately in series, or linked together, to obtain more cooling power or heating power. The p-type semiconductor and n-type semiconductor are connected by element electrode 607 or element electrode 608.

[0141] The Peltier element 609 can be easily switched between heating and cooling by reversing the direction of the supplied current. Furthermore, the switching between cooling and heating is also fast. In addition, since the Peltier element 609 has both a heating surface and a cooling surface, it is suitable for manufacturing methods in which the electrode material 614 is heated or cooled from both sides, as shown in the manufacturing method of the present invention illustrated in Figures 21, 27, etc.

[0142] The Peltier effect, like the Seebeck effect, occurs in all materials, but a configuration where n-type semiconductor 612, metal, and p-type semiconductor 611 are connected in that order is particularly efficient at heat absorption and release. When no current is flowing, the free electrons present in the metal are distributed between the p-type semiconductor 611 and the n-type semiconductor 612 according to Fermi's distribution function. When current flows, the slope of Fermi's function becomes gentler, causing the temperature to drop (cooling effect). As shown in Figure 16(a), the Peltier element 609 is mainly composed of semiconductors (n-type semiconductor 612, p-type semiconductor 611) and element electrodes 607.

[0143] When current flows from the p-type semiconductor 611 to the n-type semiconductor 612, the temperature decreases, and when current flows from the n-type semiconductor 612 to the p-type semiconductor 611, the opposite phenomenon occurs and the temperature increases. In this way, one side of the element is cooled and the other side is heated. Therefore, if the direction of the current from the voltage (current) source 112 is reversed, the heat-absorbing and heat-generating surfaces are reversed. The Peltier element 609 has the following characteristics: it can cool and heat by changing the direction of the current, it has excellent temperature response, and it allows for accurate temperature adjustment and setting.

[0144] A major feature of the Peltier element 609 is its ability to switch between cooling and heating simply by changing the direction of the current. Furthermore, it boasts high temperature responsiveness, allowing for precise temperature control. Because the element itself performs both heat absorption and heating without the use of other components, it is highly efficient. Additionally, the heating and cooling temperatures can be adjusted and set by varying the magnitude of the supplied current, making it easy to set temperature gradients and temperature differences through the thermomigration effect.

[0145] The present invention uses a Peltier element 609 to heat or cool a metal film 601, generating a temperature gradient or temperature difference between both sides of the metal film 601, thereby exhibiting a thermomigration effect and forming or producing an alloy film 603.

[0146] It is preferable to apply a silicone resin or the like between the Peltier element 609, the base electrode material (metal substrate) 602, and the metal film 601, etc., to ensure close contact between the Peltier element 609 and the base electrode material 602, thereby enabling good transfer of heat generated or absorbed from the Peltier element 609.

[0147] By changing the direction of the current flowing through the Peltier element 609, a temperature gradient is generated between both sides of the metal film 601, and by reversing its direction, a reverse thermomigration effect is generated, thereby forming or producing a good alloy film 603. By reversing the direction of the thermal gradient of thermomigration, the alloying state of the alloy film 603 is improved. Since the direction of the current flowing through the Peltier element 609 is simply reversed, the heating and cooling applied to both sides of the metal film 601 can be changed at high speed. Furthermore, the heating temperature and cooling temperature can be accurately and easily changed by adjusting or setting the magnitude of the current flowing through the Peltier element 609. The present invention involves forming a metal film 601 on a metal substrate (base metal foil, metal sheet, metal plate) 602.

[0148] In one embodiment, a nickel porous material was used as the metal substrate (base metal foil, metal sheet, base substrate, metal plate) 602. Electrolytic zinc plating, electrolytic tin plating, and electroless indium plating were performed on the nickel porous metal substrate 602.

[0149] It goes without saying that the metal film 601 is not limited to plating and may be formed by other methods and techniques such as vapor deposition, sputtering, printing, coating, and spinning.

[0150] Electrolytic zinc plating (20 μm) -> electroless indium plating (5 μm) -> electrolytic tin plating (5 μm) is performed on a metal substrate (base metal foil, metal sheet, metal plate) 602.

[0151] Next, thermomigration was performed. Alternatively, electromigration may be performed instead of thermomigration. Furthermore, thermomigration and electromigration may be performed simultaneously. The method for forming and manufacturing the metal film 601 using a plating film or the like is as follows.

[0152] In an electrolyte solution prepared by dissolving 15g of zinc and 120g of sodium hydroxide in 1 liter of deionized water, a 3cm x 6cm nickel porous material was used as the negative electrode, and a 6cm x 10cm iron plate was used as the positive electrode. At 25°C, the current density was 3A / dm². 2 A zinc plating film with a thickness of 20 μm was applied by applying a solvent. After that, the nickel porous material was washed with deionized water and dried at 70°C.

[0153] A nickel porous material was immersed in an electroless plating solution prepared by dissolving 80g of trisodium succinate dihydrate, 40g of nitrilotriacetic acid, 25g of indium chloride tetrahydrate, and 6g of titanium chloride in 1 liter of deionized water, and then adjusting the pH to 10 using ammonia water. An indium coating with a thickness of 5 μm was then applied at 80°C. Afterwards, the nickel porous material was washed with deionized water and dried at 70°C.

[0154] After washing the nickel porous material with deionized water, it was immersed in an electrolyte solution prepared by dissolving 40g of tin sulfate, 100g of sulfuric acid, 40g of potassium cresol sulfonate, 2g of gelatin, and 1g of β-naphthol in 1 liter of deionized water to form the negative electrode, and a 6cm x 10cm tin plate was used as the positive electrode. A current density of 1.5 A / dm² was achieved at 25°C. 2 A tin plating film with a thickness of 5 μm was applied by applying a solvent. After that, the nickel porous material was washed with deionized water and dried at 70°C.

[0155] As shown in Figure 17, Peltier elements 609a and 609b were placed on both sides of electrode material 614 (nickel porous plate 602 + metal film 601) to generate a temperature gradient. The Peltier element 609a on the high-temperature side was set to 100°C, and the Peltier element 609b on the low-temperature side was set to -20°C, and thermomigration was performed for 10 hours.

[0156] Furthermore, by increasing the temperature difference and temperature gradient between Peltier element 609a and Peltier element 609b, the period during which thermomigration is performed can be shortened. The EDS measurement results of the resulting material's surface are shown in Figure 13.

[0157] As another embodiment of the method for forming the metal film 601, a magnesium plate 602 was used as the metal substrate (base metal foil, metal sheet, metal plate) 602. It goes without saying that the production of the metal film 601 is not limited to plating, and the metal film 601 may also be formed by other methods and techniques such as vapor deposition, sputtering, and printing.

[0158] A magnesium plate 602, used as a metal substrate (base metal foil, metal sheet, metal plate), is subjected to electrolytic zinc plating (20 μm) -> electroless indium plating (5 μm) -> electrolytic tin plating (5 μm) -> electrolytic silver plating (1 μm). Next, thermomigration is performed. Alternatively, electromigration may be performed instead of thermomigration. Furthermore, thermomigration and electromigration may be performed simultaneously.

[0159] In an electrolyte solution prepared by dissolving 15g of zinc and 120g of sodium hydroxide in 1 liter of deionized water, a 3cm x 6cm magnesium plate (602) was used as the negative electrode, and a 6cm x 10cm iron plate was used as the positive electrode. At 25°C, the current density was 3A / dm². 2 A zinc plating film with a thickness of 20 μm was applied by applying a solvent. After that, the magnesium plate 602 was washed with deionized water and dried at 70°C.

[0160] Next, the magnesium plate 602 was immersed in an electroless plating solution prepared by dissolving 80g of trisodium succinate dihydrate, 40g of nitrilotriacetic acid, 25g of indium chloride tetrahydrate, and 6g of salt or titanium in 1 liter of deionized water, and then adjusting the pH to 10 using ammonia water. An indium coating with a thickness of 5 μm was then applied at 80°C. After that, the magnesium plate 602 was washed with deionized water and dried at 70°C.

[0161] Next, the magnesium plate 602 was washed with deionized water, and then immersed in an electrolyte solution prepared by dissolving 40g of tin sulfate, 100g of sulfuric acid, 40g of potassium cresol sulfonate, 2g of gelatin, and 1g of β-naphthol in 1 liter of deionized water to form the negative electrode. A 6cm x 10cm tin plate was used as the positive electrode, and a current density of 1.5 A / dm² was measured at 25°C. 2 A tin plating film with a thickness of 5 μm was applied by applying a solvent. After that, the porous metal was washed with deionized water and dried at 70°C.

[0162] A magnesium plate 602 was dissolved in 1 liter of deionized water with 40g of potassium silver cyanide, 150g of potassium pyrophosphate, and 5g of EDTA-4 potassium salt. This solution was then immersed in an electrolyte solution with a pH of 9 to create the negative electrode, and a 6cm x 10cm silver plate was used as the positive electrode. The circuit was run at 50°C with a current of 50 A / dm². 2 A 1 μm thick silver plating film was applied by applying a solvent. After that, the magnesium plate 602 was washed with deionized water and dried at 70°C.

[0163] As shown in Figure 1, a Peltier element 609a and a Peltier element 609b were placed on both sides of the electrode material 614 to generate a temperature gradient. The Peltier element 609a on the high-temperature side was set to 100°C, and the Peltier element 609b on the low-temperature side was set to -20°C, and thermomigration was performed for 10 hours. By increasing the temperature difference and temperature gradient between the Peltier elements 609a and 609b, the period for performing thermomigration can be shortened. The EDS measurement results of the resulting material surface are shown in Figure 14.

[0164] In another example, electroless indium plating (5 μm) -> electroless antimony plating (1 μm) -> electrolytic silver plating (1 μm) is formed on a porous zinc plate 602, and then thermomigration / electromigration is performed.

[0165] A 3cm x 6cm zinc plate was immersed in an electroless plating solution prepared by dissolving 80g of trisodium succinate dihydrate, 40g of nitrilotriacetic acid, 25g of indium chloride tetrahydrate, and 6g of titanium chloride in 1 liter of deionized water, and then adjusting the pH to 10 using ammonia water. An indium coating with a thickness of 5μm was then applied at 80°C. Afterwards, the zinc plate was washed with deionized water and dried at 70°C.

[0166] Next, the porous zinc plate was immersed in an electroless plating solution prepared by dissolving 95g of trisodium succinate dihydrate, 18g of antimony chloride, 30g of disodium EDTA dihydrate, 20g of nitrilotriacetic acid, and 6g of titanium trichloride in 1 liter of deionized water, and then adjusting the pH to 8 using ammonia water. A 1 μm antimony film was then deposited at a temperature of 20°C. After that, the zinc plate was washed with deionized water and dried at 70°C.

[0167] Next, the porous zinc plate is immersed in an electrolyte solution prepared by dissolving 40g of potassium silver cyanide, 150g of potassium pyrophosphate, and 5g of EDTA 4 potassium salt in 1 liter of deionized water, and then adjusting the pH to 8-10 to create the negative electrode. A 6cm x 10cm silver plate is used as the positive electrode, and a voltage of 50 A / dm² is applied at 50°C. 2 A 1 μm thick silver plating film was applied by applying a solvent. The porous metal was then washed with deionized water and dried at 70°C.

[0168] Subsequently, the electrode material 614 was cooled to room temperature, the high-temperature side of the thermomigration was made the cathode and the low-temperature side the anode, and the current density was set to 5 × 10⁻¹⁰. 3 A / cm 2 Electromigration was performed for 50 hours.

[0169] By increasing the applied voltage during electromigration, the operating time can be shortened. Similarly, by increasing the temperature gradient during thermomigration, the operating time can also be shortened.

[0170] Subsequently, the current flowing through the high-temperature side (heat dissipation operation) Peltier element 609a was reversed to enable heat absorption. Similarly, the current flowing through the low-temperature side (heat absorption operation) Peltier element 609b was reversed to enable heat dissipation. In other words, the thermomigration process was carried out for 10 hours with the low-temperature and high-temperature sides reversed.

[0171] By increasing the temperature gradient during thermomigration, the time required for the thermomigration process can be shortened. The EDS measurement results of the resulting material surface are shown in Figure 15.

[0172] In the embodiments of the present invention, the metal film 601 is formed by plating technology or the like. It goes without saying that the formation of the metal film 601 in the present invention is not limited to plating technology, but may also be formed or manufactured by vapor deposition technology, sputtering technology, printing technology, coating technology using a spinner, etc.

[0173] Examples of plating techniques (plating methods) for the metal film 601, which is the manufacturing method of the present invention, include electroplating and electroless plating. For example, electrolytic nickel plating using nickel is performed by the following method.

[0174] Dissolve 240-260g of nickel sulfate, 40-50g of nickel chloride, and 30-40g of boric acid in 1 liter of deionized water. Then, adjust the pH of the electrolyte to 4-5. Immerse the plated object in contact with the cathode terminal, along with the nickel plate in contact with the positive electrode terminal, in the electrolyte under conditions of 45-55°C, with a current flow rate of 4-6 A / dm². 2 Apply the current density.

[0175] Electrolytic zinc plating involves dissolving 10-15g of zinc and 100-150g of sodium hydroxide in 1 liter of deionized water. The object to be plated, in contact with the cathode terminal, is immersed in the resulting electrolyte along with an iron plate in contact with the positive electrode terminal, under a temperature of 15-35°C at a current of 2-3 A / dm². 2 Apply the current density.

[0176] Furthermore, in electrolytic tin plating, 35-45g of tin sulfate, 90-110g of sulfuric acid, 35-45g of potassium cresol sulfonate, 1.5-2.5g of gelatin, and 0.5-1.5g of β-naphthol are dissolved in 1 liter of deionized water. The object to be plated, in contact with the cathode terminal, is immersed in this electrolyte along with the tin plate in contact with the positive electrode terminal, under a temperature of 20-30°C at an A / dm² load. 2 Apply the current density.

[0177] Electrolytic gold plating involves dissolving 10-14g of potassium gold cyanide, 18-22g of potassium cyanide, 18-22g of potassium phosphate, and 18-22g of potassium carbonate in 1 liter of deionized water, then adjusting the pH of the solution to 11-13. The object to be plated, in contact with the cathode terminal, is immersed in this solution along with the gold plate in contact with the positive electrode terminal, under conditions of 65-75°C at an A / dm² load. 2 Apply the current density.

[0178] Electrolytic silver plating involves dissolving 35-45g of potassium silver cyanide, 140-160g of potassium pyrophosphate, and 4-6g of EDTA-4 potassium salt in 1 liter of deionized water, then adjusting the pH of the solution to 8-10. The object to be plated, in contact with the cathode terminal, is immersed in the electrolyte along with the silver plate in contact with the positive electrode terminal, under conditions of 45-55°C at an A / dm² load. 2 Apply the current density.

[0179] Electrolytic copper plating involves dissolving 90-110g of copper sulfate pentahydrate, 90-110g of sulfuric acid, and 45-55mg of chloride ions in 1 liter of deionized water. The object to be plated, in contact with the cathode terminal, is immersed in this electrolyte along with a copper plate in contact with the positive electrode terminal, and a current density of 5-7 A / dm2 is applied under a temperature of 25-35°C.

[0180] In one embodiment, each metal film 601 is formed or manufactured by electroless plating technology. The method for forming or manufacturing the plated film 601 by electroless plating is as follows. In the case of electroless indium plating, where the metal film 601 is formed by electroless plating, the following applies.

[0181] In 1 liter of deionized water, 75-85 g of trisodium succinate dihydrate, 35-45 g of nitrilotriacetic acid, 23-27 g of indium chloride tetrahydrate, and 5-7 g of titanium chloride are dissolved in an electrolyte solution. The pH of this solution is adjusted to 9-11 using ammonia water, and the object to be plated is immersed in this electroless plating solution, which is then used to deposit an indium layer at a temperature of 75-85°C. In the case of electroless bismuth plating, where the metal film 601 is formed by electroless plating, the following applies.

[0182] In 1 liter of deionized water, 85-95 g of trisodium succinate dihydrate, 28-32 g of EDTA, 38-42 g of nitrilotriacetic acid, 24-26 g of boron chloride, and 7-9 g of tin chloride dihydrate are dissolved to create an electroless plating solution. The pH of this solution is adjusted to 8.6-9 using ammonia water, and the object to be plated is immersed in this electroless plating solution and deposited at a temperature of 55-65°C. In the case of electroless antimony plating, where the metal film 601 is formed by electroless plating, the following applies.

[0183] In 1 liter of deionized water, 92-96 g of trisodium succinate dihydrate, 16-20 g of antimony chloride, 28-32 g of disodium EDTA dihydrate, 18-20 g of nitrilotriacetic acid, and 5-7 g of titanium trichloride are added and dissolved. The pH of this electroless plating solution is adjusted to 6.8-8.5 using ammonia water, and the object to be plated is immersed in this solution and deposited as an antimony layer at a temperature of 18-22°C.

[0184] As shown in Figure 16(b), when current flows in the direction of the n-type semiconductor and the p-type semiconductor, the lower surface of the Peltier element 609 dissipates heat (generates heat), while the upper surface of the Peltier element 609 absorbs heat (cools). Conversely, when current flows in the direction of the p-type semiconductor and the n-type semiconductor, the upper surface of the Peltier element 609 dissipates heat (generates heat), while the lower surface of the Peltier element 609 absorbs heat (cools). Figure 17 is an explanatory diagram of the manufacturing method and manufacturing apparatus for the battery electrode of the present invention for producing an alloy film (alloy coating) 603.

[0185] This diagram shows a configuration in which a metal film 601 is formed on a base metal plate 602, a Peltier element 609a is placed on the upper surface of the metal film 601, and a Peltier element 609b is placed on the lower surface of the base metal plate 602. The heat dissipated by the Peltier element 609a heats the metal film 601. The heat absorbed by the Peltier element 609b cools the base metal foil 602. The heat generation and absorption by the Peltier elements 609a and 609b create a temperature gradient in the electrode material 614, resulting in a thermomigration effect.

[0186] As shown in Figure 17, a temperature sensor 503a is placed on the metal film 601 and a temperature sensor 503b is placed on the base metal foil 602 to measure and monitor the temperature and control the magnitude of the current flowing through the Peltier element 609. Needless to say, the above can also be applied to other embodiments of the present invention.

[0187] In the connection shown in Figure 17, current flows from the (variable) current (voltage) source 112a to the Peltier element 609a, from the n-type semiconductor 612 to the p-type semiconductor 611. The element electrode 607 side of the Peltier element 609a absorbs heat, while the element electrode 608 side of the Peltier element 609a generates heat, heating the metal film 601.

[0188] In the Peltier element 609b, current flows from the (variable) current (voltage) source 112b in the direction from the n-type semiconductor 612 to the p-type semiconductor 611. The element electrode 608 side of the Peltier element 609a generates heat, and the element electrode 607 side of the Peltier element 609b absorbs heat, cooling the base metal foil 602.

[0189] When the positive and negative electrodes of the (variable) current (voltage) source 112 are swapped, the direction of current flow is reversed, and the heat-absorbing part of the Peltier element 609 is changed to a heat-dissipating part, and the heat-dissipating part of the Peltier element 609 is changed to a heat-absorbing part.

[0190] To switch the direction of the current, the present invention arranges a switch circuit 505 as shown in Figure 18. The switch circuit 505 has four switches, consisting of switch S1, switch S2, switch S3, and switch S4.

[0191] When switches S1 and S4 are turned on (closed) and switches S2 and S3 are turned off (open), current flows in the direction of the arrows in Figure 18. When switches S1 and S4 are turned off (open) and switches S2 and S3 are turned on (closed), current flows in the opposite direction of the arrows in Figure 18.

[0192] The Peltier elements 609a and 609b create a temperature gradient in the metal film (plating film, metal foil) 601, and tin (Sn) and copper (Cu) move due to the thermomigration effect. Copper (Cu) moves from the high-temperature side to the low-temperature side, and tin (Sn) moves from the low-temperature side to the high-temperature side, and a metal alloy film 603 is formed (fabricated) as shown in Figure 3(b).

[0193] By alloying the material with at least one of the following metals: indium (In), tin (Si), bismuth (Bi), zinc (Zn), lead (Pb), copper (Cu), cobalt (Co), and iron (Fe), the formation of dendrites can be suppressed, thereby preventing electrode deformation and a decrease in electrode deposition efficiency.

[0194] Figure 19 shows the current flow direction set to the opposite direction to that in Figure 18 by switching the switch S of the switch circuit 505. The element electrode 607 side of the Peltier element 609 dissipates heat, while the element electrode 608 side of the Peltier element 609 absorbs heat. The fact that the Peltier element 609 can simultaneously form a heat-generating surface and a heat-absorbing surface is advantageous for the manufacturing method of the present invention that utilizes the thermomigration effect.

[0195] As shown in Figures 18 and 19, an insulating film (insulating material) 615a is placed between the Peltier element 609a and the metal film 601. An insulating film (insulating material) 615b is placed between the Peltier element 609b and the base metal foil (metal sheet, metal plate) 602.

[0196] The Peltier element 609 has element electrodes 607 and 608 formed or arranged on its surface. An insulating film (insulating material) 615 is placed so that element electrode 607 or element electrode 608 does not come into electrical contact with the metal film 601 or base metal foil 602.

[0197] Examples of insulating films (insulating materials) 615 include films, plates, and foils made from resin materials such as polyester and polyethylene. Examples also include films, plates, and foils made from ceramic and glass materials.

[0198] It goes without saying that instead of the insulating film (insulating material) 615, a space may be created to allow for insulation by air or the like. Furthermore, it goes without saying that insulating beads or the like may be scattered between the element electrodes 607 and 608 of the Peltier element 609 and the metal film 601, and between the element electrodes 607 and 608 and the base metal foil 602 to prevent contact.

[0199] An insulating film or insulating layer may be formed on the element electrodes 607 and 608 of the Peltier element 609 to provide insulation between the element electrodes 607 and 608 of the Peltier element 609 and the metal film 601, and between the element electrodes 607 and 608 and the base metal foil 602. Examples of insulating films and insulating layers include oxide films such as SiO2 and SiNx.

[0200] In addition, the Peltier element 609 may be configured to be insulated by applying silicone resin, silicone paste, etc., between the element electrodes 607 and 608 and the metal film 601, and between the element electrodes 607 and 608 and the base metal foil 602.

[0201] By changing the magnitude of the current or voltage supplied by the (variable) current (voltage) source 112, the magnitude of heat absorption and dissipation of the Peltier element 609 can be changed, set, and adjusted. The magnitude of the current or voltage is not limited to a steady value. For example, the magnitude of the current or voltage may be set to change to a square wave, triangular wave, sine wave, etc. Alternatively, the switch S of the switch circuit 505 may be controlled by the drive control circuit 506 to switch the polarity of the applied current or voltage at predetermined intervals.

[0202] The current (voltage) source 112 will be described as a variable type, but it goes without saying that a current (voltage) source 112 that outputs or supplies a predetermined constant voltage (current) or predetermined constant current would also be acceptable.

[0203] In the embodiment shown in Figure 18, the metal film 601 side is heated and the base metal foil 602 side is cooled. The thermomigration effect transforms the metal film 601 into a metal alloy film 603. In the embodiment shown in Figure 19, the metal film 601 side is cooled and the base metal foil 602 side is heated. This results in a thermomigration effect in the reverse direction. The heating and cooling described in Figure 18 are performed on the electrode material 614 for a first period.

[0204] After the first period, the cooling and heating shown in Figure 19 are performed on the electrode foil (electrode material) 614 during the second period. By performing Figures 18 and 19, and by performing Figures 18 and 19 multiple times, a stable metal alloy film 603 can be fabricated or formed.

[0205] Figures 18 and 19 show an example in which the metal film 601 is transformed into a metal alloy film 603 by absorbing and releasing heat from the Peltier elements 609a and 609b. Figure 20 is an explanatory diagram of the manufacturing method for the electrode material 614 of the present invention, and a configuration diagram of the manufacturing apparatus for the electrode material 614.

[0206] In Figure 20, the electrode foil (electrode material) 614 is positioned between Peltier elements 609a and 609b, and between Peltier elements 609c and 609d. The electrode foil (electrode material) 614 is moved in the direction of the dotted arrow.

[0207] Peltier elements 609a and 609b heat the metal film 601 side and cool the base metal foil 602 side, thereby inducing a thermomigration effect on the electrode material 614. Peltier elements 609c and 609d cool the metal film 601 side and heat the base metal foil 602 side, thereby inducing the reverse thermomigration effect on the electrode material 614. During the thermomigration effect, the movement of the electrode foil (electrode material) 614 is stopped.

[0208] The combination of Peltier element 609a and Peltier element 609b, and the combination of Peltier element 609c and Peltier element 609d, transforms the metal film 601 into a metal alloy film 603.

[0209] The thermomigration effect transforms the metal film 601 into a metal alloy film 603. In the embodiment shown in Figure 19, the metal film 601 side is cooled and the base metal foil 602 side is heated. This results in a thermomigration effect in the reverse direction. The heating and cooling shown in Figure 18 are performed on the electrode material 614 for a first period. After the first period, the cooling and heating shown in Figure 19 are performed on the electrode foil (electrode material) 614 for a second period. By performing the steps shown in Figures 18 and 19, and by performing these steps multiple times, a stable metal alloy film 603 can be fabricated or formed.

[0210] In the embodiment shown in Figure 20, it is stated that "the movement of the electrode foil (electrode material) 614 is stopped when the thermomigration effect is being implemented," but this is not the only option. The metal film 601 may be changed to a metal alloy film 603 by the Peltier element 609a and Peltier element 609b, or by the Peltier element 609c and Peltier element 609d, while the electrode foil (electrode material) 614 is being moved.

[0211] The embodiments shown in Figures 18, 19, and 20 were examples of a method and manufacturing apparatus for transforming a single electrode foil (electrode material) 614 into a metal alloy film 603. Figure 21 is an example of a method and manufacturing apparatus for transforming multiple electrode foils (electrode materials) 614 into a metal alloy film 603.

[0212] The Peltier element 609 simultaneously absorbs and dissipates heat. For example, in Figure 16(b), the element electrode 607 side of the Peltier element 609 absorbs heat, while the element electrode 608 dissipates heat. By utilizing both the heat absorption and heat dissipation of the Peltier element 609, the power usage efficiency during the formation or fabrication of the alloy film 603 can be improved.

[0213] In the embodiment shown in Figure 21, electrode material 614a is positioned between Peltier elements 609a and 609b, electrode material 614b is positioned between Peltier elements 609b and 609c, and electrode material 614c is positioned between Peltier elements 609c and 609d.

[0214] The direction of movement of electrode materials 614a, 614b, and 614c is in the direction of the dotted arrows, and is the same direction. Electrode materials 614a, 614b, and 614c are manufactured simultaneously.

[0215] The Peltier element 609b absorbs heat (cools) from the lower surface of the electrode material 614a and dissipates heat (heats) from the upper surface of the electrode material 614b. The Peltier element 609c absorbs heat (cools) from the lower surface of the electrode material 614b and dissipates heat (heats) from the upper surface of the electrode material 614c.

[0216] In the configuration shown in Figure 21, both heat dissipation and heat absorption of the Peltier element 609b can be utilized. Both heat dissipation and heat absorption of the Peltier element 609c can also be utilized. Therefore, the power utilization efficiency of the Peltier element 609 is improved compared to the manufacturing apparatus shown in Figure 17, and multiple electrode materials 614 can be manufactured simultaneously.

[0217] In the above embodiment, the Peltier element 609 was used to implement the thermomigration effect on the electrode material 614. The present invention is not limited to this. For example, the thermomigration effect may be implemented using the heater 626 of the present invention illustrated in FIG. 22.

[0218] FIG. 22 is a plan view of the heater 626 of the present invention used in the bonding layer evaluation apparatus of the present invention. In the embodiment of FIG. 22, the heater 626 is configured in a state where three heater chips 625 (heater chip 625a, heater chip 625b, heater chip 625c) are connected.

[0219] [[ID=�]] SiC (silicon carbide) is exemplified as the base substrate of the heater 626. SiC is a compound semiconductor material composed of silicon (Si) and carbon (C). The single crystal of SiC (silicon carbide) has high thermal conductivity, a small internal temperature distribution, and also a high heat-resistant temperature. Therefore, it is preferable as the base substrate of the heater 626.

[0220] In addition, glass substrates such as sapphire glass having insulation and good thermal conductivity, and ceramic substrates made of alumina or silicon nitride are exemplified as the base substrate of the heater 626.

[0221] Materials such as SiC ceramics, AlN ceramics, or substrates filled with AlN (aluminum nitride) or AlN do not conduct electricity but conduct heat well, so they can be adopted as the base substrate of the heater 626 of the present invention.

[0222] Aluminum nitride (Aluminumnitride: AlN) is exemplified as the base substrate of the heater 626. AlN is a nitride of aluminum and is a colorless and transparent ceramic. It is also called aluminum nitride. AlN has a high thermal conductivity of 230 W / mK. BeO (beryllium oxide: commonly known as beryllia) can be used as the base substrate of the heater 626 because it has a high thermal conductivity of 270 W / mK.

[0223] AlN is sometimes processed into ceramic products by hot pressing or other methods to form discs, but its basic form is a powder. Controlling the particle size of this powder is required, and the reduction nitriding method can produce particles ranging from less than 0.1 μm to about 10 μm. When used as a filler in silicone resins, etc., combining AlN particles with different particle sizes improves the filler's packing efficiency.

[0224] The reduction nitriding method involves nitriding a mixture of alumina (Al2O3) and carbon (C) to produce AlN. Then, oxidation is performed to coat the surface of the AlN grains with an oxide film. Compared to the direct nitriding method, the thickness of the surface oxide film is twice as thick, approximately 11 angstroms. The final oxidation treatment removes imide groups (NH) and amide groups (N-H2) from the grain surface, resulting in pure AlN grains.

[0225] For the sake of clarity, this specification describes the base substrate of the heater 626 as a substrate made of SiC. It goes without saying that any substrate with good thermal conductivity and insulating or semiconducting properties can be used as the base substrate of the heater 626.

[0226] The thickness of the base substrate of the heater 626 shall be between 0.1 mm and 0.8 mm. A thinner base substrate of the heater 626 allows heat from the thin-film heater 623 to be more easily transferred to the electrode material 614. However, if the base substrate of the heater 626 is thin, a temperature distribution is likely to occur in the electrode material 614 between areas where the thin-film heater 623 is formed and areas where it is not. The thin-film heater 623 and the thin-film temperature probe 624 are formed or constructed from Ni (nickel)-P or Ni.

[0227] A thin film (Ni-P film) is formed on the back surface of the SiC substrate by Ni-P plating, and a gold plating film is formed on the surface of the Ni-P film. While the thin film is described as a Ni-P film, a thin film of Ni or Ni-B may also be formed. The thin film may be made of any material that can bond well to the electrode material 614.

[0228] Besides nickel (Ni), other examples include tin (Sn), silver (Ag), gold (Au), copper (Cu), lead (Pb), zinc (Zn), indium (In), or alloys thereof. However, an appropriate resistance must be present, as thin-film heaters such as the 623 are used as heating elements.

[0229] In this invention, Ni or Ni-P is used as an example because it can adhere closely to the electrode material 614 and has a relatively high resistance value for use as a thin-film heater 623. Hereafter, in this specification and drawings, for the sake of ease of explanation, the thin film to be formed will be described as a Ni-P film. The thickness of the Ni-P film is preferably between 1 μm and 10 μm. In particular, a thickness of 2 μm and 6 μm is preferred. The thickness of the gold plating film shall be 0.01 μm or more. The gold plating film has the function of preventing or suppressing oxidation or contamination of the Ni-P film surface.

[0230] A thin-film heater 623 and a thin-film temperature probe 624 are formed on the surface of the SiC substrate. The thin-film heater 623 and thin-film temperature probe 624 are formed from a thin film (Ni-P film) by Ni-P plating. In addition to nickel (Ni), they may be composed of or formed from platinum (Pt). Other materials such as zinc (Zn), tin (Sn), lead (Pb), and chromium (Cr) can also be used. They can also be formed from materials other than metals, such as carbon (C).

[0231] It is preferable to adopt a region where the film thickness of the thin-film heater 623 and the sheet resistance value (Ω / sq) have a linear relationship. Therefore, it is preferable that the film thickness of the thin-film heater 623 be between 0.1 (μm) and 7.5 (μm), and the sheet resistance value (Ω / sq) be between 0.25 (Ω / sq) and 1.00 (Ω / sq). Furthermore, it is preferable that the resistance value of the thin-film heater 623 be between 5Ω and 300Ω.

[0232] The thin-film temperature probe 624 is formed using the same material and process as the thin-film heater 623. If the thin-film heater 623 is a Ni-P film, the thin-film temperature probe 624 is also formed from a Ni-P film. The thin-film temperature probe 624 is formed with a narrow wiring width to increase its resistance over its entire length.

[0233] A constant current is applied to the thin-film temperature probe 624. By increasing the resistance value of the thin-film temperature probe 624, the change in resistance value becomes larger, and the voltage change across the terminals of the thin-film temperature probe 624 in response to the constant current becomes larger. Therefore, the sensitivity of the thin-film temperature probe 624 to the temperature change of the thin-film heater 623 is improved. The resistance value of the thin-film temperature probe 624 is manufactured to be between 20Ω and 1kΩ.

[0234] Temperature probe electrodes 622 are formed at both ends of the thin-film temperature probe 624. Heater electrodes 621 are formed at both ends of the thin-film heater 623. A gold plating film is formed on the surface of the temperature probe electrode 622, etc. A gold plating film is formed on the surface of the heater electrode 621, etc. The thickness of the gold plating film shall be 0.01 μm or more.

[0235] Gold plating is not formed on the thin-film heater 623 and the thin-film temperature probe 624. This is because forming a gold plating would reduce the resistance of the thin-film heater 623 and the thin-film temperature probe 624, thereby reducing their sensitivity to heat generation or temperature changes.

[0236] On the thin-film heater 623 and thin-film temperature probe 624 are SiO2 film and SiN x A film, or a silicon film, may be formed to suppress oxidation or contamination of the surfaces of the thin-film heater 623 and the thin-film temperature probe 624.

[0237] Although the thin film heater 623 is described as a thin film, it is not limited thereto. The thin film heater 623 is arranged or formed to heat the electrode material 614. As an alternative to the thin film heater 623, a surface heater incorporating a nichrome wire, a heater using a Peltier element, or the like may be used. The base substrate of the heater � can be heated by the current flowing through the surface heater incorporating a nichrome wire or the Peltier element.

[0238] FIG. 23 is a configuration diagram and a cross-sectional view showing the heater 626 disposed on the metal film 601 of the electrode material 614. As one embodiment, the heater 626 is configured with three heater chips 625 (heater chip 625a, heater chip 625b, heater chip 625c) connected.

[0239] In order to increase the area of the heater 626, the heater chips 625 are formed and arranged in a matrix. Also, a plurality of heater chips 625 may be stacked to increase the heat generation amount per unit area. The electrode material 614 is disposed on a cooler (cooling plate) 627. The cooler 627 cools the lower surface of the electrode material 614. By supplying current to the thin film heater 623 of the heater chip 625, the thin film heater 623 generates heat, and the heat is transmitted to the metal film 601 of the electrode material 614.

[0240] The electrode material 614 is cooled by the cooler (cooling plate) 627 on the lower surface and heated by the heater 626 on the upper surface. The thermomigration effect is implemented on the metal film 601 of the electrode material 614 by cooling and heating, and the metal film 601 becomes a metal alloy film 603.

[0241] The heating method and the method of generating a thermal gradient of the present invention are not limited to those using the heater 626 and the Peltier element 609. As shown in FIG. 25, alloying may be performed by irradiating the metal film 601 with laser light 632.

[0242] Figure 25 is an explanatory diagram and configuration diagram of the manufacturing method of the electrode material 614 of the present invention. The manufacturing apparatus for the electrode material 614 includes a chiller (cooling / heating device) 629, a cooler 627, and a circulating water (circulating liquid) pipe 631 that circulates between the cooler 627 and the chiller 629. The electrode material 614 is loaded onto the cooler 627. By cooling the circulating fluid in the chiller 629, the temperature of the electrode material 614 is maintained at a specified or predetermined value.

[0243] The chiller 629 is configured to maintain a constant temperature for components such as the cooler 627 by circulating water or a heat transfer fluid while controlling its temperature. While it is primarily used for cooling, it can also heat.

[0244] In this specification, the term "circulating water" is used, but it is not limited to water. Ethylene glycol, glycerin, or other substances may be used, and forced air cooling may also be employed. The chiller 629 supplies the liquid in the circulating water (circulating liquid) pipe 631 to the cooler 627, controlling the temperature within a range, for example, from minus 30°C to plus 100°C.

[0245] The electrode material 614 is sealed airtight with a sealed cover 628, and the inside of the sealed cover 628 is filled with an inert gas such as nitrogen (N2). When laser light 632 is irradiated onto the metal film 601, it may heat up and oxidation may occur. By heating the metal film 601 while it is sealed airtight with the sealed cover 628, oxidation of the metal film 601 can be suppressed.

[0246] The above issues may also occur when the metal film 601 is heated by the Peltier element 609. Therefore, even in the embodiment where the metal film 601 is heated by the Peltier element 609, it is preferable to seal it with a sealed cover 628 and to fill the sealed cover 628 with an inert gas to implement the thermomigration effect.

[0247] The metal film 601 of the electrode material 614 is heated by irradiating it with laser light 632 generated by the laser irradiator 634. The heating by the laser light 632 and the cooling by the cooler 627 create a temperature gradient in the electrode material 614, and the metal film 601 becomes a metal alloy film 603 due to the migration effect.

[0248] Figure 24 is a graph showing the relationship between a metallic material and the absorption rate (%) of YAG laser light 632. Copper (Cu) is used as an example metallic material. For metallic materials, the absorption rate (%) increases as the wavelength of the laser light 632 decreases.

[0249] The fundamental wavelength of a YAG laser is near-infrared light at 1064 nm, and the second harmonic (SHG) of a YAG laser is a green laser at 532 nm. The third harmonic (THG) of a YAG laser is an ultraviolet laser at 355 nm, and the fourth harmonic (FHG) of a YAG laser is 266 nm.

[0250] The absorption rate of YAG laser light 632 is 10%, but the absorption rate of the second harmonic (SHG) of YAG laser light 632 is 50%. The absorption rate of the third harmonic (THG) and fourth harmonic (FHG) is 70%.

[0251] Therefore, it is preferable to use the second harmonic (SHG) or third harmonic (THG) of the YAG laser light used to heat the metal film 601. The fourth harmonic (FHG) is not suitable for heating the metal film 601 because the laser light 632 is weak.

[0252] It is preferable to use femtosecond laser light. Femtosecond laser devices generally generate femtosecond laser light 632 with pulse widths ranging from sub-picoseconds to tens of femtoseconds. When a material is irradiated with ultrashort pulse laser light 632 ranging from sub-picoseconds to tens of femtoseconds, the pulse width is sufficiently short compared to the thermal diffusion characteristic time of the material, allowing the light energy to be effectively directed to the target irradiation area.

[0253] As a result, thermal effects on the surrounding area of ​​the irradiation can be localized. Furthermore, because the electric field intensity of the laser light is very high, nonlinear effects such as multiphoton absorption and multiphoton ionization can be induced spatially selectively only where the beam is focused.

[0254] In the embodiment shown in Figure 25, it goes without saying that the cooler 627 may be replaced with a Peltier element 609b, as shown in Figure 18, to cool the back surface of the electrode material 614. The embodiments described herein and in the drawings may be replaced or combined in whole or in part. It is also preferable to form the metal alloy film 603 using both the thermomigration effect and the electromigration effect. Figure 26 is an explanatory diagram of a manufacturing method and apparatus for producing electrode material 614 using both thermomigration and electromigration effects.

[0255] As shown in Figure 26, a voltage electrode 635a is placed on the metal film 601 of the electrode material 614. In addition, a voltage electrode 635b is placed on the lower surface of the base metal foil 602.

[0256] A (variable) current (voltage) source 112c is connected between voltage electrodes 635a and 635b. The (variable) current (voltage) source 112c generates an electromigration effect by supplying voltage between voltage electrodes 635a and 635b.

[0257] Furthermore, as explained in Figure 17, etc., a Peltier element 609a is placed on the upper surface of the metal film 601, and a Peltier element 609b is placed on the lower surface of the base metal plate 602. The heat dissipated by the Peltier element 609a heats the metal film 601. The heat absorbed by the Peltier element 609b cools the base metal foil 602. The heat generation and absorption by the Peltier elements 609a and 609b create a temperature gradient in the electrode material 614, and a thermomigration effect is achieved.

[0258] In the connection shown in Figure 17, current flows from the (variable) current (voltage) source 112a to the Peltier element 609a, from the n-type semiconductor 612 to the p-type semiconductor 611. The element electrode 607 side of the Peltier element 609a absorbs heat, while the element electrode 608 side of the Peltier element 609a generates heat, heating the metal film 601.

[0259] In the Peltier element 609b, current flows from the (variable) current (voltage) source 112b in the direction from the n-type semiconductor 612 to the p-type semiconductor 611. The element electrode 608 side of the Peltier element 609a generates heat, and the element electrode 607 side of the Peltier element 609b absorbs heat, cooling the base metal foil 602.

[0260] When the positive and negative electrodes of the (variable) current (voltage) source 112 are swapped, the direction of current flow is reversed, and the heat-absorbing part of the Peltier element 609 is changed to a heat-dissipating part, and the heat-dissipating part of the Peltier element 609 is changed to a heat-absorbing part.

[0261] In the embodiment shown in Figure 26, the metal film 601 is alloyed to form a metal alloy film 603 by simultaneously utilizing the thermomigration effect and the electromigration effect, or by switching between the thermomigration effect and the electromigration effect as appropriate.

[0262] The metal alloy film 603 suppresses dendrite formation, thereby preventing electrode deformation and a decrease in electrode deposition efficiency. Furthermore, it exhibits minimal changes over time, ensuring stability and extending the battery's lifespan.

[0263] Figure 27 is a configuration diagram and explanatory diagram of the manufacturing method and apparatus for the battery electrode material of the present invention, using a Peltier element 609 and a cooler 627. In the embodiment shown in Figure 27, two electrode materials, 614a and 614b, are manufactured simultaneously.

[0264] A metal film 601 is formed on the base metal plate 602 of the electrode material 614a, a Peltier element 609a is placed on the upper surface of the metal film 601, and a Peltier element 609b is placed on the lower surface of the base metal plate 602. The heat dissipated by the Peltier element 609a heats the metal film 601. The heat absorbed by the Peltier element 609b cools the base metal foil 602. The heat generation and absorption by the Peltier elements 609a and 609b create a temperature gradient in the electrode material 614, and a thermomigration effect is achieved.

[0265] In the Peltier element 609b, current flows from the (variable) current (voltage) source 112b in the direction from the n-type semiconductor 612 to the p-type semiconductor 611. The element electrode 608 side of the Peltier element 609a generates heat, and the element electrode 607 side of the Peltier element 609b absorbs heat, cooling the base metal foil 602.

[0266] A metal film 601 is formed on the base metal plate 602 of the electrode material 614b, a Peltier element 609b is placed on the upper surface of the metal film 601, and a cooler 627 is placed on the lower surface of the base metal plate 602. By cooling the circulating liquid (circulating water) in the cooler 627, the temperature of the electrode material 614 is maintained at a specified or predetermined value. The chiller (not shown) is configured to maintain a constant temperature for components such as the cooler 627 by circulating water or a heat transfer medium while controlling its temperature. It goes without saying that cooling and heating are not limited to circulating fluid (circulating water), but can also be done using dry air. The Peltier element 609b and the cooler 627 generate a temperature gradient on the electrode material 614b, thereby achieving a thermomigration effect.

[0267] By alloying the metal film 601 with at least one of the following metals—indium (In), tin (Si), bismuth (Bi), zinc (Zn), lead (Pb), copper (Cu), cobalt (Co), and iron (Fe)—the formation of dendrites can be suppressed, thereby preventing electrode deformation and a decrease in electrode deposition efficiency.

[0268] Figure 28 is a diagram illustrating the configuration of the manufacturing apparatus and the manufacturing method of the present invention, which forms a metal film 601 and a metal alloy film 603 by applying thermomigration and electromigration effects.

[0269] In Figure 28, as one embodiment, the formation of the metal film 601 is described as being performed by vapor deposition technology in a vapor deposition apparatus 638, but the present invention is not limited to this. For example, it may be formed or manufactured by sputtering technology, plating technology, printing technology, coating technology using a spinner, etc., and it goes without saying that an apparatus corresponding to each technology can be configured.

[0270] As shown in Figure 28, a metal film 601 is deposited onto the base metal foil 602 using a deposition apparatus 638, and the metal to be alloyed is also deposited. Peltier elements 609a and 609b are placed on the upper and lower surfaces of the base metal foil 602 on which the metal film 601 has been formed, and the thermomigration effect is carried out. The electrode material 614 on which the metal alloy film 603 has been formed is wound up by a roller 637.

[0271] Figure 28 illustrates a configuration in which a base metal foil 602 is supplied by a roller 636, a metal film 601 is formed on the base metal foil 602, and the resulting metal alloy film 603 is wound up by a roller 637. However, the present invention is not limited to this configuration. For example, it goes without saying that a single-sheet method may be used in which the base metal foil 602 is prepared as a single sheet and a metal alloy film 603 is formed on each sheet.

[0272] Furthermore, the thermomigration effect is not limited to the Peltier element 609; it may also be implemented using the laser light 632 in Figure 25 or the heater 626 in Figure 23. Needless to say, in addition to the thermomigration effect, the electromigration effect, as explained in Figure 6, may also be implemented. The embodiments described herein and in the drawings may be replaced or combined in whole or in part. Hereinafter, embodiments of the secondary battery of the present invention will be described with reference to the drawings.

[0273] In the drawings illustrating embodiments for carrying out the invention, elements having the same function are denoted by the same reference numerals, and their descriptions may be omitted. Furthermore, the embodiments of the present invention described herein can be combined.

[0274] The secondary battery of the present invention uses the electrode material 614 of the present invention for its electrodes. The metal alloy film 603 of the electrode material 614 suppresses the generation of dendrites, thereby suppressing electrode deformation and a decrease in electrode deposition efficiency.

[0275] In the embodiments of the present invention, a zinc secondary battery is used as an example for explanation, but the present invention is not limited to this. Needless to say, it can also be applied to other secondary batteries, such as fluoride ion batteries.

[0276] The zinc secondary battery of the present invention is not particularly limited as long as it contains zinc in the negative electrode and uses an alkaline hydroxide aqueous solution as the electrolyte. Therefore, it can be a nickel-zinc secondary battery, a silver-zinc secondary battery, a manganese-zinc secondary battery, a zinc-air secondary battery, or various other alkali-zinc secondary batteries. Needless to say, the embodiments in this specification and drawings can also be applied to fluoride-ion batteries such as all-solid-state fluoride-ion batteries.

[0277] Figure 29 is a diagram illustrating the structure and explanatory diagram of the zinc secondary battery of the present invention. The zinc secondary battery 500 has a positive electrode material 106, a negative electrode material 103, an electrolyte 108, and a separator 109 inside a battery container 101. The negative electrode 102 and negative electrode material 103 contain zinc, indium (In), tin (Sn), or copper (Cu), etc., and are alloyed with these metals to form a metal alloy film 603.

[0278] The zinc secondary battery 500 is illustrated and described, but it goes without saying that it can be replaced with a fluoride ion battery 500. Furthermore, it goes without saying that it can be replaced with any other secondary battery 500.

[0279] The zinc may be in any form, such as metal zinc, a zinc compound, or a zinc alloy, as long as it has electrochemical activity suitable for the negative electrode, and it may also be contained in the negative electrode 102 and the negative electrode material 103.

[0280] The positive electrode material 106 is selected according to the type of zinc secondary battery used. For example, in the case of a nickel-zinc secondary battery, nickel oxyhydroxide may be used; in the case of a silver-zinc secondary battery, silver oxide may be used; in the case of a manganese-zinc secondary battery, manganese dioxide may be used; and in the case of a zinc-air secondary battery, an air electrode that takes in oxygen from the air may be included.

[0281] A negative electrode 102 is formed or arranged on the negative electrode material 103, a negative terminal 104 is connected to the negative electrode 102, and the negative terminal 104 is led out to the outside of the battery container 101. The negative electrode 102 contains zinc, indium (In), or tin (Sn), etc., or is alloyed with these metals. A positive electrode 105 is formed on or arranged on the positive electrode material 106, a positive terminal 107 is connected to the positive electrode 105, and the positive terminal 107 is led out to the outside of the battery container 101.

[0282] Furthermore, the separator 109 has a conductive layer 110, and conductive terminals 111 are connected to the conductive layer 110 to supply or apply voltage or current. Although not shown in the figure, a conductive pattern is formed around the conductive layer 110. The conductive pattern is connected to the conductive terminals 111 and is configured to supply voltage or current to the conductive layer 110 without voltage drop.

[0283] The conductive layer 110 is preferably made of an alkali-resistant metal, such as titanium (alloy), iron (alloy), chromium, nickel (alloy), stainless steel, or Cu alloy casting.

[0284] As the conductive layer 110, materials other than metals can be used, such as graphite, carbon, and carbon quantum dots (CQDs). Other examples include artificial graphite, glassy carbon, amorphous carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbons, fullerene, carbon black, carbon fiber, fibrous carbon, carbon nanotubes, carbon nanohorns, Vulcan, Ketjenblack, and acetylene black. One or more of these can be used.

[0285] A metal oxide layer can also be used as the conductive layer 110. The metal oxide layer may be a single layer or may be configured or formed in multiple layers. Examples include tin, zinc, and chromium oxides. Other examples include one or more selected from indium oxide and germanium oxide.

[0286] The positive electrode material 106 and the negative electrode material 103 are immersed in or in contact with the electrolyte 108. The positive electrode material 106 and the electrolyte 108 do not necessarily need to be separate; the positive electrode material may be configured as a mixture of the positive electrode material 106 and the electrolyte. Similarly, the negative electrode material 103 and the electrolyte 108 do not necessarily need to be separate, and the negative electrode material may be configured as a mixture of the negative electrode and the electrolyte.

[0287] The positive electrode material 106, the negative electrode material 103, and the electrolyte 108 can be configured according to the type of zinc secondary battery. These materials contain zinc, indium (In), or tin (Sn), and are alloyed with these metals.

[0288] As shown in Figure 39, during charging, the Zn constituting the negative electrode generates dendrites (tree-like crystals), and these dendrites penetrate the separator 109, which prevents the positive electrode material 106 from electronically connecting to the negative electrode, and come into contact with the positive electrode material 106, causing a short circuit.

[0289] A positive electrode material 106 (NiOOH) and a negative electrode material 103 (Zn) are immersed in an electrolyte (NaOH aqueous solution) 108, with a separator 109 (a microporous membrane made of PP (polypropylene) or PE (polyethylene)) interposed between them. The separator 109 electronically insulates the positive electrode material 106 and the negative electrode material 103, and allows OH to pass through small pores (holes) 206. - It plays a role in conducting ions. The battery reaction is shown by the following equation. (positive electrode) 2NiOOH + 2H2O + 2e - -> 2Ni(OH)2+ 2OH - (1-1) (Negative electrode) Zn + 4OH - -> Zn(OH)4 2- + 2e - -> ZnO + H2O + 2OH - + 2e - (1-2) therefore, 2NiOOH + Zn + H2O -> 2Ni(OH)2 + ZnO (1-3)

[0290] In the case of discharge, in the negative electrode material 103, Zn is formed from 4 OH molecules in the electrolyte 108. - It reacts with ions to form Zn(OH)4 2- It becomes an ion. At this time, it gains two electrons (e - ) is released into the external circuit. The generated Zn(OH)4 2- The ions are in the electrolyte 108, including within the small pores 206 of the separator 109, but on the electrode, OH - It releases ions and H2O to become ZnO. In the positive electrode material 106, two electrons (e) that have passed through the external circuit - ) reacts with NiOOH and H2O in electrolyte 108 to form 2Ni(OH)2.

[0291] As shown in Figure 39, during charging, the reverse reaction described above occurs, and Zn is deposited on the negative electrode material 103. However, the current density is higher in the portion of the separator 109 facing the small pore 206, and the deposition rate is faster, forming the seeds of dendrites 205. The electric field strength at the tip of the dendrite 205 is high, causing Zn deposition to concentrate and the dendrite 205 to grow.

[0292] The tip of the dendrite 205 reaches the small pore 206 of the separator 109. Zn(OH)4 also enters the electrolyte 108 in the small pore 206 of the separator 109. 2- Ions are present. Even within the small pores 206, the dendrites 205 continue to grow, reaching the positive electrode material 106 and causing a short circuit inside the battery.

[0293] The separator 109 of the present invention has smaller pores 206 and distributes them uniformly across the entire surface of the separator 109. This reduces the bias in the current distribution and suppresses the generation of dendrite nuclei 205. As shown in Figure 39, the separator 109 is OH - It allows ions to pass through, but Zn(OH)4 2- It does not allow ions to pass through. As a result, even when the tip of dendrite 205 reaches separator 109, Zn(OH)4 remains inside the separator. 2- Since no ions are present, Zn is suppressed within separator 109. In one embodiment, the separator 109 of the battery of the present invention has a structure of three or more layers, consisting of an insulating layer 115a, a conductive layer 110, and an insulating layer 115b.

[0294] The insulating layer 115 of the separator 109 is an ion-conducting film. The ion-conducting film is stable in a strongly alkaline aqueous solution. The electron conduction resistance is 1 GΩ or more. In addition, in an alkaline aqueous solution, it allows hydroxide ions (OH-) to pass through, but not zincate ions (Zn(OH)4). 2- ) does not pass through. hydroxide ions (OH - The conductivity is 0.01 S / cm. Hydroxide ions (OH) -The small pores 206 responsible for conduction are uniformly formed across the entire film surface. This allows for uniform dissolution and deposition of electrodes.

[0295] When the conductive layer 110 is made of metal, alkali-resistant metals such as titanium (alloy), iron (alloy), chromium, nickel (alloy), stainless steel, or Cu alloy castings are used or selected. Alternatively, tin, zinc, etc., may be used or selected. Furthermore, the conductive layer 110 is not limited to foil, plate, or thin film form, but may also be in the form of a mesh, foamed copper, or perforated material.

[0296] For the conductive layer 110, materials other than metals can be used, such as graphite, carbon, or carbon quantum dots (CQDs). Carbon quantum dots (CQDs) are nanoparticles with a size of less than 10 nm.

[0297] Examples of other materials include artificial graphite, glassy carbon, amorphous carbon, graphitized carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbons, fullerene, carbon black, carbon fiber, fibrous carbon, carbon nanotubes, carbon nanohorns, Vulcan, Ketjenblack, and acetylene black, and one or more of these can be used.

[0298] When iron oxide (Fe2O3) is used as the conductive layer 110, it is preferable to disperse CQDs in the iron oxide. The presence of CQDs in the Fe2O3 film can increase the conductivity of the Fe2O3 film.

[0299] Iron oxide (Fe2O3) has disadvantages such as low chemical stability and poor conductivity. Adding, mixing, or incorporating phosphorus (P) into iron oxide (Fe2O3) stabilizes it.

[0300] The conductive layer 110 may be formed or constructed by electrodeposition, plating, vapor deposition, or screen printing. Alternatively, conductive materials such as metals may be sputtered to deposit conductive carbon material, metal oxides, phosphorus, etc.

[0301] The conductive layer 110 is formed as a thin film, and by crystallization or sintering, small pores are formed in the thin film, into which the electrolyte penetrates 206. An insulating layer 115, acting as a separator, is formed or arranged on the front and rear surfaces of the conductive layer 110.

[0302] The separator 109 used in the battery of the present invention has a multilayer structure including an insulating layer and a conductive layer. The multilayer structure only needs to include at least one insulating layer and one conductive layer.

[0303] The separator 109 of the present invention is preferably composed of a three-layer structure of insulating layer 115a / conductive layer 110 / insulating layer 115b. The separator 109 of the present invention is said to include a three-layer structure of insulating layer 115a / conductive layer 110 / insulating layer 115b, but it is sufficient that it includes at least these three layers. For example, the separator 109 of the present invention may have a four-layer structure of conductive layer / insulating layer / conductive layer / insulating layer.

[0304] The conductive layer 110 of the separator 109 only needs to have a conductivity greater than that of the electrolyte 108. Since the conductive layer 110 is formed or constitutes the entire surface of the separator 109, the sheet resistance can be kept low even if it is made of a material with low conductivity. The sheet resistance of the conductive layer 110 is preferably 1000 Ω / sq or less, and more preferably 100 Ω / sq or less. Figure 37 is an explanatory diagram of the cyclic voltammogram (CV) of a saturated perchlorate aqueous solution. An Ag / AgCl electrode was used as the reference electrode. In the CV measurement shown in Figure 37, no current flows in the flat area. This means that the water decomposition reaction is not occurring. The flat area is the potential window.

[0305] The potential window for saturated sodium perchlorate solution and saturated lithium perchlorate solution is 3.2V, and it can be seen that saturated magnesium perchlorate, saturated perchlorate solution, and saturated barium perchlorate solution also have a wide potential window (approximately 3V).

[0306] This means that saturated lithium perchlorate (LiClO4) aqueous solution, saturated sodium perchlorate (NaClO4) aqueous solution, saturated barium perchlorate (Ba(ClO4)2) aqueous solution, and saturated magnesium perchlorate (Mg(ClO4)2) aqueous solution can be used as electrolytes in secondary batteries.

[0307] As illustrated in Figure 37, saturated aqueous solutions of perchlorates, in particular, have a wide potential window. Using these aqueous solutions as electrolytes makes it possible to manipulate high applied voltages. Figure 38 is an explanatory diagram illustrating the conductivity of saturated lithium perchlorate aqueous solution and its temperature dependence. The conductivity of a saturated lithium perchlorate solution is greater than that of a saturated sodium perchlorate solution. In both cases, conductivity increases with increasing temperature.

[0308] In Figure 38, the horizontal axis of the graph represents temperature, and the vertical axis represents conductivity in millisiemens per centimeter (mS / cm). The conductivity of lithium perchlorate (LiClO4) aqueous solution is higher than that of saturated NaClO4 aqueous solution.

[0309] However, the temperature dependence of the conductivity of an aqueous lithium perchlorate (LiClO4) solution is greater than that of an aqueous saturated NaClO4 solution. Furthermore, as shown in Figure 37, the potential window of lithium perchlorate (LiClO4) is narrower than that of sodium perchlorate (NaClO4). Therefore, sodium perchlorate (NaClO4) is preferred.

[0310] While this invention primarily describes sodium perchlorate (NaClO4), it is not limited to this. As illustrated in Figure 37, aqueous lithium perchlorate (LiClO4), aqueous barium perchlorate (Ba(ClO4)2), and magnesium perchlorate (Mg(ClO4)2) may also be used. Figure 32 is an explanatory diagram illustrating the NaOH concentration (mol / L) and potential window (V) in this first zinc secondary battery.

[0311] The working electrode is GC (glassy carbon), the counter electrode is Pt, and the reference electrode is Hg / HgO / NaOH. The electrolyte is NaClO4, and the NaOH is varied. The measurement method is Linear Sweep Voltammetry (LSV), and the sweep rate is 5mV / sec.

[0312] As described above, in one embodiment, a perchlorate aqueous solution is added to an alkaline electrolyte solution NaOH. Note that this is not limited to sodium perchlorate (NaClO4), but other perchlorate aqueous solutions include lithium perchlorate (LiClO4) aqueous solution, sodium perchlorate (NaClO4) aqueous solution, barium perchlorate (Ba(ClO4)2) aqueous solution, and magnesium perchlorate (Mg(ClO4)2) aqueous solution.

[0313] Figure 32 graphs the potential window (V) as the concentration of sodium perchlorate (NaClO4) is varied, with NaOH concentration (mol / L) on the horizontal axis. pH is also indicated for supplementary information.

[0314] The diagram shows sodium perchlorate (NaClO4) concentrations of 6 mol / L, 7 mol / L, 8 mol / L, and 9 mol / L. As the mol / L concentration increases, the potential window (V) rises, but it saturates at 9 mol / L. Furthermore, the difference in the potential window between 8 mol / L and 9 mol / L is small. Therefore, it is preferable to use a concentration of 8 mol / L or higher.

[0315] Figure 33 graphs the oxygen and hydrogen evolution potentials when NaOH is 0.0001 mol / L. The potential window is ±0.05 mA. The graphs for NaClO4 = 8 mol / L and NaClO4 = 1 mol / L are shown. Note that the graphs for NaClO4 = 8 mol / L and NaClO4 = 9 mol / L are almost identical.

[0316] As shown in Figures 32 and 34, the potential window decreases as the mol / L concentration of NaClO4 decreases. From the graph in Figure 33, it is preferable to use or adopt saturated sodium perchlorate (NaClO4) in zinc secondary batteries, with a concentration of 8 mol / L or higher. Since the potential window widened in the range of 0.0001 to 0.01 mol / L for NaOH concentrations, it can be concluded that NaOH concentrations within this range are appropriate for the electrolyte.

[0317] Figure 34 is a graph showing the oxygen evolution potential in response to changes in NaOH concentration. Similar to the potential window, the oxygen evolution potential increased in the range of NaOH concentration from 0.0001 to 0.01 mol / L. In other words, it can be seen that oxygen evolution was suppressed within this concentration range. Figure 35 is a graph showing the hydrogen evolution potential in response to changes in NaOH concentration. No significant changes in the hydrogen evolution potential were observed with respect to changes in NaOH concentration.

[0318] Figure 36 is a graph showing the relationship between the potential window (V) and conductivity (ms / cm). Similar to the potential window, conductivity is high in the range of NaOH concentration from 0.0001 to 0.01 mol / L, so a concentration range of 0.0001 to 0.01 mol / L is appropriate for NaOH.

[0319] Figure 30 is a diagram illustrating the configuration and operation of the coin-type zinc secondary battery of the present invention. While Figure 30 uses a coin-type secondary battery as an example, the technical concept of the present invention is not limited to this. For example, it is also possible to use a cylindrical battery, as shown in Figure 31. Other examples include film-shaped and box-shaped batteries.

[0320] As shown in Figure 30, the separator 109 of the zinc secondary battery of the present invention is permeated and impregnated with electrolyte 108a and electrolyte 108b. A positive electrode 105 is formed or arranged on the positive electrode material 106. The positive electrode 105 is configured or arranged to be electrically connected to the positive electrode case 202 (positive terminal 107). A negative electrode 102 is formed or arranged on the negative electrode material 103. The negative electrode 102 is configured or arranged to be electrically connected to the negative electrode case 201 (negative terminal 104).

[0321] The negative electrode case 201 and the positive electrode case 202 are insulated by a gasket 203. The negative electrode case 201, the positive electrode case 202, and the gasket 203 constitute a coin-type battery, and the electrolyte 108 is sealed inside. It goes without saying that the zinc secondary battery of the present invention may be cylindrical or otherwise, as shown in Figure 31.

[0322] As shown in Figure 31, the zinc secondary battery of the present invention comprises a battery container 101, a positive electrode material 106, a negative electrode material 103, and a separator 109, and an insulating film 204 is formed or arranged as needed. An electrolyte 108 is filled between the separator 109, the positive electrode material 106, and the negative electrode material 103.

[0323] A positive electrode (not shown) is formed or arranged on the positive electrode material 106. The positive electrode is configured or arranged to be electrically connected to the positive electrode case (positive terminal 107). A negative electrode (not shown) is formed or arranged on the negative electrode material 103. The negative electrode is configured or arranged to be electrically connected to the negative electrode case (negative terminal 104).

[0324] Figure 9 is a structural diagram and explanatory diagram of the all-fixed fluoride ion battery of the present invention. In Figure 9, (a) is a cap made of SUS316L, (b) is a wave washer, and (c) is a current collector (graphite). (d) is the battery section consisting of a negative electrode (0.5 mm), a solid electrolyte (0.5 mm), and a positive electrode (0.5 mm). (e) is a current collector (graphite), (f) is a gasket (PP: polypropylene resin), and (g) is a case (SUS316L).

[0325] Figure 10 is an explanatory diagram of one embodiment of a coin-type electron. The negative electrode is (La 0.9 Ba 0.1 F 2.9 It is composed of ) + In + Sn. The thickness is 0.5 mm. A current collector (carbon film) is formed on the negative electrode. The thickness of the current collector (carbon film) is exemplified as 20 nm.

[0326] The positive electrode is composed of PbF2 and Pb. The PbF2 film thickness of the positive electrode is 1 μm, and the thickness of the positive electrode is 0.5 mm as an example. A current collector (carbon film) is formed on the positive electrode. The film thickness of the current collector (carbon film) is 20 nm as an example. A solid electrolyte is placed between the positive and negative electrodes. The solid electrolyte is La 0.9 Ba 0.1 F 2.9 Examples are given.

[0327] Figure 11 is an explanatory diagram of the method for producing electrode material 614 for a fluoride ion battery using the battery electrode manufacturing method of the present invention. Figure 11 illustrates and explains the button-type battery shown in Figure 9.

[0328] As shown in Figure 11(a), La 0.9 Ba 0.1 F 2.9 Pellet is prepared. In one embodiment, the pellet has a diameter of 10 mm and a thickness of 0.5 mm. A metal film 601a consisting of indium (In) plating is formed on the pellet as shown in Figure 11(b). The thickness of the plating is 0.5 μm.

[0329] Next, as shown in Figure 11(c), tin (Sn) is used as the metal film 601a. ​​The plating thickness is 0.5 μm. After that, thermomigration is performed as described in Figures 1 and 17. In addition, electromigration as shown in Figure 6 is performed. A metal alloy layer is formed by thermomigration and electromigration.

[0330] By implementing the present invention, which involves adding indium (In) to the LaF3 negative electrode of a fluoride-ion battery, electrolyte decomposition and internal short circuits (dendrites) can be suppressed.

[0331] Figure 12 shows the discharge curve of the prototype all-solid-state fluoride ion battery of the present invention, which is the test result. The measurement temperature was 150°C. In the graph of Figure 12, the vertical axis shows Potential (V) vs. Pb / PbF2, and the horizontal axis shows Capacity (mAh / cm²). 2 It indicates that good potential is maintained up to a capacity of 0.5 or higher.

[0332] It goes without saying that the embodiments shown in Figures 39 to 47 can be applied to fluoride-ion batteries. Similarly, it goes without saying that the embodiments shown in Figures 48 to 51 can be applied to fluoride-ion batteries.

[0333] In zinc secondary batteries, as shown in Figure 39, there is a problem in that during charging, the Zn constituting the negative electrode generates dendrites 205 (tree-like crystals), which break through the separator 109 and electrically short-circuit the positive electrode material 106 and the negative electrode. Although the following examples illustrate a zinc secondary battery, it goes without saying that the invention can also be applied to the fluoride ion battery of the present invention. Furthermore, it goes without saying that the embodiments shown in Figures 17 to 28 can also be applied to the fluoride-ion battery of the present invention.

[0334] In one embodiment, the separator 109 of the zinc secondary battery of the present invention has a structure of three or more layers: an insulating layer 115a, a conductive layer 110, and an insulating layer 115b. Furthermore, the conductive layer 110 is configured to allow current or voltage to be applied to or supplied via a conductive terminal 111.

[0335] Current or voltage is supplied between at least one of the following: the conductive layer 110 and the negative electrode 102, the conductive layer 110 and the positive electrode 105, and the negative electrode 102 and the positive electrode 105. Conductive terminals 111 are connected to or positioned on the conductive layer 110.

[0336] Figure 40 is a schematic diagram illustrating the state in which the dendrite 205 has grown and is in contact (connected) with the conductive layer 110 at the position indicated by the dotted circle. A positive electrode 105 is formed on or arranged on the positive electrode material 106, a positive terminal 107 is connected to the positive electrode 105, and the positive terminal 107 is led out to the outside of the battery container 101.

[0337] Furthermore, the separator 109 has a conductive layer 110, and conductive terminals 111 are connected to the conductive layer 110 to supply or apply voltage or current. Although not shown in the figure, a conductive pattern is formed around the conductive layer 110. The conductive pattern is connected to the conductive terminals 111 and is configured to supply voltage or current to the conductive layer 110 without voltage drop.

[0338] In Figure 40, when the switch circuit 114 is turned on (closed), the (variable) voltage (current) circuit 112 is connected between the conductive terminal 111 and the negative terminal 104. The (variable) voltage (current) circuit 112 can apply or supply at least one of voltage and current between the conductive terminal 111 and the negative terminal 104. Furthermore, the magnitude of the supplied or applied current and voltage can be changed and set.

[0339] The (variable) voltage (current) circuit 112 can vary the polarity and magnitude of the current. It can also vary the polarity and magnitude of the voltage. Furthermore, it can monitor the presence and magnitude of the current flowing and control the on (closed) and off (open) states of the switch circuit 114.

[0340] As the dendrite 205 grows and comes into contact with the conductive layer 110, a current path is generated between the negative electrode 102 and the conductive layer 110. When a current or voltage is applied by the (variable) voltage (current) circuit 112, current flows to the dendrite 205 at the location indicated by the dotted circle in Figure 40, generating heat and causing the dendrite 205 to break. Therefore, the growth of the dendrite 205 is stopped, and a short circuit between the negative electrode 102 and the positive electrode 105 can be prevented or suppressed. Figure 40 shows a (variable) voltage (current) circuit 112, which is configured and used to cut the dendrite 205, but the present invention is not limited to this.

[0341] Figure 41 shows an embodiment in which resistance is measured and monitored between at least one of the following: between the conductive layer 110 and the negative electrode 102, between the conductive layer 110 and the positive electrode 105, and between the negative electrode 102 and the positive electrode 105. In this embodiment, pulsed current or voltage is supplied between at least one of the following: between the conductive layer 110 and the negative electrode 102, between the conductive layer 110 and the positive electrode 105, and between the negative electrode 102 and the positive electrode 105.

[0342] The pulse generator 117 can vary the polarity direction and magnitude of the pulse current. It can also vary the polarity direction and magnitude of the pulse voltage. Furthermore, it can monitor the presence and magnitude of the flowing current and control the on (closed) and off (open) states of the switch circuit 114, as well as the switching of terminals a and b of the switch circuit 114. It goes without saying that the pulse generator 117 can be replaced with the (variable) voltage (current) circuit 112.

[0343] By connecting the switch circuit 114 to terminal a, the pulse generator 117 is connected between the conductive terminal 111 and the negative terminal 104. By connecting the switch circuit 114 to terminal b, the resistance meter 116 is connected between the conductive terminal 111 and the negative terminal 104.

[0344] The resistance meter 116 is a device for measuring or monitoring the resistance between the conductive terminal 111 and the negative terminal 104. However, the resistance meter is not limited to 116; the resistance can also be measured or monitored indirectly by applying a predetermined current and measuring the voltage drop.

[0345] When the dendrites 205 grow and come into contact with the conductive layer 110, a current path is generated between the negative electrode 102 and the conductive layer 110. Alternatively, the resistance value decreases. The generation of the current path and the state of its generation can be determined by measuring the resistance value with the resistance meter 116. Furthermore, the state of dendrite growth can be understood by periodically monitoring the resistance value at predetermined intervals or continuously.

[0346] The switch circuit 114 is connected to terminal b, and when the resistance value measured by the resistance meter 116 falls below a predetermined value, it is determined that a dendrite 205 has formed. The change in resistance value and the rate of change are also observed and monitored. If the rate of change exceeds a predetermined value, it is determined that a dendrite 205 has formed or will form. The resistance value is approximately M (mega) ohms (Ω) or less.

[0347] If a dendrite 205 is generated or is deemed likely to be generated, the switch circuit 114 is switched to terminal a, and a pulse generator 117 (voltage / current source 112) is connected between the conductive terminal 111 and the negative terminal 104.

[0348] In the embodiments of the present invention, a pulse generator 117 (voltage / current source 112) is connected between the conductive terminal 111 and the negative terminal 104, and the resistance value between the conductive terminal 111 and the negative terminal 104 is measured or monitored. However, the invention is not limited to this. Alternatively, a pulse generator 117 (voltage / current source 112) may be connected between the conductive terminal 111 and the positive terminal 107, and the resistance value between the conductive terminal 111 and the positive terminal 107 may be measured or monitored. Furthermore, a pulse generator 117 (voltage / current source 112) may be connected between the negative terminal 104 and the positive terminal 107, and the resistance value between the negative terminal 104 and the positive terminal 107 may be measured or monitored.

[0349] The pulses generated by the pulse generator 117 are not limited to a rectangular shape. A pulse is a signal with a relatively high peak value. It may be a sine wave, multiple pulses, a triangular wave, etc.

[0350] By applying a pulsed signal waveform with the pulse generator 117, the high-resistance dendrites 205, or the areas where the dendrites 205 and the conductive layer 110 are in contact, heat up and are cut. This cutting of the dendrites 205 destroys them and stops their growth.

[0351] Preferably, the pulse height, magnitude, current or voltage, and application period of the pulse applied by the pulse generator 117 are set or changed based on the resistance value measured or monitored by the resistance meter 116. For example, if the resistance value is relatively high, the pulse height value etc. are set lower. If the resistance value is high, the pulse height value etc. are set higher, assuming that the contact of the dendrite 205 is strong.

[0352] When current or voltage is applied using the (variable) voltage (current) circuit 112 or pulse generator 117, current flows to the dendrite 205 at the dotted circle in Figures 40 and 41, generating heat and causing the dendrite 205 to break. Therefore, the growth of the dendrite 205 is stopped, preventing or suppressing a short circuit between the negative electrode 102 and the positive electrode 105. The embodiments shown in Figures 40 and 41 involved a structure and method in which an electric current or the like was applied to the dendrite 205, causing it to be destroyed or cut by heating and melting. Figure 42 shows an embodiment of a configuration and method for moving the separator 109 and mechanically destroying the dendrite 205.

[0353] The separator 109 has small holes 206, and the electrolyte 108 enters into the small holes 206, OH - Ions are allowed to move. As the dendrite 205 grows, it either enters the pore 206 or breaks through the separator 109 and reaches the positive electrode 105. When the dendrite 205 reaches the positive electrode 105, a short circuit occurs between the positive electrode 105 and the negative electrode 102.

[0354] Figure 42 is a configuration diagram and explanatory diagram of an embodiment of the present invention that prevents short circuits using dendrites 205. As shown in Figure 42, the separator 109 is configured to move or vibrate. The dendrites 205 grow in the small holes 206 of the separator 109.

[0355] As shown in Figure 42(a), dendrite 205a penetrates and grows in the small pore 206a. Dendrite 205b penetrates and grows in the small pore 206b. When dendrite 205a or dendrite 205b comes into contact with the positive electrode 105, the positive electrode 105 and the negative electrode 102 are short-circuited.

[0356] As shown in Figure 42(b), the separator 109 moves in the direction of arrow A. By moving in the direction of arrow A, the dendrites 205a that have entered the small hole 206a are cut or destroyed. Also, the dendrites 205b that have entered the small hole 206b are cut or destroyed. By cutting or otherwise destroying the dendrites 205, the growth of the dendrites 205 can be stopped. In addition, short circuits between electrodes caused by the dendrites 205 can be prevented.

[0357] The separator 109 can be moved in direction A or direction B. Furthermore, vibration can be applied to the separator 109. The vibration is generated and applied using ultrasonic waves, such as a piezoelectric element. By moving the separator 109 and applying vibration, the growth of the dendrites 205 can be stopped, and short circuits between electrodes caused by the dendrites 205 can be prevented.

[0358] Figure 43 is an explanatory diagram of the structure and method for moving and vibrating the separator 109. As shown in Figure 43, an elastic body (elastic material, elastic agent, elastic object) 207 is formed or arranged in the battery container 101. The elastic body 207 is an object that has elasticity, and examples include rubber, springs, sponges, and sea sponges. The elastic body 207 may also be a viscous body.

[0359] In the embodiments shown in Figures 42 and 43, it is explained that when the separator 109 is pressed, the elastic body 207 is distorted or deformed, and the position of the small hole 206 in the separator 109 moves, but the invention is not limited to this.

[0360] For example, the separator 109 may be configured such that when it is deformed by compression, expansion, etc., the position of the small hole 206 in the separator 109 moves or deforms, thereby destroying or cutting the dendrite 205. In this embodiment, the elastic body 207 can be omitted.

[0361] In the embodiment shown in Figure 43, an elastic body 207 is arranged or formed in the battery container 101, and a separator 109 is placed between the elastic body 207 and the pressure cap (pressing part) 208. The pressure cap 208 is a button-shaped object made of a rubber material such as butyl rubber or silicone rubber, or a resin material such as silicone or polyester. The pressure cap 208 can be deformed by pressing it.

[0362] The pressure cap 208 is attached to the ring-shaped pressure part 209. By pressing the pressure cap 208, the separator 109 is pressed. The pressure from the separator 109 deforms the elastic body 207, causing the position of the separator 109 to change.

[0363] As shown in Figure 42, the dendrite 205 can be destroyed or cut by changing the position of the separator 109. The position of the separator 109 and the conductive layer 110 can also be changed by pulling the pressure cap 208.

[0364] In the embodiment shown in Figure 43, the separator 109 has a conductive layer 110, and conductive terminals 111 are connected to the conductive layer 110. As shown in Figures 40 and 41, a voltage or current can be applied to the dendrite 205 by a voltage / current source 112 and a pulse generator 117, thereby cutting or destroying the dendrite 205.

[0365] Figure 43 is a diagram illustrating the structure and operation of the zinc secondary battery of the present invention. The zinc secondary battery 500 has a positive electrode material 106, a negative electrode material 103, an electrolyte 108, and a separator 109 inside a battery container 101. The negative electrode material 103 contains zinc.

[0366] A negative electrode 102 is formed or arranged on the negative electrode material 103, a negative terminal 104 is connected to the negative electrode 102, and the negative terminal 104 is led out to the outside of the battery container 101. A positive electrode 105 is formed or arranged on the positive electrode material 106, a positive terminal 107 is connected to the positive electrode 105, and the positive terminal 107 is led out to the outside of the battery container 101. In addition, a conductive terminal 111 is connected to the conductive layer 110.

[0367] The positive electrode material 106 and the negative electrode material 103 are immersed in or in contact with the electrolyte 108. The positive electrode material 106 and the electrolyte 108 do not necessarily have to be separated, and the positive electrode material may be configured as a mixture of the positive electrode material 106 and the electrolyte. Similarly, the negative electrode material 103 and the electrolyte 108 do not necessarily have to be separated, and the negative electrode material may be configured as a mixture of the negative electrode and the electrolyte.

[0368] The positive electrode material 106, negative electrode material 103, and electrolyte 108 should be constructed by selecting materials and components according to the type of secondary battery, such as a zinc (secondary) battery 500 or a fluoride ion battery. Furthermore, the negative electrode 102 and negative electrode material 103 of each secondary battery contain zinc (Zn), indium (In), tin (Sn), or copper (Cu), and are alloyed with these metals to form a metal alloy film 603.

[0369] The spacing between the positive electrode material 106 and the negative electrode material 103 is configured to be variable. By shortening the distance between the positive electrode material 106 and the negative electrode material 103, the resistance between the electrodes can be reduced. The spacing between the positive electrode material 106 and the negative electrode material 103 can be set and adjusted by changing the positions of the positive terminal 107 and the negative terminal 104.

[0370] As shown in Figure 44(a), the elastic body 207 is not deformed when the pressure cap 208 is not pressed down. As shown in Figure 44(b), the elastic body 207 deforms when the pressure cap 208 is pressed down. When the elastic body 207 deforms, the position of the separator 109 in Figure 44(b) changes relative to the position of the separator 109 in Figure 44(a).

[0371] The change in the position of the separator 109 causes the position of the small hole 206 to shift, which can cut or destroy the dendrite 205, as shown in Figure 42. By cutting or otherwise destroying the dendrite 205, the growth of the dendrite 205 can be stopped. In addition, short circuits between electrodes caused by the dendrite 205 can be prevented.

[0372] Figure 44(b) shows the state in which the pressure cap 208 is pressed, while Figure 44(a) shows the state in which the pressure cap 208 is not pressed. The state shown in Figure 44(a) and Figure 44(b) can be switched by whether or not the pressure cap 208 is pressed.

[0373] Figure 45 is an explanatory diagram illustrating an embodiment in which the press-button cap 208 is pressed by attaching the zinc secondary battery 500 of the present invention to the battery box 301, and the press-button cap 208 is released from the pressed state by removing the zinc secondary battery 500 from the battery box 301.

[0374] The battery box 301 is fitted with a spring fitting 302 and a connecting fitting 303. As shown in Figure 45(a), when the zinc secondary battery 500 is not installed in the battery box 301, the press cap 208 of the zinc secondary battery 500 is not pressed. Therefore, the separator 109 is in an unpressed state.

[0375] As shown in Figure 45(b), when the zinc secondary battery 500 is installed in the battery box 301, the zinc secondary battery 500 is sandwiched between the spring fitting 302 and the connecting fitting 303. The pressure cap 208 of the zinc secondary battery 500 is pressed by the spring fitting 302. Therefore, the separator 109 is in a pressed state.

[0376] As shown in Figure 45(b), by switching between a state in which the zinc secondary battery 500 is installed in the battery box 301 and a state in which the zinc secondary battery 500 is not installed in the battery box 301, as shown in Figure 45(a), the position of the separator 109 can be changed, and as shown in Figure 42, the dendrite 205 can be cut or destroyed.

[0377] In the embodiments of the present invention, the position of the separator 109 is described as being changed. Alternatively, vibrations such as ultrasonic vibrations may be applied to the separator 109 to cause it to vibrate, thereby changing the position of the separator 109, the small hole 206, etc., and cutting or destroying the dendrite 205.

[0378] The embodiment shown in Figure 45 involved a configuration and method for preventing or suppressing short circuits caused by dendrites 205 by attaching and removing a zinc secondary battery 500 from a battery box 301. The present invention is not limited thereto. Figure 46 is an explanatory diagram of a configuration and method for achieving a change in the position of the separator 109 of the zinc secondary battery 500 in synchronization with the rotation of the rotating body 304.

[0379] The rotating body 304 has a protrusion 305 formed on or positioned on it. The rotating body 304 rotates around the center C as its axis. The rotational motion is not limited to continuous motion. As the rotating body 304 rotates, the position of the protrusion 305 moves in the direction of the arrow.

[0380] As shown in Figure 46(a), when the protrusion 305 is positioned at the location of the pressure cap 208, the pressure cap 208 is pressed, causing the position of the separator 109 to change. Alternatively, vibrations such as ultrasonic waves are applied to the separator 109. By applying or supplying vibrations, the dendrite 205 can be cut or destroyed.

[0381] As shown in Figure 46(b), when the protrusion 305 is not in contact with the pressure cap 208, the pressure cap 208 is not pressed, and the position of the separator 109 does not change. Alternatively, no vibration is applied to the separator 109.

[0382] As shown in Figure 46, the rotating body 304 rotates, causing the position of the protrusion 305 to rotate, which in turn causes the pressing cap 208 to be pressed or not pressed, and vibration is applied to the separator 109. By vibrating the separator 109, the positions of the separator 109, the small hole 206, etc. are changed, cutting or destroying the dendrite 205. By cutting or destroying the dendrite 205, the growth of the dendrite 205 can be stopped. In addition, short circuits between electrodes caused by the dendrite 205 can be prevented.

[0383] In the above embodiments, the dendrites 205 were destroyed by changing the position of the separator 109 or by vibrating the separator 109, but the present invention is not limited thereto.

[0384] Figure 47 shows an embodiment in which the position of the separator 109 is fixed, and the position of at least one of the positive electrode material 106 and the negative electrode material 103 can be changed, modified, or subjected to vibration.

[0385] The zinc secondary battery 500 has a positive electrode material 106, a negative electrode material 103, an electrolyte 108, a separator 109, etc., inside the battery container 101. The negative electrode material 103 is made of zinc, a zinc-containing metal, or a zinc alloy.

[0386] In the secondary battery of the present invention, the negative electrode 102 and negative electrode material 103 contain zinc, indium (In), tin (Sn), or copper (Cu), etc., and are alloyed with these metals to form a metal alloy film 603.

[0387] A negative electrode 102 is formed or arranged on the negative electrode material 103, a negative terminal 104 is connected to the negative electrode 102, and the negative terminal 104 is led out to the outside of the battery container 101. A positive electrode 105 is formed or arranged on the positive electrode material 106, a positive terminal 107 is connected to the positive electrode 105, and the positive terminal 107 is led out to the outside of the battery container 101. In addition, a conductive terminal 111 is connected to the conductive layer 110.

[0388] The positive electrode material 106 and the negative electrode material 103 are immersed in or in contact with an alkaline electrolyte 108. The positive electrode material 106 and the electrolyte 108 do not necessarily have to be separate, and the positive electrode material may be configured as a mixture of the positive electrode material 106 and the electrolyte, permeated, or immersed together. Similarly, the negative electrode material 103 and the electrolyte 108 do not necessarily have to be separate, and the negative electrode material may be configured as a mixture of the negative electrode and the electrolyte, permeated, or immersed together.

[0389] The positive electrode material 106, the negative electrode material 103, and the electrolyte 108 can be configured according to the type of zinc secondary battery. The distance between the positive electrode material 106 and the negative electrode material 103 is configured to be variable. By shortening the distance between the positive electrode material 106 and the negative electrode material 103, the output current of the battery can be increased.

[0390] The negative electrode material 103 is placed on the elastic body 207a, and the positive electrode material 106 is placed on the elastic body 207b. A negative electrode 102 is formed on or placed on the negative electrode material 103. A positive electrode 105 is formed on or placed on the positive electrode material 106. A negative terminal 104 is connected to the negative electrode 102, and a positive terminal 107 is connected to the positive electrode 105.

[0391] A pressure cap 208a is positioned on the negative electrode material 103 side, and the pressure cap 208a is attached to the pressure portion 209a. A pressure cap 208b is positioned on the positive electrode material 106 side, and the pressure cap 208b is attached to the pressure portion 209b.

[0392] In the embodiments of the present invention, the structure is described as a pressure cap 208, but it is not limited to a cap shape. Any configuration or method is acceptable as long as the component such as the pressure cap 208 can apply, supply, or generate mechanical pressure to the negative electrode material 103, positive electrode material 106, and separator 109. When the pressure cap 208 is not pressed down, the elastic body 207 is not deformed. When the pressure cap 208 is pressed down, the elastic body 207 deforms.

[0393] When the elastic body 207 is deformed, the position of the positive electrode material 106 or the negative electrode material 103 fluctuates or moves. By causing the position of the positive electrode material 106 or the negative electrode material 103 to fluctuate or move, the dendrites 205 can be cut or destroyed. Alternatively, the generation of dendrites 205 can be suppressed. Alternatively, the growth of dendrites 205 can be stopped by cutting or otherwise destroying them. Furthermore, short circuits between electrodes caused by dendrites 205 can be prevented.

[0394] Furthermore, by vibrating the positive electrode material 106 or the negative electrode material 103, the dendrites 205 can be cut or otherwise damaged, thereby stopping their growth. This also prevents short circuits between electrodes caused by the dendrites 205.

[0395] Figures 48, 49, and 50 are configuration diagrams and explanatory diagrams of a battery unit having multiple zinc secondary batteries according to the present invention. In Figures 48, 49, and 50, the zinc secondary battery 500 is shown as battery B. The capacity of the zinc secondary batteries 500 is not limited to being the same. The capacities of the zinc (secondary) batteries 500 may be different.

[0396] Figure 48 is an explanatory diagram of the battery unit of the present invention. As shown in Figure 48, the battery unit of the present invention has a battery unit 307a and a battery unit 307b configured or arranged within a housing 509.

[0397] As one embodiment shown in Figure 48, battery unit 307a has two batteries B. Battery unit 307b has twelve batteries B. The batteries B are connected to the negative terminal 104 and the positive terminal 107 by connecting wires 306a, 306b, and 306c.

[0398] Battery B of battery unit 307a is connected to the positive terminal 107b of housing 509 and to the negative terminal 104 of housing 509. Battery B of battery unit 307b is connected to the positive terminal 107a of housing 509 and to the negative terminal 104 of housing 509.

[0399] In the embodiment shown in Figure 48, battery unit 307a and battery unit 307b share a common negative terminal 104. The positive terminal 107b of battery unit 307a and the positive terminal 107a of battery unit 307b are independent. Battery unit 307a has 2 batteries B, and battery unit 307b has 12 batteries B, so the capacity of battery unit 307b is greater than the capacity of battery unit 307a.

[0400] In the embodiment shown in Figure 48, the negative terminal 104 of battery unit 307a and the negative terminal 104 of battery unit 307b are made common, the positive terminal of battery unit 307a is connected to the positive terminal 107b, and the positive terminal of battery unit 307b is connected to the positive terminal 107a. This allows for the configuration of multiple battery units 307 with the same voltage value but different power capacities. Battery units of different capacities can be used in a single housing 509.

[0401] Figure 49 is an explanatory diagram of the battery unit of the present invention in another embodiment. As shown in Figure 49, the battery unit of the present invention has a battery unit 307a and a battery unit 307b configured or arranged within a housing 509.

[0402] As one embodiment shown in Figure 49, battery unit 307a has four batteries B. Battery unit 307b has twelve batteries B. The batteries B are connected to the negative terminal 104 or the positive terminal 107 by connecting wires 306a, 306b, and 306c.

[0403] Two batteries B in battery unit 307a are connected to the positive terminal 107b, and the other two batteries B in battery unit 307a are connected to the positive terminal 107c. All four batteries B in battery unit 307a are connected to the common negative terminal 104b. The batteries B in battery unit 307b are connected to the positive terminal 107a and the negative terminal 104a.

[0404] In the embodiment shown in Figure 49, battery units 307a and 307b are separated into negative terminals 104a and 104b. The positive terminal 107a of battery unit 307a and the positive terminals 107b and 107c of battery unit 307b are kept separate. Battery unit 307a has 4 batteries B, and battery unit 307b has 12 batteries B, so the capacity of battery unit 307b is greater than the capacity of battery unit 307a.

[0405] In the embodiment shown in Figure 49, by separating the negative terminal 104b of battery unit 307a from the negative terminal 104a of battery unit 307b, connecting the positive terminal of battery unit 307b to the positive terminal 107a, and connecting the positive terminal of battery unit 307a to either the positive terminal 107b or the positive terminal 107c, multiple battery units 307 with the same voltage value but different power capacities can be configured. Furthermore, power supply units 307a and 307b can be used as batteries with independent potentials.

[0406] The embodiment shown in Figure 50 has a battery device configured with a switch circuit 505 in a housing 509. Turning the switch circuit 505 on (closed) connects battery B to the positive terminal 107. Turning the switch circuit 505 off (open) disconnects battery B from the positive terminal 107. The on / off state of the switch circuit 505 is controlled by the drive control circuit 506 based on the magnitude of the current output from the positive terminal 107. The magnitude of the current is measured and monitored by a current sensor 508, as shown in Figure 51.

[0407] Figure 50(a) shows an embodiment in which the battery unit 307 has six batteries. It goes without saying that the number of batteries is not limited to six; it can be six or fewer, or six or more. Switch circuits 505 (switch circuits S1 to S6) are arranged for batteries 500 (batteries B1 to B6). In Figure 50(a), switch circuit S6 is open, and the other switch circuits are closed. The more switch circuits 505 that are turned on, the larger the current value that can be output from the positive terminal 107 can be.

[0408] The negative electrodes of the six batteries 500 are connected to the negative terminal 104, which is connected to ground "GND". The positive electrodes of the six batteries 500 are connected to the positive terminals 107a and 107b, which output a (predetermined) voltage "V1". The positive terminals 107a and 107b are located at both ends of the battery unit 307.

[0409] If there is a difference between the voltage "V1" at positive terminal 107a and the voltage "V1" at positive terminal 107b, the drive control circuit 506 controls the position and number of switches 505 to be turned on, so that the voltage "V1" at positive terminal 107a and the voltage "V1" at positive terminal 107b become the same.

[0410] Figure 50(b) shows an embodiment in which battery B is arranged in two series stages, with six sets of these two-stage battery configurations. Note that this is not limited to two stages; three or more stages are also possible. Furthermore, it goes without saying that batteries can be connected in parallel or series.

[0411] Figure 50(b) shows one embodiment in which there are six sets of two-stage series connections. A switch circuit 505 (switch circuits S1 to S6) is arranged for the batteries 500 (batteries B1a to B6a, batteries B1b to B6b).

[0412] In Figure 50(b), switch circuits S4 and S6 are open, while the other switch circuits are closed. The more switch circuits 505 that are turned on, the larger the current that can be output from the positive terminal 107.

[0413] The negative electrodes of the four battery sets located on the left side of Figure 50(b) are connected to negative terminal 104a, which is connected to ground 1 "GND1". The negative electrodes of the two battery sets located on the right side of the figure are connected to negative terminal 104b, which is connected to ground 2 "GND2".

[0414] In Figure 50(b), the positive electrodes of the four sets of batteries located on the left are connected to the positive terminal 107a, which outputs a voltage of 1"V1". The positive electrodes of the two sets of batteries located on the right are connected to the positive terminal 107b, which outputs a voltage of 2"V2". However, in the embodiment shown in Figure 50(b), since the number of battery stages is the same at 2 stages, there is no difference between voltages V1 and V2. To make voltages V1 and V2 different, the number of stages of battery B must be different.

[0415] Furthermore, if negative terminal 104a is designated as "GND1" and negative terminal 104b is designated as "GND2", it goes without saying that voltages "V1" and "V2" can be made to have different potentials. Figure 51 is a block diagram and explanatory diagram relating to the circuit or control of the electric bicycle and electric assist bicycle of the present invention.

[0416] In Figure 51, battery unit 307 is a battery unit consisting of the zinc (secondary) battery 500 of the present invention. Battery unit 308 is a battery unit consisting of a lithium-ion secondary battery. In addition, a large-capacity capacitor 507 is included to handle steep current output.

[0417] Electric bicycles and electric assist bicycles are equipped with motor 501. Motor 501 is a three-phase brushless motor and is located on the front wheel. However, motor 501 is not limited to a three-phase brushless motor. A two-pole DC motor 501 or the like may also be used. The electric vehicle and electric assist bicycle of the present invention are equipped with a regenerative charging function that charges the battery unit 307 with electricity generated from the motor 501 during braking.

[0418] For example, when a rider is operating an electric bicycle, if they apply the brakes, the regenerative braking charging function is activated, and the electricity generated from the motor 501 charges the battery unit 307.

[0419] The drive control circuit 506 is fitted with or positioned a position detection sensor 502 for the motor 501 (which performs functions such as detecting the rotation state and measuring the rotation speed). The output of the position detection sensor 502 is input to a vehicle speed input circuit (not shown).

[0420] The inverter circuit 504 includes an H-side FET (Ssu) and an L-side FET (Smu) for switching the U-phase of the motor 501, an H-side FET (Ssv) and an L-side FET (Smv) for switching the V-phase of the motor 501, and an H-side FET (Ssw) and an L-side FET (Smw) for switching the W-phase of the motor 501.

[0421] The H side is sometimes called the upper side, and the L side is sometimes called the lower side. The inverter circuit 504 is equipped with a temperature sensor 503a, and the motor 501 is equipped with a temperature sensor 503b.

[0422] The inverter circuit 504 is connected to one end of the capacitor 507, and the other end of the capacitor 507 is grounded. The capacitance of the capacitor 507 is relatively large.

[0423] The switch circuit 505 is located between the inverter circuit 504 and the battery unit, and operates to isolate the battery unit from the inverter circuit 504 in response to instructions from the drive control circuit 506. It also electrically connects the battery unit and the inverter circuit 504.

[0424] By controlling the on-time of the transistor in the inverter circuit 504, the power applied to the motor 501 can be adjusted. Furthermore, the voltage (power) generated by the motor 501 can be adjusted.

[0425] The switch circuit 505 is connected to the inverter circuit 504. A current sensor 508 is placed in the power path to the inverter circuit 504, allowing for the measurement of the input current and output current to the inverter circuit 504. The operation (open / closed) of switches SWa and SWb in the switch circuit 505 is varied or set based on the current value measured by the current sensor 508.

[0426] Lithium-ion batteries are susceptible to overcharging and over-discharging. Furthermore, because the electrolyte liquid is flammable, high temperatures can cause violent chemical reactions inside, leading to ignition. At sub-zero temperatures, not only does the discharge capacity decrease, but the electrolyte liquid can freeze, damaging the internal components and potentially leading to fire.

[0427] Zinc-ion batteries use an aqueous electrolyte, making them highly safe. Furthermore, zinc-ion batteries are highly recyclable and have an energy density approximately twice that of lead-acid batteries. However, repeated charging and discharging can cause zinc to precipitate from the negative electrode, potentially leading to a short circuit with the positive electrode.

[0428] The battery housing 509 of the present invention has a battery unit 307 made of a zinc secondary battery and a battery unit 308 made of a lithium-ion battery. A temperature sensor 503c is located in the battery housing 509. The temperature sensor 503c measures the temperature of the battery housing 509.

[0429] If the temperature is within a predetermined range, the switch SWa of the switch circuit 505 is turned on, and power from the battery unit 308, which consists of a lithium-ion battery, is used. Also, if there is a large change in the output current, power from the battery unit 308 is used.

[0430] If the temperature is above or below a predetermined value, switch SWb of the switch circuit 505 is turned on, and power from the battery unit 307, which consists of a zinc secondary battery, is used. Also, if the output current is stable and large, power from the battery unit 307 is used. If a large output current is required, both switches SWa and SWb of the switch circuit 505 are turned on. [Industrial applicability]

[0431] The zinc secondary battery of this invention enables faster charging and discharging compared to lithium-ion batteries and the like. It has excellent high-power characteristics. It is expected to have applications in various fields, such as energy storage for new energy sources. Furthermore, it is inexpensive. In addition, it does not experience short-circuit failures, has a long lifespan, and is expected to be used in a variety of fields. [Explanation of symbols]

[0432] 101 Battery container 102 Negative electrode 103 Negative electrode material 104 negative terminal 105 Positive electrode 106 Cathode material 107 Positive terminal 108 Electrolyte 109 Separator 110 Conductive layer 111 Conductive terminals 112 (Variable) Voltage (Current) Source 114 Switch Circuit 115 Insulating layer 116 Resistance meter 117 Pulse Generator 201 Negative Electrode Case 202 Positive Electrode Case 203 Gasket 204 Insulating film 205 Dendrites 206 Small hole (small hole) 207 Elastic material (elastic material, elastic agent) 208 Pressing cap (pressing part, pressing material) 209 Pressing part 301 Battery Box (Battery Storage Container) 302 Spring fittings 303 Connecting fittings 304 Rotating body 305 Convex part 306 Connection Wiring 307 Battery Unit 308 Battery Unit 500 batteries 501 Motor 502 Position detection sensor 503 Temperature Sensor 504 Inverter Circuit 505 Switch Circuit 506 Drive Control Circuit 507 Capacitor 508 Current Sensor 509 cabinets 601 Metal films (plating films, metal foils, metal layers) 602 Base metal foil (metal sheet, metal plate, metal film, substrate, electrode material) 603 Metal alloy film (metal alloy foil) 604 Electrode 605 Electrode 606 Electrolyte 607 Element Electrode 608 element electrodes 609 Cooling and heating element (Peltier element) 611 p-type semiconductor 612 n-type semiconductor 614 Electrode foil (electrode material, electrode substrate, electrode film, electrode sheet) 615 Insulating film (insulating material) 621 Heater electrode 622 Temperature probe electrode 623 Thin-film heater 624 Thin Film Temperature Probe 625 Heater Tip 626 Heater 627 Cooler (cooling plate) 628 Sealed cover 629 Chiller 631 Circulating fluid pipe (circulating water pipe) 632 Laser light 634 Laser irradiator 635 Voltage Electrode 636 Roller 637 Roller 638 Vapor deposition equipment

Claims

[Claim 1] A first step of forming a metal film on a base substrate, A method for manufacturing an electrode for a secondary battery, characterized by comprising a second step of generating a temperature gradient between the metal film and the base substrate by thermomigration, thereby alloying the metal film or the base substrate with the metal film.

Images