Liquid hydrogen carrier, method for producing liquid hydrogen carrier, charge / discharge cell, secondary battery, hydrogen filling device, power generation device, hydrogen filling and power generation device, hydrogen filling system, power generation system, hydrogen filling and power generation system, energy transport method

Abstract

A hydrogen carrier having fluidity according to the present invention includes a hydrogen absorbing alloy and an alkaline electrolyte.

Description

Technical Field

[0001] The present invention relates to a fluid hydrogen carrier, a method for producing a fluid hydrogen carrier, a charge-discharge cell, a secondary battery, a hydrogen filling device, a power generation device, a hydrogen filling and power generation device, a hydrogen filling system, a power generation system, a hydrogen filling and power generation system, and an energy transport method.

Background Art

[0002] In recent years, from the viewpoint of environmental problems, the introduction of power generation using renewable energy has been actively promoted. When transporting electricity generated by power generation facilities such as solar panels and wind turbines, there are costs for constructing and maintaining the infrastructure required for power transmission and power transmission losses. Therefore, an energy operation method has been studied in which renewable energy is converted into hydrogen, and the converted hydrogen is transported to a battery or the like for power generation.

[0003] As a method for transporting hydrogen, for example, Patent Document 1 proposes a method of compressing hydrogen at high pressure for transportation. In the method of Patent Document 1, by compressing at high pressure, the volume can be reduced, and furthermore, it can be filled into a high-pressure tank of a fuel cell vehicle or the like at that pressure, so that a large amount of hydrogen can be transported.

[0004] Patent Document 2 proposes a method of liquefying hydrogen for transportation. In the method of Patent Document 2, liquid hydrogen has a high density and no shape, so the filling rate into a container is also high, and a large amount of transportation can be easily performed.

[0005] Non-Patent Document 1 proposes a method of extracting hydrogen using an organic hydride method. The organic hydride method is a technique in which, for example, toluene and hydrogen are reacted to produce methylcyclohexane, methylcyclohexane is transported by a tanker, and hydrogen is extracted by a dehydrogenation process that returns methylcyclohexane to toluene. In the method of Non-Patent Document 1, hydrogen can be transported as a liquid. Liquid hydrogen has a high density and no shape, so the filling rate into a container is also high, and it can be efficiently transported in large quantities.

[0006] In Patent Document 3, a method of storing hydrogen in a tank containing a hydrogen storage alloy and transporting it has been proposed. In the method of Patent Document 3, by storing hydrogen in the hydrogen storage alloy, hydrogen can be densified and transported at a pressure lower than that of the high-pressure tank method, enabling a large amount of transportation.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0008]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0009] However, in the technology of Patent Document 1, since a large amount of energy is required to compress hydrogen to a high pressure, high-efficiency transportation is difficult.

[0010] In the technology of Patent Document 2, since a cryogenic environment of -253°C is required to liquefy hydrogen for transportation, a large amount of energy is required and high-efficiency transportation is difficult.

[0011] In the technology of Non-Patent Document 1, since a large amount of energy such as heating at 350°C to 400°C is required when desorbing hydrogen from an organic hydride, high-efficiency operation is difficult when considering the use of hydrogen after transportation.

[0012] In the technology of Patent Document 3, since temperature or pressure control is required when adsorbing and desorbing hydrogen, it is difficult to precisely control the amount of hydrogen supplied to the cell stack. Therefore, there is a possibility that the pressure may rise above the expected value, and the pressure resistance design of the tank containing the hydrogen storage alloy has to be increased, resulting in an increase in the weight of the tank itself. In addition, since the tank is rigid, there is a problem that the filling efficiency of the tank into tankers, containers, etc. during transportation is lower than that of liquids.

[0013] One aspect of the present invention has been made in view of the above circumstances, and an object thereof is to provide a fluid hydrogen carrier capable of transporting a large amount of hydrogen with high efficiency at normal temperature and normal pressure.

Means for Solving the Problems

[0014] One aspect of the fluid hydrogen carrier according to the present invention includes a hydrogen storage alloy and an alkaline electrolyte.

[0015] One aspect of the present invention is a fluid hydrogen carrier including a hydrogen storage alloy and an alkaline electrolyte.

[0016] Another aspect of the present invention is a method for manufacturing a fluid hydrogen carrier using the above fluid hydrogen carrier, which includes a step of heating at 80 °C or higher.

[0017] Another aspect of the present invention is a method for manufacturing a fluid hydrogen carrier using the above fluid hydrogen carrier, which includes a step of pulverizing the hydrogen storage alloy in a state where the hydrogen storage alloy and the alkaline solution are mixed.

[0018] Another aspect of the present invention is a charge and discharge cell including a negative electrode current collector, a positive electrode current collector, an oxygen electrode catalyst, and an ion permeable membrane, A part of the negative electrode current collector is electrically connected to the above-mentioned fluid hydrogen carrier. A part of the positive electrode current collector is electrically connected to the oxygen electrode catalyst. A part of the oxygen electrode catalyst is ionically connected to the ion permeable membrane. The ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector. A part of the fluid hydrogen carrier is ionically connected to the ion permeable membrane in a charge-discharge cell.

[0019] Another aspect of the present invention is A secondary battery including the above charge-discharge cell.

[0020] Another aspect of the present invention is A negative electrode current collector, a negative electrode void capable of filling the above-mentioned fluid hydrogen carrier, a positive electrode current collector, a positive electrode void, an oxygen generation electrode, and an ion permeable membrane, The negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane, The positive electrode void is in contact with the oxygen generation catalyst, A part of the positive electrode current collector is electrically connected to the oxygen generation catalyst, A part of the oxygen generation catalyst is in contact with an aqueous alkali solution, A part of the oxygen generation catalyst is ionically connected to the ion permeable membrane, The ion permeable membrane is a hydrogen filling device provided so as to isolate the negative electrode current collector and the positive electrode current collector.

[0021] Another aspect of the present invention is A negative electrode current collector, a negative electrode void capable of filling the above-mentioned fluid hydrogen carrier filled with hydrogen, a positive electrode current collector, a positive electrode void, an oxygen reduction catalyst, and an ion permeable membrane, The negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane, The positive electrode void is in contact with the oxygen reduction catalyst, A part of the positive electrode current collector is electrically connected to the oxygen reduction catalyst, A part of the oxygen reduction catalyst is ionically connected to the ion permeable membrane, A part of the oxygen reduction catalyst is in contact with air, The ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector, and it is a power generation device.

[0022] Another aspect of the present invention is It includes a negative electrode current collector, a negative electrode void that can be filled with the above-mentioned fluid hydrogen carrier, a positive electrode current collector, a positive electrode void, a binary catalyst capable of both oxygen generation and oxygen reduction, and an ion permeable membrane. The negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane, The positive electrode void is in contact with the binary catalyst, A part of the positive electrode current collector is electrically connected to the binary catalyst, A part of the binary catalyst is in contact with air or an alkaline aqueous solution, The ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector, and it is a hydrogen filling and power generation device.

[0023] Another aspect of the present invention is It includes a negative electrode current collector, a negative electrode void that can be filled with a fluid hydrogen carrier, a positive electrode current collector, a positive electrode void, and an ion permeable membrane. The negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane, The positive electrode void is in contact with both the positive electrode current collector and the ion permeable membrane, The ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector, and it is a hydrogen filling and power generation device.

[0024] Another aspect of the present invention is It has a tank for storing the fluid hydrogen carrier, a fluid nickel hydroxide slurry, or an alkaline electrolyte, The tank is connected to the positive electrode or the negative electrode void of the hydrogen filling device according to claim 13. A hydrogen filling system having a pressurizing / de-pressurizing device capable of filling / discharging a fluid hydrogen carrier, a fluid nickel hydroxide slurry, air, oxygen, or an alkaline electrolyte into / from the positive or negative electrode voids.

[0025] Another aspect of the present invention is having a tank for storing the fluid hydrogen carrier, the fluid nickel hydroxide slurry, or the alkaline electrolyte, the tank being connected to the positive or negative electrode voids of the above-described power generation device, a power generation system having a pressurizing / de-pressurizing device capable of filling / discharging a fluid hydrogen carrier, a fluid nickel hydroxide slurry, air, oxygen, or an alkaline electrolyte into / from the positive or negative electrode voids.

[0026] Another aspect of the present invention is having a tank for storing the fluid hydrogen carrier, the fluid nickel hydroxide slurry, or the alkaline electrolyte, the tank being connected to the positive or negative electrode voids of the above-described hydrogen filling and power generation device, a hydrogen filling and power generation system having a pressurizing / de-pressurizing device capable of filling / discharging a fluid hydrogen carrier, a fluid nickel hydroxide slurry, air, oxygen, or an alkaline electrolyte into / from the positive or negative electrode voids.

[0027] Another aspect of the present invention is an energy transportation method of extracting the hydrogen-filled fluid hydrogen carrier or the fluid hydrogen carrier and the fluid nickel hydroxide slurry from the above-described power generation system and transporting the hydrogen-filled fluid hydrogen carrier or the fluid hydrogen carrier and the fluid nickel hydroxide slurry.

[0028] Another aspect of the present invention is an energy transportation method of extracting the hydrogen-filled fluid hydrogen carrier or the fluid hydrogen carrier and the fluid nickel hydroxide slurry from the above-described hydrogen filling and power generation system and transporting the hydrogen-filled fluid hydrogen carrier or the fluid hydrogen carrier and the fluid nickel hydroxide slurry.

Advantages of the Invention

[0029] One aspect of the fluid hydrogen carrier according to the present invention can transport a large amount of hydrogen at high efficiency under normal temperature and pressure.

Brief Description of the Drawings

[0030]

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Embodiments for Carrying Out the Invention

[0031] Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. For the sake of easy understanding of the description, the same reference numerals are given to the same components in each drawing, and duplicate descriptions are omitted. Also, the scales of the respective members in the drawings may be different from the actual ones. In this specification, "~" indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value, unless otherwise specified.

[0032] <Fluid hydrogen carrier> The fluid hydrogen carrier according to this embodiment will be described. FIG. 1 is a schematic cross-sectional view showing the configuration of the fluid hydrogen carrier according to an embodiment of the present invention. As shown in FIG. 1, the fluid hydrogen carrier 10 according to an embodiment of the present invention is a mixture containing a hydrogen storage alloy 11 and an alkaline electrolyte 12, and may optionally contain additive components such as a dispersant, a thickener, a surfactant, and an electrically conductive filler in an appropriate arbitrary amount. The fluid hydrogen carrier 10 contains the hydrogen storage alloy 11 in a state of being dispersed in the alkaline electrolyte 12.

[0033] Note that the fluid hydrogen carrier 10 may have a low viscosity or a high viscosity, and the viscosity of the fluid hydrogen carrier 10 can be appropriately set according to the ratio of the hydrogen storage alloy and the alkaline electrolyte contained in the fluid hydrogen carrier 10. The fluid hydrogen carrier 10 may have a high viscosity such that it becomes, for example, creamy or whipped. In the present embodiment, even if the viscosity of the fluid hydrogen carrier 10 is high, for example, when the fluid hydrogen carrier 10 is dropped onto a flat plate and the plate is tilted and the fluid hydrogen carrier 10 hardly flows, it may be included in the fluid hydrogen carrier 10 as long as it can be flowed by a conveying device such as a pump.

[0034] (hydrogen storage alloy) The hydrogen storage alloy 11 contained in the fluid hydrogen carrier according to the present embodiment has a function of reversibly performing hydrogen storage and release and has a substantially particulate shape.

[0035] The material of the hydrogen storage alloy 11 is not particularly limited as long as it can absorb and release hydrogen. Examples of the hydrogen storage alloy 11 include La-Ni alloys, La-Nd-Ni alloys, La-Gd-Ni alloys, La-Y-Ni alloys, La-Co-Ni alloys, La-Ce-Ni alloys, La-Ni-Ag alloys, La-Ni-Fe alloys, La-Ni-Cr alloys, La-Ni-Pd alloys, La-Ni-Cu alloys, La-Ni-Al alloys, La-Ni-Mn alloys, La-Ni-In alloys, La-Ni-Sn alloys, La-Ni-Ga alloys, La-Ni-Si alloys, La-Ni-Ge alloys, La-Ni-Al-Co alloys, La-Ni-Al-Mn alloys, La-Ni-Al-Cr alloys, La-Ni-Al-Cu alloys, La-Ni-Al-Si alloys, La-Ni-Al-Ti alloys, La-Ni-Al-Zr alloys, La-Ni-Mn-Zr alloys, La-Ni-Mn-Ti alloys, La-Ni-Mn-V alloys, La-Ni-Cr-Mn alloys, La-Ni-Cr-Zr alloys, La-Ni-Fe-Zr alloys, La-Ni-Cu-Zr alloys, and alloys in which the La element in the above alloys is replaced with mischmetal (a mixture of rare earth elements mainly composed of Ce and La); alloys composed of combinations of two or more of Ti, Fe, Mn, Al, Ce, Ca, Mg, Zr, Nb, V, Co, Ni, Cr elements such as Ti-Zr-Mn-Mo alloys, Zr-Fe-Mn alloys, Mg-Ni alloys; metals that form hydrides (having hydrogen storage properties) such as Ti, V, Zr, La, Pd, Pt; hydrides (substances that have absorbed hydrogen) of the above alloys or the above metals, etc. These may be used alone or in combination of two or more.

[0036] The shape of the hydrogen storage alloy 11 is not particularly limited, and may be, for example, spherical, ellipsoidal, spindle-shaped, crushed, plate-shaped, columnar, etc.

[0037] The average particle diameter of the hydrogen storage alloy 11 is 50 μm or less. When it is larger than 50 μm, in the process of filling hydrogen into the fluid hydrogen carrier 10, problems such as the hydrogen storage alloy 11 clogging the flow path and having a high sedimentation rate will occur. In the range of 50 μm or less, the average particle diameter of the hydrogen storage alloy 11 can be set as appropriate. For example, 1 μm to 50 μm is preferable, 5 μm to 40 μm is more preferable, and 10 μm to 20 μm is even more preferable. When the average particle diameter is too small, the viscosity of the fluid hydrogen carrier 10 increases, which hinders fluidity. If the average particle diameter of the hydrogen storage alloy 11 is within the above-preferred range, the hydrogen storage alloy 11 can be well dispersed in the alkaline electrolyte 12 while maintaining the contact area with the alkaline electrolyte 12.

[0038] Note that the average particle diameter refers to the volume average particle diameter by the effective diameter, and the average particle diameter is measured, for example, by a laser diffraction / scattering method or a dynamic light scattering method. The average particle diameter may be the particle diameter (median diameter) when the cumulative amount occupies 50% by volume from the smaller particles in the particle size distribution curve obtained by measuring the particle size distribution of the hydrogen storage alloy 11.

[0039] The hydrogen storage alloy 11 may be a porous body or a non-porous body, and is appropriately selected according to the material used.

[0040] When the hydrogen storage alloy 11 is a porous body, its specific surface area is not particularly limited and may be arbitrarily set as appropriate according to the type, size, etc. of the hydrogen storage alloy 11. The specific surface area can be measured, for example, by a specific surface area measuring device using the gas adsorption method.

[0041] The content of the hydrogen storage alloy 11 is 15% by volume or more with respect to the flowable hydrogen carrier 10. If it is less than this, the energy density as the flowable hydrogen carrier 10 will decrease. Also, if it is less than this, the ratio of the metal component in the flowable hydrogen carrier 10 will decrease, and the electrical conductivity of the flowable hydrogen carrier 10 will decrease, so that electrochemical hydrogen filling and power generation cannot be sufficiently performed. The content of the hydrogen storage alloy 11 only needs to be 15% by volume or more with respect to the flowable hydrogen carrier 10. For example, 15% by volume to 50% by volume is preferable, and 20% by volume to 40% by volume is more preferable.

[0042] (Alkaline electrolyte) The alkaline electrolyte 12 contains a supporting electrolyte and water.

[0043] The supporting electrolyte is dissolved in water.

[0044] The supporting electrolyte may be, for example, potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), etc. These may be used alone or in combination of two or more.

[0045] The supporting electrolyte is preferably contained in the alkaline electrolyte 12 at, for example, 1 mol / L to 12 mol / L, more preferably 5 mol / L to 10 mol / L, and even more preferably 6 mol / L to 8 mol / L. If the supporting electrolyte is contained in the alkaline electrolyte 12 at 1 mol / L to 20 mol / L, the ionic conductivity of the alkaline electrolyte 12 can be increased. If the supporting electrolyte is contained in the alkaline electrolyte 12 at 5 mol / L to 8 mol / L, the ionic conductivity of the alkaline electrolyte 12 can be increased most.

[0046] (Thickening agent) The flowable hydrogen carrier 10 contains a thickening agent.

[0047] The viscosity of the flowable hydrogen carrier 10 is at a shear rate of 100 sec ―1It is preferable that the viscosity at this time is 100 mPa·sec or more. When the viscosity is lower than this, the precipitation of the hydrogen storage alloy is remarkable and the fluidity deteriorates.

[0048] The thickener may be used alone as one kind of organic polymer dissolved in the alkaline electrolyte 12, or may be used in combination of two or more kinds. Preferably, in order to enhance the thickening effect more, a water-soluble organic polymer having a weight average molecular weight of 1500 or more is good. More preferably, it is preferable to use polyacrylate as the water-soluble organic polymer, and it is further preferable to use sodium polyacrylate as the water-soluble organic polymer.

[0049] (Thixotropic agent) The fluid hydrogen carrier 10 contains a thixotropic agent. A thixotropic agent is an additive that exhibits thixotropy by being mixed with a liquid, and thixotropy is a property in which the viscosity decreases when a shear stress is applied and the viscosity increases in a stationary state. By adding a thixotropic agent, the precipitation of the hydrogen storage alloy 11 in the fluid hydrogen carrier 10 in a stationary state can be suppressed.

[0050] The thixotropic agent is not particularly limited as long as it is a material capable of expressing thixotropy in the fluid hydrogen carrier 10. Examples of the thixotropic agent include silica fine particles, bentonite, calcium carbonate, castor oil, fatty acid ester, polyether, glycol ether, carbon black, etc. These may be used alone or in combination of two or more kinds. More preferably, carbon black is used. Among the above thixotropic agents, carbon black has high electrical conductivity by itself. Therefore, it not only suppresses the precipitation of the hydrogen storage alloy 11, but also has an effect of increasing the electrical conductivity of the fluid hydrogen carrier 10.

[0051] In order to exhibit thixotropy with a smaller addition amount, it is better to use fine particles of the thixotropic agent. By using smaller particles, a dense network is formed during standing, so that the sedimentation suppressing effect of the hydrogen storage alloy 11 becomes greater. Although there is no particular limitation on the particle size, it is preferably 1 μm or less.

[0052] (Method for manufacturing a fluid hydrogen carrier) The method for manufacturing the fluid hydrogen carrier 10 is not particularly limited. For example, it includes a step of heating to 80°C or higher in a state where at least the hydrogen storage alloy 11 and the alkaline electrolyte 12 are mixed. This has the effect of removing the non-conductive oxide film on the surface of the hydrogen storage alloy 11 and the effect of forming a nickel-rich layer with high electrical conductivity on the surface of the hydrogen storage alloy 11.

[0053] When the raw material of the hydrogen storage alloy 11 contains coarse particles of 50 μm or more, it is necessary to grind it. The hydrogen storage alloy 11 can be ground by a ball mill, a jet mill, etc. However, when grinding in the air, the surface is oxidized. Since the specific surface area becomes larger as the particle size becomes smaller, there is a risk of heat generation and explosion during oxidation when a large amount of the hydrogen storage alloy 11 is ground. Therefore, when grinding the hydrogen storage alloy, it is carried out in a state where the hydrogen storage alloy 11 and the alkaline electrolyte 12 are mixed. The equipment used for grinding is not limited, but a ball mill, a jet mill, etc. can be used.

[0054] Thus, the fluid hydrogen carrier 10 contains the hydrogen storage alloy 11 in the alkaline electrolyte 12 and contains the hydrogen storage alloy 11 in a state of being dispersed in the alkaline electrolyte 12. By dispersing the hydrogen storage alloy 11 in the alkaline electrolyte 12, the fluid hydrogen carrier 10 can store hydrogen at a high density while having fluidity at normal temperature and normal pressure. In addition, the fluid hydrogen carrier 10 can generate electricity (discharge) simultaneously with the release of hydrogen.

[0055] Therefore, when the fluid hydrogen carrier 10 is transported by a transport ship such as a tanker, it can efficiently transport a large amount of hydrogen at a high filling rate without being restricted by the shape. In addition, the fluid hydrogen carrier 10 can repeatedly absorb and release hydrogen.

[0056] <Charge and discharge cell> A charge and discharge cell to which the fluid hydrogen carrier according to the present embodiment is applied will be described. FIG. 2 is a diagram showing the charge and discharge cell. As shown in FIG. 2, the charge and discharge cell 20 has a negative electrode current collector 21, a positive electrode current collector 22, an oxygen electrode catalyst 23, an ion permeable membrane 24, and a sealing material 25, and a fluid hydrogen carrier 26 is filled in a space formed by the negative electrode current collector 21, the ion permeable membrane 24, and the sealing material 25. The fluid hydrogen carrier 26 is a mixture containing a hydrogen storage alloy 261 in an alkaline electrolyte 262. Since the fluid hydrogen carrier 26 is the fluid hydrogen carrier 10 according to the above-described present embodiment, details thereof are omitted.

[0057] (Negative electrode current collector) The negative electrode current collector 21 may be manufactured, for example, by subjecting the surface of a nickel plate, a steel plate, a stainless steel plate, etc. to roughened nickel plating, or by etching the surface of a nickel plate or nickel foil, or by using a nickel mesh, a nickel foam, or a nickel porous body, or by subjecting the surface of a steel plate or stainless steel plate whose surface has been roughened in advance by etching or the like to nickel plating. Further, unevenness may be formed on the surface, or it may be porous.

[0058] The negative electrode current collector 21 only needs to be arranged so as to be electrically connected to the fluid hydrogen carrier 26 and ionically connected to the ion permeable membrane 24. Note that ionically connected means that ion conduction is not blocked between the fluid hydrogen carrier 26 and the ion permeable membrane 24.

[0059] (Positive electrode current collector) The positive electrode current collector 22 is arranged such that a part of it is electrically connected to the oxygen electrode catalyst 23. The positive electrode current collector 22 is not particularly limited in terms of material and shape as long as it has electrical conductivity. For example, it may be a nickel plate, nickel mesh, nickel porous body, stainless steel mesh, stainless steel porous body, stainless steel felt, etc., carbon felt, carbon paper, or it may be manufactured by applying roughened nickel plating to their surfaces, or by etching the surfaces of nickel plates or nickel foils, or by applying nickel plating to the surface of stainless steel whose surface has been roughened in advance by etching or the like.

[0060] (Oxygen electrode catalyst) The oxygen electrode catalyst 23 is arranged such that a part of it is ionically connected to the ion permeable membrane 24. Note that ionically connected means that ion conduction is not blocked between the oxygen electrode catalyst 23 and the ion permeable membrane 24.

[0061] The oxygen electrode catalyst 23 may be one that generates hydroxide ions from oxygen, a catalyst that generates hydroxide ions from oxygen, or both. For example, platinum, rhodium, palladium, iridium, osmium, ruthenium, rhenium, gold, silver, nickel, cobalt, molybdenum, lanthanum, strontium, yttrium, bismuth iridium oxide, azaphthalocyanine-based metal complexes, etc. can be applied. The catalyst may be used alone or in combination of two or more.

[0062] The oxygen electrode catalyst 23 may be a catalyst layer composed of a catalyst supported on a carrier or a catalyst carrier without a carrier and a binder having ionic conductivity, which is coated on a base material such as a titanium mesh, titanium porous body, nickel mesh, nickel porous body, carbon paper, positive electrode current collector 22, etc.

[0063] As the carrier, acetylene black, Ketjen black, carbon nanotubes, carbon nanohorns, graphene, graphene oxide, nickel particles, etc. can be applied. To support the catalyst on the carrier, methods such as the impregnation method can be applied. Also, not only the structure in which the catalyst is supported on the carrier, but it is also possible to use a mixture of catalyst particles and particles that can serve as the carrier. In this case, the particles that can serve as the carrier may have a catalytic function, but it is not necessarily required to have one. Also, the particles that can serve as the carrier are preferably formed using a highly electrically conductive material.

[0064] The oxygen electrode catalyst 23 is disposed in electrical connection with the positive electrode current collector 22. Here, the electrically connected state means that there only needs to be an electrical connection between the oxygen electrode catalyst 23 and the positive electrode current collector 22, and a material having electrical conductivity may be interposed therebetween. For example, the oxygen electrode catalyst 23 may be formed on carbon paper, and the carbon paper and the oxygen electrode catalyst 23 may be connected.

[0065] The oxygen electrode catalyst 23 is disposed in an ionically connected state to the ion permeable membrane 24. Here, the ionically connected state means a state in which ion conduction is not blocked between the oxygen electrode catalyst 23 and the ion permeable membrane 24. For example, an electrolyte solution or water may be present between the oxygen electrode catalyst 23 and the ion permeable membrane 24.

[0066] (Ion Permeable Membrane) The ion permeable membrane 24 is disposed between the negative electrode current collector 21 and the positive electrode current collector 22 and isolates the negative electrode current collector 21 and the positive electrode current collector 22. The shape of the ion permeable membrane 24 is not particularly limited and may have any arbitrary shape as appropriate.

[0067] The ion-permeable membrane 24 can use both an anion exchange membrane and an anion exchange membrane and a cation exchange membrane. When using two sheets of an anion exchange membrane and a cation exchange membrane, the anion exchange membrane is arranged on the negative electrode current collector 21 side, and the cation exchange membrane is arranged on the positive electrode current collector 22 side. In this case, a space may be provided between the anion exchange membrane and the cation exchange membrane, or the anion exchange membrane and the cation exchange membrane may be in contact with each other.

[0068] (Sealing material) A pair of sealing materials 25 are provided at both ends of the ion-permeable membrane 24 so as to connect between the negative electrode current collector 21 and the ion-permeable membrane 24. The sealing material 25 prevents the leakage of the fluid hydrogen carrier 26 or the alkaline electrolyte 262. The material and shape of the sealing material 25 only need to be able to prevent the leakage of the fluid hydrogen carrier 26 or the alkaline electrolyte 262, and the material and shape are not limited.

[0069] As the material of the sealing material 25, for example, silicone rubber, acrylic rubber, butyl rubber, polyvinylidene fluoride, fluorine rubber, butadiene rubber, styrene-butadiene rubber, styrene-ethylene / butylene-styrene block copolymer rubber, maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer rubber, acid-modified styrene-ethylene / butylene-styrene block polymer, polybutene, etc. can be used. These may be used alone or in combination of two or more.

[0070] In the charge and discharge cell 20, when charging, when a current flows through the positive electrode current collector 22, since the positive electrode current collector 22 and the oxygen electrode catalyst 23 are electrically connected, the electrons flowing in the positive electrode current collector 22 flow to the outside through the positive electrode current collector 22. Further, since the oxygen electrode catalyst 23 is ionically connected to the ion-permeable membrane 24, hydroxide ions (OH -) is supplied to the surface of the oxygen electrode catalyst 23 through the ion permeable membrane 24. On the surface of the oxygen electrode catalyst 23, as shown in the following formula (1), electrons are withdrawn from the hydroxide ions, and oxygen and water are generated. 4OH - -4e - →O 2 + 2H 2 ···(1)

[0071] Also, in the present embodiment, a part of the negative electrode current collector 21 is electrically connected to the fluid hydrogen carrier 26, and a part of the fluid hydrogen carrier 26 is ionically connected to the ion permeable membrane 24. Ionically connected means that ion conduction is not blocked between the fluid hydrogen carrier 26 and the ion permeable membrane 24.

[0072] Therefore, when charging, as shown in the following formula (2), by the reaction between the water in the fluid hydrogen carrier 26 and the hydrogen storage alloy 261, the hydrogen storage alloy 261 stores hydrogen, and hydroxide ions (OH - ) are generated. M+H 2 O+e - →MH+OH - (2) (In the formula, M is a hydrogen storage alloy.)

[0073] Since a part of the negative electrode current collector 21 is electrically connected to the fluid hydrogen carrier 26, the fluid hydrogen carrier 26 can exchange electrons. Since a part of the fluid hydrogen carrier 26 is ionically connected to the ion permeable membrane 24, the generated hydroxide ions can quickly move to the positive electrode current collector 22 side, which is the positive electrode side. During discharge, the reverse reaction proceeds.

[0074] The charge / discharge cell 20 can be connected to the tank 31 (see FIG. 4) or the pump 32 (see FIG. 4) to easily discharge the fluid hydrogen carrier 26 out of the charge / discharge cell 20 and circulate it between the charge / discharge cell 20, the tank 31 (see FIG. 4), and the pump 32 (see FIG. 4). Thereby, the charge / discharge cell 20 can store the fluid hydrogen carrier 26 charged (hydrogen-stored) in the tank 31 (see FIG. 4). Further, when the charge (hydrogen storage amount) of the charge / discharge cell 20 is insufficient, the fluid hydrogen carrier 26 can be circulated through the charge / discharge cell 20 again to perform additional charging. In the charge / discharge cell 20, the absorption of hydrogen into the fluid hydrogen carrier 26 or the release of hydrogen from the fluid hydrogen carrier 26 is electrochemically performed within the charge / discharge cell 20.

[0075] Therefore, the charge / discharge cell 20 includes a negative electrode current collector 21, a positive electrode current collector 22, an oxygen electrode catalyst 23, an ion permeable membrane 24, and a sealing material 25, and includes a fluid hydrogen carrier 26 in the space formed by the negative electrode current collector 21, the ion permeable membrane 24, and the sealing material 25. Thereby, since the charge / discharge cell 20 can electrochemically absorb and release hydrogen into the fluid hydrogen carrier 26 in the space, more precise control can be performed compared to the case of controlling the temperature and pressure.

[0076] The charge / discharge cell 20 contains a hydrogen storage alloy 261 in the fluid hydrogen carrier 26, and the hydrogen storage alloy 261 can reversibly absorb and release hydrogen, for example, as in the case of being used as the negative electrode active material of a nickel-hydrogen secondary battery. Therefore, the charge / discharge cell 20 can be suitably used as a battery cell for a secondary battery.

[0077] In this embodiment, as shown in FIG. 3, the charge / discharge cell 20 may be connected to the joint 27 by a pair of sealing materials 25.

[0078] The joint 27 may be formed in a tubular shape. The joint 27 may have a structure that can inject and discharge the fluid hydrogen carrier 26 into the sealing material 25. The joint 27 may be located at a position where it can be connected to the sealing material 25, and the connection location of the joint 27 is not particularly limited.

[0079] As the material of the joint 27, any material that does not corrode or dissolve in the alkaline electrolyte 262 may be used. Examples of such materials include nickel, stainless steel, polyethylene, polypropylene, acrylic, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, etc., and they can be selected. It may be used alone or in combination of two or more kinds.

[0080] <Secondary battery> A secondary battery including the charge-discharge cell according to this embodiment will be described. FIG. 4 is a diagram showing the configuration of the secondary battery including the charge-discharge cell according to this embodiment. As shown in FIG. 4, the secondary battery 30A has a charge-discharge cell 20, a tank 31, and a pump 32, and circulates the fluid hydrogen carrier 26 through the joint 27 between the charge-discharge cell 20 and the tank 31 and the pump 32.

[0081] The joint 27 only needs to be configured to circulate the fluid hydrogen carrier 26 between the charge-discharge cell 20 and the tank 31 and the pump 32. In this embodiment, the joint 27 has a joint 27A connecting one sealing material 25 and the tank 31, a joint 27B connecting the tank 31 and the pump 32, and a joint 27C connecting the other sealing material 25 and the pump 32. A flow rate control valve (not shown) may be provided in the joint 27A, the joint 27B, and the joint 27C to control the flow rate.

[0082] The tank 31 may be formed of a material that is not corroded or dissolved by the alkaline electrolyte 262 contained in the fluid hydrogen carrier 26. The material constituting the tank 31 is not particularly limited, and examples include nickel, stainless steel, polyethylene, polypropylene, acrylic, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, etc. These may be used alone or in combination of two or more kinds.

[0083] In addition, in order to improve the wear resistance of the inner wall of the tank 31, a coating layer may be formed on the inner wall of the tank 31 with a coating agent. Examples of the coating agent include diamond-like carbon (DLC), polytetrafluoroethylene, melamine resin, urea resin, polyacetal, polyphenylene sulfide, ultra-high molecular weight polyethylene, etc. These may be used alone or in combination of two or more. Further, since gas is generated with charging and discharging, the internal pressure in the tank 31 rises, and in order to suppress damage to the secondary battery 30A, a pressure regulating valve (not shown) or the like may be provided in the tank 31.

[0084] The pump 32 only needs to be able to send the fluid hydrogen carrier 26, and examples thereof include a centrifugal pump, a propeller pump, a reciprocating pump, and a rotary pump. Examples of the centrifugal pump include a volute pump and a turbine pump. Examples of the propeller pump include an axial flow pump, a mixed flow pump, and a cascade pump. Examples of the reciprocating pump include a piston pump, a flapper pump, a diaphragm pump, a tube pump, and a wing pump. Examples of the rotary pump include a gear pump, an eccentric pump, and a screw pump. These may be used alone or in combination of two or more.

[0085] In the secondary battery 30A, by operating the pump 32, the fluid hydrogen carrier 26 can be injected from the tank 31 into the charge / discharge cell 20 and discharged from the charge / discharge cell 20 into the tank 31. Thereby, the fluid hydrogen carrier 26 can be circulated between the charge / discharge cell 20, the tank 31, and the pump 32 via the joint 27. Also, the fluid hydrogen carrier 26 can be stored in the tank 31 by closing a flow rate adjustment (not shown) provided in the joint 27B.

[0086] Thus, since the secondary battery 30A includes the charge / discharge cell 20 and can electrochemically store and release hydrogen, the control of charge / discharge (hydrogen storage and release) can be easily and simply performed. Further, since the fluid hydrogen carrier 26 of the secondary battery 30A has fluidity at normal temperature and normal pressure, it can be easily handled. Therefore, the secondary battery 30A can transport the fluid hydrogen carrier 26 with high efficiency.

[0087] Another configuration of the secondary battery 30A including the charge / discharge cell 20 according to this embodiment will be described. FIG. 5 is a diagram showing another configuration of the secondary battery 30A. As shown in FIG. 5, the secondary battery 30B has a sealing material 34, a partition wall 35, a joint 36, a tank 37, and a pump 38 on the side opposite to the fluid hydrogen carrier 26 side of the ion permeable membrane 24 in the secondary battery 30A shown in FIG. 4. The secondary battery 30B has a space inside by the positive electrode current collector 22, the sealing material 34, and the partition wall 35, and supplies the alkaline electrolyte 262 to the space.

[0088] The sealing material 34 is provided in a pair at both ends of the partition wall 35 so as to connect between the positive electrode current collector 22 and the partition wall 35 on the surface of the positive electrode current collector 22 opposite to the ion permeable membrane 24. The sealing material 34 prevents the leakage of the alkaline electrolyte 262 supplied to the space formed by the positive electrode current collector 22, the sealing material 34, and the partition wall 35. Since the sealing material 34 is the same as the sealing material 25, the details are omitted.

[0089] The partition wall 35 is provided on the side opposite to the positive electrode current collector 22 of the sealing material 34, and a space is formed inside by the positive electrode current collector 22, the sealing material 34, and the partition wall 35.

[0090] As the material for forming the partition wall 35, any material that does not corrode or dissolve in the alkaline electrolyte 262 may be used, and the same material as the joint 27 or the like may be used.

[0091] The joint 36 is connected to a pair of sealing materials 34 and is coupled to the tank 37 and the pump 38. The joint 36 only needs to be configured to circulate the alkaline electrolyte 262 between the charge and discharge cell 20, the tank 37, and the pump 38. In the present embodiment, the joint 36 includes a joint 36A that connects one sealing material 34 and the tank 37, a joint 36B that connects the tank 37 and the pump 38, and a joint 36C that connects the other sealing material 34 and the pump 38. A flow control valve (not shown) may be provided in the joints 36A, 36B, and 36C to control the flow rate.

[0092] The joint 36 may be formed in a tubular shape. The joint 36 only needs to have a structure that can inject and discharge the alkaline electrolyte 262 to and from the sealing material 34. The joint 27 only needs to be at a position where it can be connected to the sealing material 34, and the connection location of the joint 36 is not particularly limited. Since the joint 36 uses the same material as the joint 27, the details are omitted.

[0093] The tank 37 and the pump 38 are each connected to the joint 36 and are used as the tank and the pump for the positive electrode. Since the tank 37 and the pump 38 are the same as the tank 31 and the pump 32, the details are omitted.

[0094] In the secondary battery 30B, by providing the sealing material 34 and the partition wall 35, a space formed by the positive electrode current collector 22, the sealing material 34, and the partition wall 35 can be formed. Therefore, during charging, the alkaline electrolyte 262 can be supplied, and during discharging, air or oxygen can be supplied.

[0095] Therefore, also in the secondary battery 30B, similar to the secondary battery 30A, by providing the charge and discharge cell 20, the sealing material 34, and the partition wall 35, the control of charge and discharge (hydrogen absorption and release) can be easily and simply performed, and it can be transported with high efficiency.

[0096] <Hydrogen filling device for a fluid hydrogen carrier> The hydrogen filling device for a fluid hydrogen carrier according to this embodiment will be described. FIG. 6 is a diagram showing the hydrogen filling device. As shown in FIG. 6, the hydrogen filling device 100A may include a negative electrode current collector 101, a negative electrode void 102 capable of filling a fluid hydrogen carrier, a positive electrode current collector 103, a positive electrode void 104, an oxygen generation electrode 105, an ion permeable membrane 106, a sealing material 107, and a joint 108, and may be composed of these. The hydrogen filling device 100A fills hydrogen into the fluid hydrogen carrier 10.

[0097] (Negative electrode current collector) The negative electrode current collector 101 may be manufactured, for example, by applying roughened nickel plating to the surface of a nickel plate, a steel plate, a stainless steel plate, etc., or by etching the surface of a nickel plate or a nickel foil, or using a nickel mesh, a nickel foam, or a nickel porous body, or by applying nickel plating to the surface of a steel plate or a stainless steel plate whose surface has been roughened by etching or the like in advance. Also, unevenness may be formed on the surface, or it may be porous.

[0098] The negative electrode current collector 101 only needs to be arranged so as to be in contact with the negative electrode void 102.

[0099] (Negative electrode void) The negative electrode void 102 is provided for filling the fluid hydrogen carrier 10 when performing a hydrogen filling operation. When the fluid hydrogen carrier 10 is filled into the negative electrode void 102, it is sufficient that the fluid hydrogen carrier 10 is electrically connected to the negative electrode current collector and ionically connected to the ion exchange membrane. Note that ionically connected means that ion conduction is not blocked between the fluid hydrogen carrier 10 and the ion permeable membrane 106.

[0100] (Positive electrode current collector) The positive current collector 103 is arranged such that a part of it is electrically connected to the oxygen generation electrode 105. The positive current collector 103 is not particularly limited in terms of material and shape as long as it has electrical conductivity. For example, it may be made of nickel, stainless steel, carbon, titanium, or may be manufactured by applying roughened nickel plating to their surfaces, or may be manufactured by etching the surfaces of nickel plates or nickel foils, or may be manufactured by applying nickel plating to the surface of stainless steel whose surface has been roughened by etching or the like in advance.

[0101] (Oxygen generation electrode) The oxygen generation electrode 105 only needs to have oxygen generation activity on its surface. The oxygen generation activity is the action of oxidizing hydroxide ions to generate oxygen, and an oxygen generation catalyst is used. The oxygen generation electrode 105 may use this oxygen generation catalyst alone, or may use the oxygen generation catalyst supported on a substrate. A catalyst layer composed of an oxygen generation catalyst, a binder having ion conductivity, and a conductive agent may be applied onto a substrate such as a nickel mesh, a nickel porous body, carbon paper, a titanium mesh, a titanium punching metal, a stainless steel mesh, a stainless steel porous body, the positive current collector 103, etc.

[0102] Examples of catalysts having oxygen generation activity include platinum, rhodium, palladium, iridium, osmium, ruthenium, rhenium, gold, silver, nickel, cobalt, molybdenum, lanthanum, strontium, yttrium, iron oxide, cobalt ferrite, copper ferrite, nickel ferrite, calcium ferrite, nickel oxide, nickel sulfide, double hydroxides of nickel and cobalt, iron nickel tungsten oxide, carbon nitride, iridium oxide, bismuth iridium oxide, titanium dioxide, lithium-containing nickel oxide, cobalt lanthanum oxide, etc. The catalyst may be used alone or in combination of two or more.

[0103] The oxygen generation electrode 105 is arranged such that a part of it is ionically connected to the ion permeable membrane 106 and a part of it is electrically connected to the positive electrode current collector 103, and it only needs to be in contact with the positive electrode gap 104. Note that ionically connected means that ion conduction is not blocked between the oxygen generation electrode 105 and the ion permeable membrane 106.

[0104] With such a structure, electrons move from the positive electrode current collector 103 to the oxygen generation electrode, and the electrons can oxidize the hydroxide ions supplied from the ion permeable membrane 106 to generate oxygen.

[0105] (Ion Permeable Membrane) The ion permeable membrane 106 is arranged between the negative electrode current collector 101 and the positive electrode current collector 103, between the negative electrode gap 102 and the positive electrode gap 104, and between the negative electrode gap 102 and the oxygen generation electrode, and isolates the negative electrode current collector 101 and the positive electrode current collector 103.

[0106] The shape of the ion permeable membrane 106 is not particularly limited and may have any appropriate shape.

[0107] As the ion permeable membrane 106, an anion exchange membrane, a bipolar membrane in which an anion exchange membrane and a cation exchange membrane are laminated, a non-woven fabric, etc. can be used. When using two sheets of an anion exchange membrane and a cation exchange membrane, the anion exchange membrane is arranged on the negative electrode current collector 101 side and the cation exchange membrane is arranged on the positive electrode current collector 103 side. When using a non-woven fabric, it is preferably pores smaller than the particle diameter of the hydrogen storage alloy 11.

[0108] (Sealing Material) The sealing material 107 can be used for the purpose of preventing leakage of the fluid hydrogen carrier 10 or the alkaline electrolyte 12. The material and shape of the sealing material 25 only need to be able to prevent leakage of the fluid hydrogen carrier 10 or the alkaline electrolyte 12, and the material and shape are not limited.

[0109] As the material of the sealing material 107, for example, silicone rubber, acrylic rubber, butyl rubber, polyvinylidene fluoride, fluororubber, butadiene rubber, styrene-butadiene rubber, styrene-ethylene / butylene-styrene block copolymer rubber, maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer rubber, acid-modified styrene-ethylene / butylene-styrene block polymer, polybutene, etc. can be used. These may be used alone or in combination of two or more.

[0110] (Joint) The joint 108 may be installed to fill or discharge the fluid hydrogen carrier 10 and the alkaline electrolyte 12 into the negative electrode void 102 and the positive electrode void 104.

[0111] The joint 108 only needs not to prevent the filling or discharging of the fluid hydrogen carrier 10 and the alkaline electrolyte 12 into the negative electrode void 102 and the positive electrode void 104. As the material of the joint 108, any material that does not corrode or dissolve in the alkaline electrolyte 12 may be used. As such a material, for example, it can be selected from nickel, stainless steel, polyethylene, polypropylene, acrylic, polytetrafluoroethylene, polyvinylidene fluoride, polyether ether ketone, etc., and may be used alone or in combination of two or more.

[0112] (Method for filling hydrogen into the fluid hydrogen carrier) The method for filling hydrogen into the fluid hydrogen carrier according to this embodiment will be described. FIG. 7 is an explanatory diagram showing an example of filling hydrogen into the fluid hydrogen carrier using a hydrogen filling device. As shown in FIG. 7, the hydrogen filling device 100A includes the negative electrode current collector 101, the fluid hydrogen carrier 10, the positive electrode current collector 103, the positive electrode void 104, the oxygen generation electrode 105, the ion permeable membrane 106, the sealing material 107, and the joint 108 as described above. The negative electrode void 102 and the positive electrode void 104 of the hydrogen filling device 100A in FIG. 6 are filled with the fluid hydrogen carrier 10 and the alkaline electrolyte 12, respectively.

[0113] In the hydrogen filling device 100A, when a voltage of a negative potential is applied to the negative electrode current collector 101 and a positive potential is applied to the positive electrode current collector 103, since the positive electrode current collector 103 and the oxygen generation electrode 105 are electrically connected, at the oxygen generation electrode, as shown in the following formula (1), electrons are withdrawn from hydroxide ions (OH - ), and oxygen and water are generated. 4OH - →O 2 +4e - +2H 2 O···(1)

[0114] Also, in the present embodiment, a part of the negative electrode current collector 101 is electrically connected to the fluid hydrogen carrier 10. Therefore, when a voltage of a negative potential is applied to the negative electrode current collector 101 and a positive potential is applied to the positive electrode current collector 103, as shown in the following formula (2), due to the reaction between water in the fluid hydrogen carrier 10 and the hydrogen storage alloy 11, the hydrogen storage alloy 11 is filled with hydrogen, and hydroxide ions (OH - ) are generated. 4M+4H 2 O+4e - →4MH+4OH - ···(2) (In the formula, M is the hydrogen storage alloy 11.)

[0115] Also, in the present embodiment, a part of the fluid hydrogen carrier 10 is ionically connected to the ion permeable membrane 106, and a part of the oxygen generation electrode 105 is ionically connected to the ion permeable membrane 106. Therefore, the generated hydroxide ions can quickly move to the surface of the oxygen generation electrode 105. Accordingly, the reactions of formula (1) and formula (2) can occur continuously.

[0116] By the above method, in the present embodiment, in the hydrogen filling device 100A, by applying a voltage of a negative potential to the negative electrode current collector 101 and a positive potential to the positive electrode current collector 103, it is possible to fill the hydrogen storage alloy 11 in the fluid hydrogen carrier 10 with hydrogen.

[0117] In addition, in the present embodiment, by installing the joint 108, it is possible to inject or discharge the fluid hydrogen carrier 10 and the alkaline electrolyte 12 from the outside of the hydrogen filling device 100A. By performing the hydrogen filling operation while flowing the fluid hydrogen carrier 10 and the alkaline electrolyte 12, it is possible to continuously fill a large amount of the fluid hydrogen carrier 10 with hydrogen.

[0118] As described above, the hydrogen filling device 100A has a negative electrode current collector 101, a negative electrode void 102, a positive electrode current collector 103, a positive electrode void 104, an oxygen generation electrode 105, and an ion permeable membrane 106. By applying a voltage with a negative potential to the negative electrode current collector 101 and a positive potential to the positive electrode current collector 103, hydrogen can be filled into the hydrogen storage alloy 11 in the fluid hydrogen carrier 10.

[0119] <Power generation device using a fluid hydrogen carrier> A power generation device using a fluid hydrogen carrier according to the present embodiment will be described. FIG. 8 is a diagram showing the power generation device. As shown in FIG. 8, the power generation device 200A using a fluid hydrogen carrier may include a negative electrode current collector 101, a negative electrode void 102 capable of filling the fluid hydrogen carrier, a positive electrode current collector 103, a positive electrode void 104, an oxygen reduction electrode 201, an ion permeable membrane 106, a sealing material 107, and a joint 108, and may be composed of these. The power generation device 200A generates power using a fluid hydrogen carrier.

[0120] (Oxygen reduction electrode) The oxygen reduction electrode 201 only needs to have oxygen reduction activity on its surface. The oxygen reduction activity is an action of reducing oxygen to generate hydroxide ions, and an oxygen reduction catalyst is used. The oxygen reduction electrode 201 may use this oxygen reduction catalyst alone, or may use the oxygen reduction catalyst supported on a substrate. A catalyst layer composed of an oxygen reduction catalyst and a binder having ion conductivity may be coated on a substrate such as a nickel mesh, a nickel porous body, a carbon paper, a titanium mesh, a titanium punching metal, a stainless steel mesh, a stainless steel porous body, and the positive electrode current collector 103.

[0121] Examples of catalysts having oxygen reduction activity include platinum, rhodium, palladium, iridium, osmium, ruthenium, rhenium, gold, silver, nickel, cobalt, molybdenum, lanthanum, strontium, yttrium, bismuth iridium oxide, nitrogen-containing metal complexes, cobalt phthalocyanine, iron tetraazaannulene, a composite of carbon quantum dots and nanosheet-like graphene oxide, trioxotriangulene compounds, bismuth chloride, boron nitride, zirconium oxide having oxygen deficiency, azaphthalocyanine-based metal complexes, and the like. The catalyst may be used alone or in combination of two or more kinds.

[0122] The oxygen reduction electrode 201 is arranged such that a part of it is ionically connected to the ion permeable membrane 106 and a part of it is electrically connected to the positive electrode current collector 103, and it may be in contact with the positive electrode void 104. Note that ionically connected means that ion conduction is not blocked between the oxygen reduction electrode 201 and the ion permeable membrane 106.

[0123] With such a structure, electrons can move from the positive electrode current collector to the oxygen reduction electrode 201, and by these electrons, oxygen can be reduced to generate hydroxide ions.

[0124] Since the other components are the same as those of the hydrogen filling device, detailed description thereof is omitted.

[0125] (Power Generation Method Using a Fluid Hydrogen Carrier) The power generation method using a fluid hydrogen carrier according to this embodiment will be described. FIG. 9 is a diagram showing a power generation method using a fluid hydrogen carrier in a power generation device. As shown in FIG. 9, the negative electrode void 102 and the positive electrode void 104 of the power generation device 200A shown in FIG. 8 are each filled with a hydrogen-filled fluid hydrogen carrier 14 and an oxygen-containing substance 202.

[0126] (Oxygen-Containing Substance) The oxygen-containing substance 202 only needs to contain oxygen, and air or a liquid with a high oxygen solubility containing a perfluorocarbon and a surfactant may be used. Furthermore, humidified oxygen or air can also be used. When using air, a device for removing or adsorbing carbon dioxide in the air may be connected.

[0127] In the power generation device 200A, when a load is connected to the negative electrode current collector 101 and the positive electrode current collector 103, since the positive electrode current collector 103 and the oxygen reduction electrode 201 are electrically connected, at the oxygen reduction electrode, as shown in the following formula (3), electrons are given to oxygen (reduced), consuming water to generate hydroxide ions (OH - ). O 2 +4e - +2H 2 O→4OH - ···(3)

[0128] Also, in this embodiment, a part of the negative electrode current collector 101 is electrically connected to the hydrogen-filled fluid hydrogen carrier 14. Therefore, when a load is connected to the negative electrode current collector 101 and the positive electrode current collector 103, as shown in the following formula (4), hydrogen is desorbed from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled fluid hydrogen carrier 14, and electrons can be extracted. 4MH+4OH - →4M+4H 2 O+4e - ···(4) (In the formula, M is the hydrogen storage alloy 11.)

[0129] Also, in this embodiment, a part of the hydrogen-filled fluid hydrogen carrier 14 is ionically connected to the ion permeable membrane 106, and a part of the oxygen reduction electrode 201 is ionically connected to the ion permeable membrane 106. Therefore, the hydroxide ions generated at the oxygen reduction electrode 201 can quickly move to the surface of the hydrogen-filled fluid hydrogen carrier 14. Accordingly, the reactions of formula (3) and formula (4) can occur continuously.

[0130] According to the above method, in this embodiment, in the power generation device 200A, by connecting a load between the negative electrode current collector 101 and the positive electrode current collector 103, hydrogen can be extracted from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled fluid hydrogen carrier 14 to generate power.

[0131] Also, in this embodiment, by installing the coupling 28, it is possible to inject or discharge the hydrogen-filled fluid hydrogen carrier 14 and the oxygen-containing substance 202 from outside the power generation device 200A. By performing the power generation operation while flowing the hydrogen-filled fluid hydrogen carrier 14 and the oxygen-containing substance 202, it is possible to generate power for a long time and in a large capacity.

[0132] In this way, the power generation device 200A has a negative electrode current collector 101, a negative electrode gap 102, a positive electrode current collector 103, a positive electrode gap 104, an oxygen reduction electrode 201, and an ion permeable membrane 106. By connecting a load between the negative electrode current collector 101 and the positive electrode current collector 103, hydrogen can be extracted from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled fluid hydrogen carrier 14 to generate power.

[0133] <Hydrogen filling and power generation device using a fluid hydrogen carrier> According to this embodiment, a hydrogen filling and power generation device capable of performing hydrogen filling and power generation with one device can be provided. The hydrogen filling and power generation device using the fluid hydrogen carrier according to this embodiment will be described. FIG. 10 is a diagram showing the hydrogen filling and power generation device. As shown in FIG. 10, the hydrogen filling and power generation device 300A using a fluid hydrogen carrier includes a negative electrode current collector 101, a negative electrode gap 102 capable of filling the fluid hydrogen carrier, a positive electrode current collector 103, a positive electrode gap 104, a binary electrode 301 capable of oxygen reduction and oxygen generation, an ion permeable membrane 106, a sealing material 107, and a joint 108.

[0134] (Binary electrode capable of oxygen reduction and oxygen generation) The binary electrode 301 only needs to have both oxygen reduction activity and oxygen evolution activity on its surface. The binary electrode 301 may be composed of one type of catalyst having oxygen reduction activity and oxygen evolution activity, or may be composed of two or more different types of catalysts for oxygen reduction and oxygen generation. A single catalyst may be used, or the catalyst may be supported on a substrate for use. A catalyst layer composed of a catalyst and a binder having ion conductivity may be applied onto a substrate such as a nickel mesh, a nickel porous body, a carbon paper, a titanium mesh, a titanium perforated metal, a stainless steel mesh, a stainless steel porous body, the positive electrode current collector 103, etc.

[0135] As catalysts having both oxygen reduction and oxygen evolution activities, for example, nickel compounds, cobalt compounds, pyrochlore-type bismuth iridium oxides, pyrochlore-type bismuth ruthenium composite oxides, etc. are applicable. Only one type of catalyst or a combination of two or more types may be used.

[0136] A part of the binary electrode 301 is arranged to be ionically connected to the ion permeable membrane 106, and a part of it is electrically connected to the positive electrode current collector 103, and it only needs to be in contact with the positive electrode void 104. Note that ionically connected means that ion conduction is not blocked between the oxygen reduction electrode 201 and the ion permeable membrane 106.

[0137] With such a structure, electrons move from the positive electrode current collector 103 to the binary electrode 301, and by these electrons, oxygen is reduced to generate hydroxide ions. Electrons move from the positive electrode current collector to the binary electrode 301, and by these electrons, the hydroxide ions supplied from the ion permeable membrane 106 are oxidized to generate oxygen.

[0138] Since other components are the same as those of the hydrogen filling device, detailed descriptions are omitted.

[0139] (Hydrogen filling and power generation method using a fluid hydrogen carrier) The hydrogen filling and power generation method has the same mechanism as the hydrogen filling device and the power generation device, so detailed description thereof will be omitted.

[0140] Thus, the hydrogen filling and power generation device 300A has a negative electrode current collector 101, a negative electrode gap 102, a positive electrode current collector 103, a positive electrode gap 104, a binary electrode 301, and an ion permeable membrane 106. The hydrogen filling and power generation device 300A reduces oxygen by electrons that move electrons from the positive electrode current collector 103 to the binary electrode 301 to generate hydroxide ions, and oxidizes hydroxide ions supplied from the ion permeable membrane 106 by electrons that move electrons from the positive electrode current collector to the binary electrode 301 to generate oxygen.

[0141] <Second Hydrogen Filling and Power Generation Device Using a Fluid Hydrogen Carrier> According to the present embodiment, a hydrogen filling and power generation device capable of performing hydrogen filling and power generation with one device without oxygen generation and oxygen reduction can be provided. A second hydrogen filling and power generation device using a fluid hydrogen carrier according to the present embodiment will be described. FIG. 11 is a diagram showing the second hydrogen filling and power generation device. As shown in FIG. 11, the second hydrogen filling and power generation device 300B using a fluid hydrogen carrier is composed of a negative electrode current collector 101, a negative electrode gap 102 capable of filling the fluid hydrogen carrier, a positive electrode current collector 103, a positive electrode gap 104, an ion permeable membrane 106, a sealing material 107, and a joint 108.

[0142] It is a structure in which the binary electrode 301 of the hydrogen filling and power generation device 300A shown in FIG. 10 is removed, and since the other configuration is the same as that of the hydrogen filling and power generation device 300A, detailed description thereof will be omitted.

[0143] (Second Hydrogen Filling and Power Generation Method Using a Fluid Hydrogen Carrier) The hydrogen filling and power generation method according to this embodiment will be described. FIG. 12 is a diagram showing the hydrogen filling method. As shown in FIG. 12, the negative electrode void 102 and the positive electrode void 104 of the second hydrogen filling and power generation device 300B shown in FIG. 11 are filled with a fluid hydrogen carrier 10 and a nickel hydroxide-containing slurry 302, respectively. FIG. 13 is a diagram showing the power generation method. As shown in FIG. 13, the negative electrode void 102 and the positive electrode void 104 of the second hydrogen filling and power generation device 300B shown in FIG. 11 are filled with a hydrogen-filled fluid hydrogen carrier 14 and a nickel oxyhydroxide-containing slurry 304, respectively.

[0144] (Nickel hydroxide-containing slurry) The nickel hydroxide-containing slurry 302 according to the embodiment of the present invention is a mixture containing a nickel hydroxide-containing substance 303 and an alkaline electrolyte 12, and may further contain optional components such as a dispersant, a thickener, a surfactant, and an electrically conductive filler in an appropriate arbitrary amount. The nickel hydroxide-containing slurry 302 contains the nickel hydroxide-containing substance 303 in a state of being dispersed in the alkaline electrolyte 12.

[0145] (Nickel hydroxide-containing substance) The nickel hydroxide-containing substance 303 contained in the nickel hydroxide-containing slurry 302 according to this embodiment can be reversibly oxidized and reduced to nickel hydroxide by oxidizing to nickel oxyhydroxide and reducing the nickel oxyhydroxide.

[0146] In addition, the nickel hydroxide-containing substance 303 contained in the nickel hydroxide-containing slurry 302 according to this embodiment preferably contains cobalt. Nickel hydroxide has poor electrical conductivity, and adding cobalt improves the electrical conductivity.

[0147] The shape of the nickel hydroxide-containing substance 303 is not particularly limited, and may be, for example, spherical, ellipsoidal, spindle-shaped, crushed, plate-shaped, columnar, or the like.

[0148] The average particle diameter of the nickel hydroxide inclusion 303 is 50 μm or less. When it is larger than 50 μm, in the process of filling the nickel hydroxide-containing slurry 302 with hydrogen and filling it into the power generation device, problems such as clogging of the nickel hydroxide inclusion 303 in the flow path and a high sedimentation rate occur. The average particle diameter of the nickel hydroxide inclusion 303 can be appropriately set within the range of 50 μm or less. For example, 10 nm to 50 μm is preferable, 20 nm to 25 μm is more preferable, and 50 nm to 20 μm is even more preferable. When the average particle diameter is too small, the viscosity of the nickel hydroxide-containing slurry 302 increases, which hinders fluidity. If the average particle diameter of the nickel hydroxide inclusion 303 is within the above preferable range, the nickel hydroxide inclusion 303 can be well dispersed in the alkaline electrolyte 12 while maintaining the contact area with the alkaline electrolyte 12.

[0149] (Hydrogen filling method by the second hydrogen filling and power generation device) In the second hydrogen filling and power generation device 300B, when a voltage with a negative potential is applied to the negative electrode current collector 101 and a positive potential is applied to the positive electrode current collector 103, since the positive electrode current collector 103 and the nickel hydroxide-containing slurry 302 are electrically connected, in the nickel hydroxide inclusion 303, as shown in the following formula (5), electrons are withdrawn from nickel hydroxide (Ni(OH) 2 ) to generate nickel oxyhydroxide (NiOOH) and water. Ni(OH) 2 +OH - →NiOOH+H 2 O+e - ···(5)

[0150] Also, in this embodiment, a part of the negative electrode current collector 101 is electrically connected to the fluid hydrogen carrier 10. Therefore, when a voltage with a negative potential is applied to the negative electrode current collector 101 and a positive potential is applied to the positive electrode current collector 103, as shown in the following formula (2), due to the reaction between water in the hydrogen-filled fluid hydrogen carrier 14 and the hydrogen storage alloy 11, the hydrogen storage alloy 11 is filled with hydrogen, and hydroxide ions (OH - ) are generated. 4M+4H 2 O+4e -→4MH + 4OH - ···(2) (wherein, M is the hydrogen storage alloy 11.)

[0151] Further, in the present embodiment, since a part of the hydrogen-filled fluid hydrogen carrier 14 is ionically connected to the ion permeable membrane 106 and a part of the oxygen generation electrode 105 is ionically connected to the ion permeable membrane 106, the generated hydroxide ions can quickly move to the surface of the nickel hydroxide-containing slurry 302. Therefore, the reactions of formula (5) and formula (2) can be continuously caused to occur.

[0152] By the above method, in the present embodiment, in the second hydrogen filling and power generation device 300B, by applying a voltage of a negative potential to the negative electrode current collector 101 and a positive potential to the positive electrode current collector 103, it is possible to fill hydrogen into the hydrogen storage alloy 11 in the fluid hydrogen carrier 10 (see FIG. 7).

[0153] Further, in the present embodiment, by installing the joint 108, it is possible to inject or discharge the hydrogen-filled fluid hydrogen carrier 14 and the alkaline electrolyte 12 from the outside of the hydrogen filling device 100A. By performing the hydrogen filling operation while flowing the fluid hydrogen carrier 10 and the alkaline electrolyte 12, it is possible to continuously fill hydrogen into a large amount of the fluid hydrogen carrier 10.

[0154] Thus, the second hydrogen filling and power generation device 300B has a negative electrode current collector 101, a negative electrode gap 102, a positive electrode current collector 103, a positive electrode gap 104, and an ion permeable membrane 106. By applying a voltage of a negative potential to the negative electrode current collector 101 and a positive potential to the positive electrode current collector 103, respectively, it is possible to fill hydrogen into the hydrogen storage alloy 11 in the fluid hydrogen carrier 10 (see FIG. 7). Therefore, the second hydrogen filling and power generation device 300B can perform hydrogen filling without having the dual electrode 301 and without performing oxygen generation and oxygen reduction in the hydrogen filling and power generation device 300A.

[0155] (Power generation method by the second hydrogen filling and power generation device) In the second hydrogen filling and power generation device 300B, when a load is connected to the negative current collector 101 and the positive current collector 103, since the positive current collector 103 and the nickel oxyhydroxide-containing slurry 304 are electrically connected, as shown in the following formula (6), nickel oxyhydroxide (NiOOH) and water give electrons to water, thereby generating nickel hydroxide (Ni(OH) 2 ), and hydroxide ions are generated. NiOOH + H 2 O + e - → Ni(OH) 2 + OH - ···(6)

[0156] Also, in the present embodiment, a part of the negative current collector 101 is electrically connected to the hydrogen-filled fluid hydrogen carrier 14. Therefore, when a load is connected to the negative current collector 101 and the positive current collector 103, as shown in the following formula (4), hydrogen is desorbed from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled fluid hydrogen carrier 14, and electrons can be extracted. 4MH + 4OH - → 4M + 4H 2 O + 4e - ···(4) (In the formula, M is the hydrogen storage alloy 11.)

[0157] Also, in the present embodiment, since a part of the hydrogen-filled fluid hydrogen carrier 14 is ionically connected to the ion permeable membrane 106, and a part of the oxygen reduction electrode 201 is ionically connected to the ion permeable membrane 106, the hydroxide ions generated in formula (6) can quickly move to the surface of the hydrogen-filled fluid hydrogen carrier 14. Therefore, the reactions of formula (6) and formula (4) can occur continuously.

[0158] By the above method, in the present embodiment, in the second hydrogen filling and power generation device 300B, by connecting a load between the negative current collector 101 and the positive current collector 103, hydrogen can be extracted from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled fluid hydrogen carrier 14, and power generation becomes possible.

[0159] Also, in this embodiment, by installing the joint 108, it is possible to inject or discharge the hydrogen-filled fluid hydrogen carrier 14 and the nickel oxyhydroxide-containing slurry 304 from the outside of the second hydrogen filling and power generation device 300B. By performing the power generation operation while flowing the hydrogen-filled fluid hydrogen carrier 14 and the nickel oxyhydroxide-containing slurry 304, it is possible to perform power generation with a large capacity for a long time.

[0160] Thus, the second hydrogen filling and power generation device 300B has a negative electrode current collector 101, a negative electrode gap 102, a positive electrode current collector 103, a positive electrode gap 104, and an ion permeable membrane 106. By connecting a load between the negative electrode current collector 101 and the positive electrode current collector 103, hydrogen can be extracted from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled fluid hydrogen carrier 14 to generate power. Therefore, the second hydrogen filling and power generation device 300B can generate power without having a dual electrode 301 and without performing oxygen generation and oxygen reduction in the hydrogen filling and power generation device 300A.

[0161] <Second Hydrogen Filling Device for Fluid Hydrogen Carrier> The second hydrogen filling device for the fluid hydrogen carrier according to this embodiment will be described. FIG. 14 is a diagram showing the second hydrogen filling device. As shown in FIG. 14, the second hydrogen filling device 100B is composed of a negative electrode current collector 101, a negative electrode gap 102 capable of filling the fluid hydrogen carrier, a positive electrode current collector 103, a positive electrode gap 104, an oxygen generation electrode 105, an ion permeable membrane 106, a sealing material 107, a joint 108, a porous negative electrode current collector 111, and a porous positive electrode current collector 112.

[0162] (Porous Negative Electrode Current Collector) The porous negative electrode current collector 111 has through-holes in the thickness direction and is arranged to be in contact with the ion permeable membrane 106. By having through-holes in the thickness direction, it enables the mass transfer of hydroxide ions generated during the hydrogen filling of the fluid hydrogen carrier. Also, by arranging it to be in contact with the ion permeable membrane 106, the distance from the positive electrode collector is reduced, and the cell resistance can be decreased. Furthermore, deformation of the ion permeable membrane 106 during actual use can be suppressed.

[0163] The porous negative electrode current collector 111 only needs to be porous and have electrical conductivity. For example, nickel mesh, nickel foam, nickel porous body, nickel non-woven fabric, carbon non-woven fabric, carbon paper, stainless steel mesh, stainless steel foam, stainless steel porous body, stainless steel non-woven fabric, etc. can be used.

[0164] (Porous positive electrode current collector) The porous positive electrode current collector 112 has through-holes in the thickness direction and is arranged to be in contact with the ion permeable membrane 106. By having through-holes in the thickness direction, it enables the mass transfer of hydroxide ions generated during the hydrogen filling of the fluid hydrogen carrier. Also, by arranging it to be in contact with the ion permeable membrane 106, the distance from the positive electrode collector is reduced, and the cell resistance can be decreased. Furthermore, deformation of the ion permeable membrane 106 during actual use can be suppressed.

[0165] The porous positive electrode current collector 112 only needs to be porous and have electrical conductivity. For example, nickel mesh, nickel foam, nickel porous body, nickel non-woven fabric, carbon non-woven fabric, carbon paper, stainless steel mesh, stainless steel foam, stainless steel porous body, stainless steel non-woven fabric, etc. can be used.

[0166] The structure is the same as that of the first hydrogen filling device except that the porous negative electrode current collector 111 and the porous positive electrode current collector 112 are used.

[0167] Thus, the second hydrogen filling device 100B has a porous negative current collector 111 and a porous positive current collector 112 in the hydrogen filling device 100A. Similar to the hydrogen filling device 100A, the second hydrogen filling device 100B can fill hydrogen into the hydrogen storage alloy 11 in the mobile hydrogen carrier 10 (see FIG. 7) by applying a negative potential to the negative current collector 101 and a positive potential to the positive current collector 103, respectively.

[0168] <Second power generation device using a mobile hydrogen carrier> The second power generation device for the mobile hydrogen carrier according to this embodiment will be described. FIG. 15 is a diagram showing the second power generation device. As shown in FIG. 15, the second power generation device 200B includes a negative current collector 101, a negative electrode gap 102 capable of filling a mobile hydrogen carrier, a positive current collector 103, a positive electrode gap 104, an oxygen reduction electrode 201, an ion permeable membrane 106, a sealing material 107, a joint 108, a porous negative current collector 111, and a porous positive current collector 112.

[0169] It has the same configuration as the first power generation device except for using the porous negative current collector 111 and the porous positive current collector 112.

[0170] Thus, the second power generation device 200B has a porous negative current collector 111 and a porous positive current collector 112 in the power generation device 200A. Thereby, similar to the power generation device 200A, the second power generation device 200B can extract hydrogen from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled mobile hydrogen carrier 14 and generate electricity by connecting a load between the negative current collector 101 and the positive current collector 103.

[0171] <Third hydrogen filling and power generation device using a mobile hydrogen carrier> A third hydrogen filling and power generation device using a fluid hydrogen carrier according to this embodiment will be described. FIG. 16 is a diagram showing the third hydrogen filling and power generation device. As shown in FIG. 16, the third hydrogen filling and power generation device 300C includes a negative electrode current collector 101, a negative electrode void 102 capable of filling a fluid hydrogen carrier, a positive electrode current collector 103, a positive electrode void 104, a binary electrode 301, an ion permeable membrane 106, a sealing material 107, a joint 108, a porous negative electrode current collector 111, and a porous positive electrode current collector 112.

[0172] It is the same as the first hydrogen filling and power generation device except that a porous negative electrode current collector 111 and a porous positive electrode current collector 112 are used.

[0173] Therefore, the third hydrogen filling and power generation device 300C has a porous negative electrode current collector 111 and a porous positive electrode current collector 112 in the hydrogen filling and power generation device 300A. Similar to the hydrogen filling and power generation device 300A, the third hydrogen filling and power generation device 300C can reduce oxygen to generate hydroxide ions by electrons that move electrons from the positive electrode current collector 103 to the binary electrode 301, and can oxidize hydroxide ions supplied from the ion permeable membrane 106 by electrons that move electrons from the positive electrode current collector to the binary electrode 301 to generate oxygen.

[0174] <Fourth Hydrogen Filling and Power Generation Device Using a Fluid Hydrogen Carrier> A fourth hydrogen filling and power generation device using a fluid hydrogen carrier according to this embodiment will be described. FIG. 17 is a diagram showing the fourth hydrogen filling and power generation device. As shown in FIG. 17, the fourth hydrogen filling and power generation device 300D includes a negative electrode current collector 101, a negative electrode void 102 capable of filling a fluid hydrogen carrier, a positive electrode current collector 103, a positive electrode void 104, an ion permeable membrane 106, a sealing material 107, a joint 108, a porous negative electrode current collector 111, and a porous positive electrode current collector 112.

[0175] It is the same as the second hydrogen charging and power generation device except that the porous negative electrode current collector 111 and the porous positive electrode current collector 112 are used.

[0176] Therefore, the fourth hydrogen charging and power generation device 300D has a porous negative electrode current collector 111 and a porous positive electrode current collector 112 in the second hydrogen charging and power generation device 300B. Similar to the second hydrogen charging and power generation device 300B, the fourth hydrogen charging and power generation device 300D can charge hydrogen into the hydrogen storage alloy 11 in the mobile hydrogen carrier 10 (see FIG. 7) by applying a negative potential to the negative electrode current collector 101 and a positive potential to the positive electrode current collector 103, respectively. Further, the fourth hydrogen charging and power generation device 300D can extract hydrogen from the hydrogen-charged hydrogen storage alloy 13 in the hydrogen-charged mobile hydrogen carrier 14 and generate power by connecting a load between the negative electrode current collector 101 and the positive electrode current collector 103. Therefore, similar to the second hydrogen charging and power generation device 300B, the fourth hydrogen charging and power generation device 300D does not have a bipolar electrode 301 and can perform hydrogen charging and power generation without performing oxygen generation and oxygen reduction.

[0177] <Third Hydrogen Charging Device for Mobile Hydrogen Carrier> The third hydrogen charging device for the mobile hydrogen carrier according to the present embodiment will be described. FIG. 18 is a diagram showing the third hydrogen charging device. As shown in FIG. 18, the third hydrogen charging device 100C has a structure in which two second hydrogen charging devices are stacked via a bipolar plate 121, and the components are the same as those of the second hydrogen charging device except for the bipolar plate 121.

[0178] In the present embodiment, a structure in which two devices are connected in series is shown as an example, but the number of devices connected in series may be two or more and is not limited thereto. By connecting two or more hydrogen charging devices in series, a voltage that is several times the number of connected devices can be generated. That is, the current flowing can be reduced with the same amount of energy, and heat generation can be suppressed.

[0179] (Bipolar Plate) The bipolar plate 121 may be used when connecting two or more hydrogen filling devices in series, and it combines the functions of the negative electrode current collector 101 and the positive electrode current collector 103. That is, any material used for the negative electrode current collector 101 and the positive electrode current collector 103 can be used without particular limitation.

[0180] Therefore, the third hydrogen filling device 100C may include a plurality (two in this embodiment) of the second hydrogen filling devices 100B via the bipolar plate 121. Similar to the second hydrogen filling device 100B, by applying a negative potential to the negative electrode current collector 101 and a positive potential to the positive electrode current collector 103 respectively, hydrogen can be filled into the hydrogen storage alloy 11 in the flowing hydrogen carrier 10 (see FIG. 7).

[0181] <The Third Power Generation Device Using a Flowing Hydrogen Carrier> The third power generation device using a flowing hydrogen carrier according to this embodiment will be described. FIG. 19 is a diagram showing the third power generation device. As shown in FIG. 19, the third power generation device 200C has a structure in which two second power generation devices are stacked via a bipolar plate 121, and the components other than the bipolar plate 121 are the same as those of the second power generation device.

[0182] In this embodiment, a structure in which two devices are connected in series is shown as an example, but the number of devices connected in series may be two or more and is not limited thereto. By connecting two or more hydrogen filling devices in series, a voltage that is several times the number of connected devices can be generated. That is, if the same amount of energy is used, the current flowing can be reduced, and heat generation can be suppressed.

[0183] Therefore, the third power generation device 200C may include a plurality (two in this embodiment) of the second power generation devices 200B via the bipolar plate 121. Similar to the second power generation device 200B, by connecting a load between the negative electrode current collector 101 and the positive electrode current collector 103, hydrogen can be extracted from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled flowing hydrogen carrier 14 to generate electricity.

[0184] <Fifth Hydrogen Charging and Power Generation Device Using a Fluid Hydrogen Carrier> The fifth hydrogen charging and power generation device using a fluid hydrogen carrier according to this embodiment will be described. FIG. 20 is a diagram showing the fifth hydrogen charging and power generation device. As shown in FIG. 20, the fifth hydrogen charging and power generation device 300E has a structure in which two third hydrogen charging and power generation devices are stacked via a bipolar plate 121, and the components other than the bipolar plate 121 are the same as those of the third hydrogen charging and power generation device.

[0185] In this embodiment, a structure in which two devices are connected in series is shown as an example, but the number of devices connected in series may be two or more and is not limited thereto. By connecting two or more hydrogen charging devices in series, a voltage that is a multiple of the number of connected devices can be generated. That is, if the same amount of energy is used, the current flowing can be reduced, and heat generation can be suppressed.

[0186] Therefore, the fifth hydrogen charging and power generation device 300E includes a plurality (two in this embodiment) of third hydrogen charging and power generation devices 300C in series via a bipolar plate 121, so that hydrogen charging into the hydrogen storage alloy 11 in the fluid hydrogen carrier 10 (see FIG. 7) and power generation generated by extracting hydrogen from the hydrogenated hydrogen storage alloy 13 in the hydrogenated fluid hydrogen carrier 14 can be performed while suppressing heat generation with the same amount of energy.

[0187] <Sixth Hydrogen Charging and Power Generation Device Using a Fluid Hydrogen Carrier> The sixth hydrogen charging and power generation device using a fluid hydrogen carrier according to this embodiment will be described. FIG. 21 is a diagram showing the sixth hydrogen charging and power generation device. As shown in FIG. 21, the sixth hydrogen charging and power generation device 300E has a structure in which two fourth hydrogen charging and power generation devices are stacked via a bipolar plate 121, and the components other than the bipolar plate 121 are the same as those of the fourth hydrogen charging and power generation device.

[0188] In this embodiment, a structure in which two devices are connected in series is shown as an example. However, the number of devices connected in series may be two or more, and is not limited thereto. By connecting two or more hydrogen filling devices in series, a voltage that is several times the number of connected devices can be generated. That is, if the same amount of energy is used, the current flowing can be reduced, and heat generation can be suppressed.

[0189] <Hydrogen filling and power generation system> A hydrogen filling and power generation system using the fluid hydrogen carrier 10 according to this embodiment will be described. It can be applied to any of the hydrogen filling device 100A, power generation device 200A, hydrogen filling and power generation device 300A, second hydrogen filling and power generation device 300B, second hydrogen filling device 100B, second power generation device 200B, third hydrogen filling and power generation device 300C, fourth hydrogen filling and power generation device 300D, third hydrogen filling device 100C, third power generation device 200C, fifth hydrogen filling and power generation device 300E, and sixth hydrogen filling and power generation device 300E. However, in this embodiment, the sixth hydrogen filling and power generation device 300E will be used for the description.

[0190] FIG. 22 is a diagram showing a hydrogen filling and power generation system. As shown in FIG. 22, the hydrogen filling and power generation system 400A includes a sixth hydrogen filling and power generation device 300E in which four hydrogen filling and power generation devices are connected in series, a negative electrode tank 410, a negative electrode pressure increasing / decreasing device 420, a positive electrode tank 430, a positive electrode pressure increasing / decreasing device 440, an inter-device flow path 450, and a device flow path 460. The inter-device flow path 450 and the device flow path 460 may be installed outside the hydrogen filling and power generation device or built into the hydrogen filling and power generation device.

[0191] (Negative electrode tank) The negative electrode tank 410 is used to store the fluid hydrogen carrier 10. It may be formed of a material that is not corroded or dissolved by the alkaline electrolytic solution 12 contained in the fluid hydrogen carrier 10. The material constituting the negative electrode tank 410 is not particularly limited. For example, nickel, stainless steel, polyethylene, polypropylene, acrylic, polyvinyl chloride, ABS resin, polyoxymethylene, polycarbonate, polystyrene, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, polyether ether ketone, etc. may be mentioned. These may be used alone or in combination of two or more.

[0192] Also, in order to improve the wear resistance of the inner wall of the negative electrode tank 410, a coating layer may be formed on the inner wall of the negative electrode tank 410 with a coating agent. As the coating agent, for example, diamond-like carbon (DLC), polytetrafluoroethylene, melamine resin, urea resin, polyacetal, polyphenylene sulfide, ultra-high molecular weight polyethylene, etc. can be used. These may be used alone or in combination of two or more. Further, since gas is generated with charge and discharge, the internal pressure of the negative electrode tank 410 rises, and in order to prevent the hydrogen filling and power generation system 400A from being damaged, a pressure regulating valve (not shown) or the like may be provided in the negative electrode tank 410. Also, one or more cocks (not shown) capable of discharging the fluid hydrogen carrier 10 in the negative electrode tank 410 or injecting the fluid hydrogen carrier 10 into the negative electrode tank 410 may be provided.

[0193] (Negative electrode pressurizing / de-pressurizing device) The negative electrode pressurizing / de-pressurizing device 420 only needs to be able to feed the flowing hydrogen carrier 10. For example, a centrifugal pump, a propeller pump, a reciprocating pump, a rotary pump, etc. can be mentioned. Examples of centrifugal pumps include volute pumps, turbine pumps, etc. Examples of propeller pumps include axial flow pumps, mixed flow pumps, cascade pumps, etc. Examples of reciprocating pumps include piston pumps, plunger pumps, diaphragm pumps, tube pumps, wing pumps, etc. Examples of rotary pumps include gear pumps, eccentric pumps, screw pumps, etc. These may be used alone or in combination of two or more.

[0194] (Positive electrode tank) The positive electrode tank 430 may or may not be used depending on the application. When it is necessary to store the alkaline electrolyte 12, the nickel hydroxide-containing slurry 302, or the nickel oxyhydroxide-containing slurry 304, it may be formed of a material that is not corroded or dissolved by the alkaline electrolyte 12. The material constituting the positive electrode tank 430 at that time is not particularly limited. For example, nickel, stainless steel, polyethylene, polypropylene, acrylic, polyvinyl chloride, ABS resin, polyoxymethylene, polycarbonate, polystyrene, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, etc. can be mentioned. These may be used alone or in combination of two or more.

[0195] (Positive electrode pressurizing / de-pressurizing device) The positive electrode pressurizing / de-pressurizing device 440 only needs to be able to transport the alkaline electrolytic solution 12, the nickel hydroxide-containing slurry 302, the nickel oxyhydroxide-containing slurry 304, and the oxygen-containing substance 202. For example, a centrifugal pump, a propeller pump, a reciprocating pump, a rotary pump, etc. can be mentioned. Examples of the centrifugal pump include a volute pump, a turbine pump, etc. Examples of the propeller pump include an axial flow pump, a mixed flow pump, a cascade pump, etc. Examples of the reciprocating pump include a piston pump, a flapper pump, a diaphragm pump, a tube pump, a wing pump, etc. Examples of the rotary pump include a gear pump, an eccentric pump, a screw pump, etc. These may be used alone or in combination of two or more.

[0196] (Inter-device flow path) The inter-device flow path 450 is a flow path installed for transporting / distributing the mobile hydrogen carrier 10, the alkaline electrolytic solution 12, the nickel hydroxide-containing slurry 302, the nickel oxyhydroxide-containing slurry 304, and the oxygen-containing substance 202 to each device when a plurality of devices are connected in series.

[0197] The material constituting the inter-device flow path 450 is not particularly limited. For example, nickel, stainless steel, polyethylene, polypropylene, acrylic, polyvinyl chloride, ABS resin, polyoxymethylene, polycarbonate, polystyrene, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, stainless steel, nickel, carbon steel, etc. can be mentioned. These may be used alone or in combination of two or more.

[0198] The shape of the inter-device flow path 450 is not particularly limited. It may be in a tube shape or may be formed on a member in the hydrogen filling or power generation device.

[0199] (Device flow path) The device flow path 460 is a flow path for transporting the fluid hydrogen carrier 10, the alkaline electrolyte 12, the nickel hydroxide-containing slurry 302, the nickel oxyhydroxide-containing slurry 304, and the oxygen-containing substance 202 branched from the inter-device flow path 450 to the negative electrode gap 102 or the positive electrode gap 104 within the device.

[0200] The material constituting the device flow path 460 is not particularly limited. For example, nickel, stainless steel, polyethylene, polypropylene, acrylic, polyvinyl chloride, ABS resin, polyoxymethylene, polycarbonate, polystyrene, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, polyether ether ketone, stainless steel, nickel, carbon steel, etc. may be mentioned. These may be used alone or in combination of two or more.

[0201] In order to make the flow rate inside the device flow uniformly between the stacked devices, it is better that As represented by the following formula (7) is smaller. Preferably As < 1, more preferably As < 0.1, and even more preferably As < 0.01. As = [minimum cross-sectional area of the device flow path 460] / [maximum cross-sectional area of the inter-device flow path 450] ··· (7)

[0202] The fluid hydrogen carrier 10 of the present invention is a liquid having electrical conductivity. In the hydrogen filling and power generation system 400A according to this embodiment, the devices are connected in series, and a short circuit current flows between the devices through the fluid hydrogen carrier 10 in the inter-device flow path 450 and the device flow path 460. This causes a decrease in energy efficiency.

[0203] That is, in the short-circuit current path of the hydrogen filling and power generation system 400A according to the present embodiment, in the paths of the continuous inter-device flow path 450 and the device flow path 460 between adjacent hydrogen filling and power generation devices sandwiching the bipolar plate 121 (the dashed line in FIG. 22), there is a region made of an insulating material, and the shortest distance of the flow path made of the insulating material needs to be 50 cm or more. In the present embodiment, only the electrical conductivity of the fluid hydrogen carrier 10 is described in detail. However, since the nickel hydroxide-containing slurry 302 and the nickel oxyhydroxide-containing slurry 304 also have electrical conductivity in the same manner, a flow path made of an insulating material is required.

[0204] Thus, by having the above-described structure, the hydrogen filling and power generation system 400A can reduce the short-circuit current and perform hydrogen filling and power generation with high energy efficiency.

[0205] <Second hydrogen filling and power generation system> A second hydrogen filling and power generation system using the fluid hydrogen carrier 10 according to the present embodiment will be described. It can be applied to any of the hydrogen filling device 100A, the power generation device 200A, the hydrogen filling and power generation device 300A, the second hydrogen filling and power generation device 300B, the second hydrogen filling device 100B, the second power generation device 200B, the third hydrogen filling and power generation device 300C, the fourth hydrogen filling and power generation device 300D, the third hydrogen filling device 100C, the third power generation device 200C, the fifth hydrogen filling and power generation device 300E, and the sixth hydrogen filling and power generation device 300E. In the present embodiment, the description will be made using the sixth hydrogen filling and power generation device 300E.

[0206] FIG. 23 is a diagram showing the second hydrogen filling and power generation system. As shown in FIG. 23, the second hydrogen filling and power generation system 400B has the same structure as the first hydrogen filling and power generation system except that a liquid separation device 461 is provided in the device flow path 460.

[0207] (Liquid separation device) The liquid interruption device 461 is provided in the device flow path 460 which is a short - current path, and is provided to interrupt the continuity of the fluid hydrogen carrier 10 or the nickel hydroxide - containing slurry 302 and the nickel oxyhydroxide - containing slurry 304 that cause a short circuit. Here, interruption means blocking the short - circuit path by mixing gases such as air, nitrogen, and oxygen with low electrical conductivity into the continuous path of the fluid hydrogen carrier 10 or the nickel hydroxide - containing slurry 302 and the nickel oxyhydroxide - containing slurry 304 having electrical conductivity. The means for blocking the short - circuit path by mixing is not limited. For example, a structure for dropping the fluid hydrogen carrier 10 or the nickel hydroxide - containing slurry 302 and the nickel oxyhydroxide - containing slurry 304 like a drip chamber used in medical treatment etc. can be used. By dropping the electrically conductive fluid, the short - circuit path is blocked and the short - current does not flow.

[0208] Therefore, by having the above - described structure, the second hydrogen filling and power generation system 400B can reduce the short - current, similar to the hydrogen filling and power generation system 400A, and can perform hydrogen filling and power generation with high energy efficiency.

[0209] <The Third Hydrogen Filling and Power Generation System> The third hydrogen filling and power generation system using the fluid hydrogen carrier 10 according to this embodiment will be described. It can be applied to any of the hydrogen filling device 100A, the power generation device 200A, the hydrogen filling and power generation device 300A, the second hydrogen filling and power generation device 300B, the second hydrogen filling device 100B, the second power generation device 200B, the third hydrogen filling and power generation device 300C, the fourth hydrogen filling and power generation device 300D, the third hydrogen filling device 100C, the third power generation device 200C, the fifth hydrogen filling and power generation device 300E, and the sixth hydrogen filling and power generation device 300E. In this embodiment, the sixth hydrogen filling and power generation device 300E will be used for explanation.

[0210] FIG. 24 is a diagram showing a third hydrogen filling and power generation system. As shown in FIG. 24, the third hydrogen filling and power generation system 400C has the same structure as the first hydrogen filling and power generation system, except that 300462 is provided in the device flow path 460.

[0211] (Openable and closable valve) The openable and closable valve 462 is provided in the device flow path 460 which is a short-circuit current path, and is provided to interrupt the continuity of the fluid hydrogen carrier 10 or the nickel hydroxide-containing slurry 302 and the nickel oxyhydroxide-containing slurry 304 that cause short circuits. Here, interruption means blocking the continuous path of the fluid hydrogen carrier 10 having electrical conductivity or the nickel hydroxide-containing slurry 302 and the nickel oxyhydroxide-containing slurry 304 by the valve. Also, at the same time, only the valve connected to one device among the devices connected in series can be opened simultaneously.

[0212] Therefore, by having the above structure, the third hydrogen filling and power generation system 400C can reduce the short-circuit current and perform hydrogen filling and power generation with high energy efficiency, similar to the hydrogen filling and power generation system 400A.

[0213] <Fourth hydrogen filling and power generation system> The fourth hydrogen filling and power generation system using the fluid hydrogen carrier 10 according to this embodiment will be described. It can be applied to any of the hydrogen filling device 100A, the power generation device 200A, the hydrogen filling and power generation device 3A, the second hydrogen filling and power generation device 300B, the second hydrogen filling device 100B, the second power generation device 200B, the third hydrogen filling and power generation device 300C, the fourth hydrogen filling and power generation device 300D, the third hydrogen filling device 100C, the third power generation device 200C, the fifth hydrogen filling and power generation device 300E, the sixth hydrogen filling and power generation device 300E, the hydrogen filling and power generation system 400A, the second hydrogen filling and power generation system 400B, and the third hydrogen filling and power generation system 400C. However, in this embodiment, the sixth hydrogen filling and power generation device 300E will be used for the description.

[0214] FIG. 25 is a diagram showing a fourth hydrogen filling and power generation system. As shown in FIG. 25, the fourth hydrogen filling and power generation system 400D has the same structure as the first hydrogen filling and power generation system, except that it includes a second negative electrode tank 470 and a second positive electrode tank 480. It is also possible to use only the second negative electrode tank 470. According to this structure, the negative electrode tank for storing the hydrogen-filled fluid hydrogen carrier 14 can store the fluid hydrogen carrier separately from the fluid hydrogen carrier 10 before hydrogen filling. Also, according to this structure, the positive electrode tank for storing the nickel hydroxide-containing slurry 302 can store the fluid hydrogen carrier separately from the nickel oxyhydroxide-containing slurry 304.

[0215] (Second negative electrode tank) Since the second negative electrode tank 470 has the same structure as the negative electrode tank 410, a detailed description thereof will be omitted. A sixth hydrogen filling and power generation device 300E is disposed between the second negative electrode tank 470 and the negative electrode tank 410. With this arrangement, the fluid hydrogen carrier 10 before hydrogen filling and the hydrogen-filled fluid hydrogen carrier 14 can be stored separately.

[0216] (Second positive electrode tank) Since the second positive electrode tank 480 has the same structure as the positive electrode tank 430, a detailed description thereof will be omitted. A sixth hydrogen filling and power generation device 300E is disposed between the second positive electrode tank 480 and the positive electrode tank 430. With this arrangement, the nickel hydroxide-containing slurry 302 and the nickel oxyhydroxide-containing slurry 304 can be stored separately.

[0217] Therefore, the fourth hydrogen filling and power generation system 400D has the above structure, so that when the hydrogen carrier is taken out as a tank, the fluid hydrogen carriers before and after hydrogen filling do not mix, and thus it can be easily used as a hydrogen carrier.

[0218] As described above, each embodiment has been explained. However, each of the above embodiments is presented as an example, and the present invention is not limited by each of the above embodiments. Each of the above embodiments can be implemented in various other forms, and various combinations, omissions, replacements, changes, etc. can be made without departing from the gist of the invention. These embodiments and their modifications are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalent scope thereof.

Example

[0219] Hereinafter, examples and comparative examples will be shown to more specifically explain the embodiments. However, the embodiments are not limited by these examples and comparative examples.

[0220] <Example 1-1> [Preparation of Fluid Hydrogen Carrier] 0.2 wt% of carboxymethyl cellulose (CMC) was mixed with a 6 mol / L aqueous potassium hydroxide solution and stirred overnight to dissolve the CMC. 8.125 g of the solution was mixed with 2.5 g of the hydrogen storage alloy 261, and the operation of stirring at 2000 rpm for 3 minutes using a rotary mixer was repeated 3 times to prepare a fluid hydrogen carrier.

[0221] [Preparation of Charge and Discharge Cell] A charge and discharge cell 20 including the secondary battery 30B shown in FIG. 5 was prepared. Carbon paper was used as the positive current collector 22, nickel-plated stainless steel was used as the negative current collector 21, platinum-supported carbon was used as the oxygen electrode catalyst 23, an anion exchange membrane was used as the ion permeable membrane 24, butyl rubber was used as the ion permeable membrane 24, stainless steel containers were used as the tank 31 which is the negative electrode side tank and the tank 37 which is the positive electrode side tank, a uniaxial eccentric screw pump was used as the pump 32 which is the negative electrode side pump and the pump 38 which is the positive electrode side pump, and a nickel plate was used as the partition wall 35. The joints 27 and 36 were made of stainless steel pipes, and the charge and discharge cell 20, the tank 31, and the pump 32 were connected, and the charge and discharge cell 20, the tank 37, and the pump 38 were connected.

[0222] [Charging] 10 g of the alkaline electrolytic solution 262 was put into the tank 37, and 10 g of the fluid hydrogen carrier 26 was put into the tank 31, followed by charging with a current of 10 mA. At this time, the flow rates of the pumps 32 and 38 were both set to 5 mL / min for both the positive electrode and the negative electrode. The charging curve at this time is shown in Fig. 26. In Fig. 26, the vertical axis represents the voltage and the horizontal axis represents the charge capacity.

[0223] As shown in Fig. 26, the electrochemical reaction was proceeding at a constant voltage of about 1.55 V. This is considered to be because, although overvoltage is also involved, oxygen generation occurs at the positive electrode current collector 22 and hydrogen storage in the hydrogen storage alloy 261 occurs at the negative electrode current collector 21.

[0224] [Withdrawal of the fluid hydrogen carrier] A part of the negative electrode pipe was removed, and the fluid hydrogen carrier 26 was taken out by driving the negative electrode side pump.

[0225] [Discharge] 3 g of the charged fluid hydrogen carrier 26 was injected into the tank of a cell different from the charge-discharge cell used for charging, and only the negative electrode side pump was circulated at a flow rate of 5 mL / min. The inside of the positive electrode side cell was filled only with air. In this state, discharge was performed at a current density of 10 mA. The discharge curve at this time is shown in Fig. 27. In Fig. 27, the vertical axis represents the voltage and the horizontal axis represents the discharge capacity.

[0226] As shown in Fig. 27, the electrochemical reaction was proceeding at a constant voltage of about 0.75 V. This is considered to be because oxygen reduction occurred at the positive electrode current collector 22 and hydrogen release from the hydrogen storage alloy 261 occurred at the negative electrode current collector 21.

[0227] From Figs. 26 and 27, it was confirmed that the fluid hydrogen carrier 26 according to the present embodiment has fluidity at normal temperature and normal pressure, so that the charge-discharge cell 20 according to the present embodiment can easily extract and transfer the charged (hydrogen-stored) fluid hydrogen carrier 26, and hydrogen can be released (discharged) from the fluid hydrogen carrier 26 even thereafter.

[0228] The hydrogen carrier with fluidity according to this embodiment can densify hydrogen at normal temperature and pressure, so it can transport a large amount of hydrogen. In addition, since the hydrogen carrier with fluidity according to this embodiment has fluidity at normal temperature and pressure, it can be easily handled and transported with high efficiency. A charge-discharge cell equipped with the hydrogen carrier with fluidity according to this embodiment can electrochemically occlude and release hydrogen, so it can form a simple system that can easily control charge and discharge (hydrogen occlusion and release).

[0229] <Example 1-2> [Preparation of Hydrogen Carrier with Fluidity] A 6 mol / L aqueous potassium hydroxide solution and 5 wt% of sodium polyacrylate (PAANa) with a weight average molecular weight of 2700 were mixed and stirred overnight to dissolve PAANa. This solution and 20 vol% of a hydrogen storage alloy 11 with a median diameter of 15 μm were mixed, and the operation of stirring at 2000 rpm for 3 minutes using a rotating and revolving mixer was repeated three times to prepare a slurry. The hydrogen storage alloy was obtained by pulverizing and classifying it in an inert atmosphere. By heating this slurry at 100 °C for 2 hours, a hydrogen carrier with fluidity 10 was prepared. The viscosity of the hydrogen carrier with fluidity 10 of Example 1-2 was measured with a rheometer manufactured by Anton Paar. As a result, the viscosity at a shear rate of 100 sec ―1 was 450 mPa·sec.

[0230] [Preparation of Hydrogen Filling Device] A hydrogen filling device 100A shown in FIG. 6 was prepared. Nickel-plated stainless steel was used as the positive electrode current collector 103, a nickel porous electrode with nickel sulfide formed on the surface was used as the oxygen generation electrode 105, nickel-plated stainless steel was used as the negative electrode current collector 21, an anion exchange membrane was used as the ion permeation membrane 106, and butyl rubber was used as the sealing material 107.

[0231] [Preparation of Hydrogen Filling System] A hydrogen filling system as shown in Fig. 22 was fabricated. A polypropylene tank was used as the negative electrode tank 410, a tube pump was used as the negative electrode pressurizing / de-pressurizing device 420, a polypropylene tank was used as the positive electrode tank 430, a tube pump was used as the positive electrode pressurizing / de-pressurizing device 440, and a φ1.5 mm polypropylene tube was used as the device flow path 460. Since Examples 1-2 are not laminated cells, the inter-device flow path was not used.

[0232] [Hydrogen filling into the fluid hydrogen carrier] 12 mL of the fluid hydrogen carrier 10 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / de-pressurizing device 420, and the 6 mol / L potassium hydroxide aqueous solution was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / de-pressurizing device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and charging was performed up to a capacity of 6.624 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the introduced fluid hydrogen carrier was 12 mL, the capacity density corresponds to 552 Ah / L. The charging curve during hydrogen filling according to Example 1-2 is shown in Fig. 28.

[0233] [Fabrication of the power generation device] The power generation device 200A shown in Fig. 8 was fabricated. Nickel-plated stainless steel was used as the positive electrode current collector 103, water-repellent treated carbon paper with platinum-supported carbon coated on the surface was used as the oxygen reduction electrode 201, nickel-plated stainless steel was used as the negative electrode current collector 21, an anion exchange membrane was used as the ion permeable membrane 106, and butyl rubber was used as the sealing material 107.

[0234] [Fabrication of the power generation system] A power generation system as shown in FIG. 22 was fabricated. A polypropylene tank was used as the negative electrode tank 410, a tube pump was used as the negative electrode pressurizing / de-pressurizing device 420, a tube pump was used as the positive electrode pressurizing / de-pressurizing device 440, and a φ1.5 mm polypropylene tube was used as the device flow path 460. In Examples 1-2, since the power generation devices were not stacked, the flow path between the devices was not used. Also, in Examples 1-2, the positive electrode tank 430 was not used because air was flowed.

[0235] [Power Generation Using a Mobile Hydrogen Carrier] The hydrogen-filled mobile hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled mobile hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / de-pressurizing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / de-pressurizing device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and discharging was performed until a voltage of 0.4 V was reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 5.492 Ah, and the average discharge voltage was 0.77 V. When the volume of the mobile hydrogen carrier 10 introduced into the power generation device of Examples 1-2 was measured, it was 10 mL. That is, the discharge capacity density corresponded to 549 Ah / L. The Ah efficiency in Examples 1-2 was 99.5%. The discharge curve during power generation according to Examples 1-2 is shown in FIG. 29.

[0236] In the power generation cell of the present invention, it was confirmed that the mobile hydrogen carrier composed of the hydrogen storage alloy and the alkaline electrolyte of the present invention is useful as a highly efficient hydrogen carrier.

[0237] Examples regarding the content of the hydrogen storage alloy in the mobile hydrogen carrier will be described below.

[0238] <Example 2> In the production of the fluid hydrogen carrier of Example 2, it is the same as Example 1-2 except that 15% by volume of the hydrogen storage alloy 11 is mixed. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system are the same as those of Example 1-2.

[0239] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into the fluid hydrogen carrier according to Example 2 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 2 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurization / decompression device 420, and the 6 mol / L potassium hydroxide aqueous solution was flowed at a flow rate of 5 mL / min by the positive electrode pressurization / decompression device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and charged up to a capacity of 4.968 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the volume of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 414 Ah / L.

[0240] [Power generation using the fluid hydrogen carrier] A power generation method according to Example 2 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative electrode pressurization / decompression device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurization / decompression device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and 30 mA / cm 2Discharge was performed until a voltage of 0.4 V was reached at the current value. The discharge capacity was 4.637 Ah, and the average discharge voltage was 0.71 V. When the volume of the mobile hydrogen carrier 10 introduced into the power generation device of Example 2 was measured, it was 11.2 mL. That is, the discharge capacity density corresponded to 412 Ah / L. The Ah efficiency in Example 2 was 99.7%.

[0241] <Example 3> In the production of the mobile hydrogen carrier of Example 3, it was the same as in Examples 1-2 except that the hydrogen storage alloy 11 was mixed at 25% by volume. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system were the same as in Examples 1-2.

[0242] [Hydrogen filling into the mobile hydrogen carrier] A method for filling hydrogen into the mobile hydrogen carrier according to Example 3 will be described. 12 mL of the mobile hydrogen carrier 10 of Example 3 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution was introduced into the positive electrode tank 430. The mobile hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurization / decompression device 420, and the 6 mol / L potassium hydroxide aqueous solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurization / decompression device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and 30 mA / cm 2 Charge was performed up to a capacity of 8.280 Ah at the current value. Note that since the volume of the introduced mobile hydrogen carrier was 12 mL, the capacity density corresponded to 690 Ah / L.

[0243] [Power generation using the mobile hydrogen carrier] The power generation method according to Example 3 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative electrode pressure increasing / decreasing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressure increasing / decreasing device 440.

[0244] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and a current value of 30 mA / cm was applied with respect to the area of the ion permeable membrane 106 until a voltage of 0.4 V was reached. Discharge was carried out. The discharge capacity was 7.086 Ah, and the average discharge voltage was 0.80 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 3 was measured, it was 10.3 mL. That is, the discharge capacity density corresponded to 687 Ah / L. The Ah efficiency in Example 3 was 99.7%. 2 The discharge capacity was 7.086 Ah, and the average discharge voltage was 0.80 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 3 was measured, it was 10.3 mL. That is, the discharge capacity density corresponded to 687 Ah / L. The Ah efficiency in Example 3 was 99.7%.

[0245] <Example 4> In the production of the fluid hydrogen carrier of Example 4, it was the same as in Examples 1-2 except that 30% by volume of the hydrogen storage alloy 11 was mixed. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system were the same as in Examples 1-2.

[0246] [Hydrogen filling into the fluid hydrogen carrier] The method of filling hydrogen into the fluid hydrogen carrier according to Example 4 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 4 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressure increasing / decreasing device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min by the positive electrode pressure increasing / decreasing device 440.

[0247] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge and discharge device manufactured by Hokuto Electric Works, respectively, and charged up to a capacity of 9.936 Ah at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. Note that since the amount of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 828 Ah / L. 2 The charging was performed up to a capacity of 9.936 Ah at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. Note that since the amount of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 828 Ah / L.

[0248] [Power Generation Using Fluid Hydrogen Carrier] The power generation method according to Example 4 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was caused to flow at a flow rate of 5 mL / min by the negative pressure / pressure reduction device 420, and air was caused to flow at a flow rate of 5 mL / min by the positive pressure / pressure reduction device 440.

[0249] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge and discharge device manufactured by Hokuto Electric Works, respectively, and discharged until a voltage of 0.4 V is reached at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. The discharge capacity was 4.322 Ah, and the average discharge voltage was 0.82 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 4 was measured, it was 6.0 mL. That is, the discharge capacity density corresponds to 720 Ah / L. The Ah efficiency in Example 4 was 87.0%. 2 The discharge capacity was 4.322 Ah, and the average discharge voltage was 0.82 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 4 was measured, it was 6.0 mL. That is, the discharge capacity density corresponds to 720 Ah / L. The Ah efficiency in Example 4 was 87.0%.

[0250] [Comparative Example 1] In the preparation of the fluid hydrogen carrier of Comparative Example 1, it was the same as in Examples 1-2 except that 10% by volume of the hydrogen storage alloy 11 was mixed. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system were the same as in Examples 1-2.

[0251] [Hydrogen Filling into Fluid Hydrogen Carrier] A method for filling hydrogen into a fluid hydrogen carrier according to Comparative Example 1 will be described. 12 mL of the fluid hydrogen carrier 10 of Comparative Example 1 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and the 6 mol / L potassium hydroxide aqueous solution was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and a current value of 30 mA / cm 2 was used for charging up to a capacity of 3.312 Ah. Note that since the volume of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 276 Ah / L.

[0252] [Power Generation Using Fluid Hydrogen Carrier] A power generation method according to Comparative Example 1 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440.

[0253] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and discharging was performed until a voltage of 0.4 V was reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 2.390 Ah, and the average discharge voltage was 0.71 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Comparative Example 1 was measured, it was 11.5 mL. That is, the discharge capacity density corresponds to 208 Ah / L. The Ah efficiency in Comparative Example 1 was 75.3%.

[0254] Examples 1-2, Examples 2 to 4, and Comparative Example 1 show the results of comparing the hydrogen filling and power generation characteristics of the fluid hydrogen carrier with different contents of the hydrogen storage alloy 11 in Table 1.

[0255] [Table 1]

[0256] When the hydrogen storage alloy content in Comparative Example 1 is 10% by volume, the Ah efficiency is low and the average discharge voltage is also low. From the result of the low average discharge voltage, it is predicted that the resistance is high. That is, when the hydrogen storage alloy content is 10% by volume, the amount of the hydrogen storage alloy with high electrical conductivity is small, and it is considered that the electrical conduction of the fluid hydrogen carrier itself is insufficient. In Examples 1-2, Example 2, and Example 3 where the hydrogen storage alloy content is 15% by volume or more, the Ah efficiency was 99% or more. From this, the hydrogen storage alloy content in the fluid hydrogen carrier is preferably 15% by volume or more. When the hydrogen storage alloy content in Example 4 is 30% by volume, the discharge capacity density during power generation is high, but the Ah efficiency is lower than that of Examples 1-2, Example 2, and Example 3. Also, in Example 4, the volume of the fluid hydrogen carrier that could be withdrawn from the tank of the hydrogen filling device to the power generation device was smaller than that of other levels. This is because the viscosity of the fluid hydrogen carrier increased due to the increase in the hydrogen storage alloy content.

[0257] Examples of the particle diameter of the hydrogen storage alloy of the fluid hydrogen carrier will be described below.

[0258] [Example 5] In the preparation of the fluid hydrogen carrier of Example 5, it is the same as Example 1-2 except that the hydrogen storage alloy 11 with a median diameter of 5 μm is used. Also, the configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system are the same as those of Example 1-2.

[0259] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into a fluid hydrogen carrier according to Example 5 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 5 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / decompressing device 420, and the 6 mol / L potassium hydroxide aqueous solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / decompressing device 440.

[0260] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and a current value of 30 mA / cm 2 was used to charge up to a capacity of 6.624 Ah. Note that since the volume of the introduced fluid hydrogen carrier was 12 mL, the capacity density corresponded to 552 Ah / L.

[0261] [Power Generation Using Fluid Hydrogen Carrier] A power generation method according to Example 5 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / decompressing device 420, and air was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / decompressing device 440.

[0262] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and a current value of 30 mA / cm 2 was used to discharge until a voltage of 0.4 V was reached. The discharge capacity was 4.943 Ah, and the average discharge voltage was 0.80 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 5 was measured, it was 9.3 mL. That is, the discharge capacity density corresponded to 532 Ah / L. The Ah efficiency in Example 5 was 96.3%.

[0263] <Example 6> In the preparation of the fluid hydrogen carrier of Example 6, it is the same as in Examples 1-2 except that the hydrogen storage alloy 11 with a median diameter of 25 μm is used. Also, the configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system are the same as in Examples 1-2.

[0264] [Hydrogen filling into the fluid hydrogen carrier] The method for filling hydrogen into the fluid hydrogen carrier according to Example 6 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 6 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative pressure / pressure reduction device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min with the positive pressure / pressure reduction device 440.

[0265] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and charged to a capacity of 6.624 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the volume of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 552 Ah / L.

[0266] [Power generation using the fluid hydrogen carrier] The power generation method according to Example 6 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min with the negative pressure / pressure reduction device 420, and air was flowed at a flow rate of 5 mL / min with the positive pressure / pressure reduction device 440.

[0267] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and 30 mA / cm 2Discharge was carried out until a voltage of 0.4 V was reached at the current value. The discharge capacity was 5.646 Ah, and the average discharge voltage was 0.78 V. When the volume of the mobile hydrogen carrier 10 introduced into the power generation device of Example 6 was measured, it was 10.3 mL. That is, the discharge capacity density corresponded to 548 Ah / L. The Ah efficiency in Example 6 was 99.3%.

[0268] <Example 7> In the production of the mobile hydrogen carrier of Example 7, it was the same as in Examples 1-2 except that the hydrogen storage alloy 11 with a median diameter of 35 μm was used. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system were the same as in Examples 1-2.

[0269] [Hydrogen filling into the mobile hydrogen carrier] A method for filling hydrogen into the mobile hydrogen carrier according to Example 7 will be described. 12 mL of the mobile hydrogen carrier 10 of Example 7 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution was introduced into the positive electrode tank 430. The mobile hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurization / decompression device 420, and the 6 mol / L potassium hydroxide aqueous solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurization / decompression device 440.

[0270] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and 30 mA / cm with respect to the area of the ion permeable membrane 106 2 The charging was carried out up to a capacity of 6.624 Ah at the current value. Since the volume of the introduced mobile hydrogen carrier was 12 mL, the capacity density corresponded to 552 Ah / L.

[0271] [Power generation using the mobile hydrogen carrier] The power generation method according to Example 7 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440.

[0272] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and discharging was performed until a voltage of 0.4 V was reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 5.744 Ah, and the average discharge voltage was 0.75 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 7 was measured, it was 10.5 mL. That is, the discharge capacity density corresponds to 547 Ah / L. The Ah efficiency in Example 7 was 99.1%.

[0273] <Example 8> In the production of the fluid hydrogen carrier of Example 8, it was the same as in Examples 1-2 except that the hydrogen storage alloy 11 having a median diameter of 45 μm was used. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system were the same as in Examples 1-2.

[0274] [Hydrogen filling into the fluid hydrogen carrier] The method for filling hydrogen into the fluid hydrogen carrier according to Example 8 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 8 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440.

[0275] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and charged to a capacity of 6.624 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the amount of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 552 Ah / L.

[0276] [Power Generation Using Fluid Hydrogen Carrier] The power generation method according to Example 8 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative pressure / pressure reduction device 420, and air was flowed at a flow rate of 5 mL / min by the positive pressure / pressure reduction device 440.

[0277] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and discharged until a voltage of 0.4 V is reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 5.841 Ah, and the average discharge voltage was 0.75 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 8 was measured, it was 10.7 mL. That is, the discharge capacity density corresponds to 545 Ah / L. The Ah efficiency in Example 8 was 98.9%.

[0278] [Comparative Example 2] In the production of the fluid hydrogen carrier of Comparative Example 2, it is the same as in Examples 1-2 except that the hydrogen storage alloy 11 having a median diameter of 55 μm is used. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system are the same as in Examples 1-2.

[0279] [Hydrogen Filling into Fluid Hydrogen Carrier] A method for hydrogen charging the fluid hydrogen carrier 10 according to Comparative Example 2 will be described. 12 mL of the fluid hydrogen carrier 10 of Comparative Example 2 was introduced into the negative electrode tank 410 of the hydrogen charging system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / decompressing device 420, and the 6 mol / L potassium hydroxide aqueous solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / decompressing device 440.

[0280] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen charging device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106 2 was used for charging. As a result, the flow of the fluid hydrogen carrier 10 stopped during charging. The cause of the stop was clogging of the flow path due to aggregation of the hydrogen storage alloy 11.

[0281] Examples 1-2, Examples 5-8, and Comparative Example 2 compared the hydrogen charging and power generation characteristics of the fluid hydrogen carrier when the median diameter of the hydrogen storage alloy 11 was changed. The results are shown in Table 2.

[0282]

Table 2

[0283] In the fluid hydrogen carrier 10 using the hydrogen storage alloy 11 with a median diameter of 55 μm in Comparative Example 2, the hydrogen storage alloy 11 aggregated during the flow. In other examples, substantially equivalent power generation characteristics were obtained. That is, it is preferable that the median diameter of the hydrogen storage alloy 11 according to the present invention is 50 μm or less. Further, in the fluid hydrogen carrier 10 using the hydrogen storage alloy 11 with a median diameter of 55 μm in Example 5, since the viscosity increased, the amount of the fluid hydrogen carrier that could be withdrawn to the power generation device was slightly less than other levels. That is, a more preferable median diameter is 10 μm or more and 50 μm or less, and still more preferably, 10 μm or more and 20 μm or less.

[0284] The following describes an example of an additive for a flowing hydrogen carrier to an alkaline electrolyte solution.

[0285] <Example 9> In the preparation of the flowing hydrogen carrier of Example 9, it was the same as in Examples 1-2 except that an aqueous potassium hydroxide solution of 6 mol / L and 3 wt% of sodium polyacrylate (PAANa) with a weight average molecular weight of 2700 were mixed. Also, the configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as in Examples 1-2. The viscosity of the flowing hydrogen carrier of Example 9 at a shear rate of 100 sec ―1 was 150 mPa·sec.

[0286] [Hydrogen filling into the flowing hydrogen carrier] A method for filling hydrogen into the flowing hydrogen carrier according to Example 9 will be described. 12 mL of the flowing hydrogen carrier 10 of Example 9 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of an aqueous potassium hydroxide solution of 6 mol / L was introduced into the positive electrode tank 430. The flowing hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / decompressing device 420, and the aqueous potassium hydroxide solution of 6 mol / L was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / decompressing device 440.

[0287] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and charged up to a capacity of 6.624 Ah at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. 2 Note that since the volume of the introduced flowing hydrogen carrier was 12 mL, the capacity density corresponded to 552 Ah / L.

[0288] [Power generation using the flowing hydrogen carrier] The power generation method according to Example 9 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative pressure / pressure reduction device 420, and air was flowed at a flow rate of 5 mL / min by the positive pressure / pressure reduction device 440.

[0289] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device were connected to the positive and negative electrodes of the charge / discharge device manufactured by Hokuto Denko, respectively, and 30 mA / cm with respect to the area of the ion permeable membrane 106 2 Discharge was performed until a voltage of 0.4 V was reached at a current value of. The discharge capacity was 5.191 Ah, and the average discharge voltage was 0.80 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 9 was measured, it was 10.2 mL. That is, the discharge capacity density corresponds to 509 Ah / L. The Ah efficiency in Example 9 was 92.2%.

[0290] <Example 10> In the production of the fluid hydrogen carrier of Example 10, it was the same as in Examples 1-2 except that a 6 mol / L aqueous potassium hydroxide solution and 7 wt% of sodium polyacrylate (PAANa) having a weight average molecular weight of 2700 were mixed. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system are the same as in Examples 1-2. The viscosity of the fluid hydrogen carrier of Example 10 at a shear rate of 100 sec ―1 was 750 mPa·sec.

[0291] [Hydrogen filling into the fluid hydrogen carrier] The method for filling hydrogen into the fluid hydrogen carrier according to Example 10 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 10 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative pressure / pressure reduction device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min by the positive pressure / pressure reduction device 440.

[0292] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge and discharge device manufactured by Hokuto Electric Works, respectively, and a current value of 30 mA / cm is applied with respect to the area of the ion permeable membrane 106 until a charge of 6.624 Ah is reached. The capacity of 6.624 Ah corresponds to a capacity density of 552 Ah / L because the introduced fluid hydrogen carrier is 12 mL. 2 The capacity of 6.624 Ah corresponds to a capacity density of 552 Ah / L because the introduced fluid hydrogen carrier is 12 mL.

[0293] [Power Generation Using Fluid Hydrogen Carrier] The power generation method according to Example 10 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier was flowed at a flow rate of 5 mL / min by the negative pressure / pressure reduction device 420, and air was flowed at a flow rate of 5 mL / min by the positive pressure / pressure reduction device 440.

[0294] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge and discharge device manufactured by Hokuto Electric Works, respectively, and a current value of 30 mA / cm is applied with respect to the area of the ion permeable membrane 106 until a voltage of 0.4 V is reached. The discharge capacity was 5.669 Ah, and the average discharge voltage was 0.73 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 10 was measured, it was 10.3 mL. That is, the discharge capacity density corresponds to 550 Ah / L. The Ah efficiency in Example 10 was 99.7%. 2 The discharge capacity was 5.669 Ah, and the average discharge voltage was 0.73 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 10 was measured, it was 10.3 mL. That is, the discharge capacity density corresponds to 550 Ah / L. The Ah efficiency in Example 10 was 99.7%.

[0295] [Comparative Example 3] In the preparation of the fluid hydrogen carrier of Comparative Example 3, it was the same as in Examples 1-2 except that a 6 mol / L aqueous potassium hydroxide solution and 5 wt% of sodium polyacrylate (PAANa) having a weight average molecular weight of 1200 were mixed. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system were the same as in Examples 1-2. The shear rate of the fluid hydrogen carrier of Comparative Example 3 was 100 sec ―1The viscosity at that time was 10 mPa·sec.

[0296] [Hydrogen filling into the fluid hydrogen carrier] The method of hydrogen filling into the fluid hydrogen carrier according to Comparative Example 3 will be described. 12 mL of the fluid hydrogen carrier 10 of Comparative Example 3 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / decompressing device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / decompressing device 440.

[0297] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and charged to a capacity of 6.624 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the amount of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 552 Ah / L.

[0298] [Power generation using the fluid hydrogen carrier] The power generation method according to Comparative Example 3 will be described. The hydrogen-filled fluid hydrogen carrier was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / decompressing device 420, and air was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / decompressing device 440.

[0299] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and charged to a capacity of 6.624 Ah at a current value of 30 mA / cm 2Discharge was performed until a voltage of 0.4 V was reached at the current value. The discharge capacity was 0.597 Ah, and the average discharge voltage was 0.47 V. When the volume of the mobile hydrogen carrier 10 introduced into the power generation device of Comparative Example 3 was measured, it was 10.5 mL. That is, the discharge capacity density corresponded to 57 Ah / L. The Ah efficiency in Comparative Example 3 was 10.3%.

[0300] <Comparative Example 4> In the preparation of the mobile hydrogen carrier of Comparative Example 4, it was the same as in Examples 1-2 except that a 6 mol / L aqueous potassium hydroxide solution and 10 wt% of sodium polyacrylate (PAANa) having a weight average molecular weight of 1200 were mixed. Also, the configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as in Examples 1-2. The shear rate of the mobile hydrogen carrier of Comparative Example 4 was 100 sec ―1 The viscosity at that time was 30 mPa·sec.

[0301] [Hydrogen filling into the mobile hydrogen carrier] A method for filling hydrogen into the mobile hydrogen carrier according to Comparative Example 4 will be described. 12 mL of the mobile hydrogen carrier 10 of Comparative Example 4 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The mobile hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / decompressing device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / decompressing device 440.

[0302] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and 30 mA / cm was applied with respect to the area of the ion permeable membrane 106 2 Charging was performed up to a capacity of 6.624 Ah at the current value. Note that since the volume of the introduced mobile hydrogen carrier was 12 mL, the capacity density corresponded to 552 Ah / L.

[0303] [Power generation using the mobile hydrogen carrier] The power generation method according to Comparative Example 4 will be described. A hydrogen-filled fluid hydrogen carrier was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative pressure / pressure reduction device 420, and air was flowed at a flow rate of 5 mL / min by the positive pressure / pressure reduction device 440.

[0304] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and 30 mA / cm with respect to the area of the ion permeable membrane 106 2 Discharge was performed until a voltage of 0.4 V was reached at a current value of. Immediately after the start of discharge, the set voltage was reached, and power generation was not possible in Example 12.

[0305] <Example 11> In the preparation of the fluid hydrogen carrier of Example 11, it was the same as in Examples 1-2 except that a 6 mol / L aqueous potassium hydroxide solution and 1 wt% of sodium polyacrylate (PAANa) having a weight average molecular weight of 20,000 were mixed. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system were the same as in Examples 1-2. The viscosity of the fluid hydrogen carrier of Example 11 at a shear rate of 100 sec ―1 was 270 mPa·sec.

[0306] [Hydrogen filling into the fluid hydrogen carrier] The method for filling hydrogen into the fluid hydrogen carrier according to Example 11 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 11 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative pressure / pressure reduction device 420, and a 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min by the positive pressure / pressure reduction device 440.

[0307] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and charged to a capacity of 6.624 Ah at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. Note that since the amount of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 552 Ah / L. 2 The charging was performed up to a capacity of 6.624 Ah at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. Since the amount of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 552 Ah / L.

[0308] [Power Generation Using Fluid Hydrogen Carrier] The power generation method according to Example 11 will be described. A hydrogen-filled fluid hydrogen carrier was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative pressure / pressure reduction device 420, and air was flowed at a flow rate of 5 mL / min by the positive pressure / pressure reduction device 440. In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and discharged until a voltage of 0.4 V is reached at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. The discharge capacity was 5.436 Ah, and the average discharge voltage was 0.78 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 11 was measured, it was 10.7 mL. That is, the discharge capacity density corresponds to 538 Ah / L. The Ah efficiency in Example 11 was 97.5%. 2 In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and discharged until a voltage of 0.4 V is reached at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. The discharge capacity was 5.436 Ah, and the average discharge voltage was 0.78 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 11 was measured, it was 10.7 mL. That is, the discharge capacity density corresponds to 538 Ah / L. The Ah efficiency in Example 11 was 97.5%.

[0309] [Example 12] In the preparation of the fluid hydrogen carrier of Example 12, it was the same as in Examples 1-2 except that a 6 mol / L aqueous potassium hydroxide solution and 5 wt% of hydroxyethyl cellulose (HEC) were mixed. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system were the same as in Examples 1-2. The viscosity of the fluid hydrogen carrier of Example 12 at a shear rate of 100 sec ―1 was 330 mPa·sec.

[0310] [Hydrogen Filling into Fluid Hydrogen Carrier] The method for filling hydrogen into the fluid hydrogen carrier according to Example 12 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 12 was put into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was put into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440.

[0311] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and a current value of 30 mA / cm 2 was used to charge up to a capacity of 6.624 Ah. Note that since the volume of the fluid hydrogen carrier introduced was 12 mL, the capacity density corresponds to 552 Ah / L.

[0312] [Power Generation Using Fluid Hydrogen Carrier] The power generation method according to Example 12 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and put into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440.

[0313] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and discharging was performed until a voltage of 0.4 V was reached at a current value of 30 mA / cm 2 The discharge capacity was 4.787 Ah, and the average discharge voltage was 0.71 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 12 was measured, it was 10.3 mL. That is, the discharge capacity density corresponds to 465 Ah / L. The Ah efficiency in Example 12 was 84.2%.

[0314] <Comparative Example 5> In the preparation of the fluid hydrogen carrier of Comparative Example 5, it was the same as in Examples 1-2 except that a 6 mol / L aqueous potassium hydroxide solution and 5 wt% sodium lignosulfonate (LSANa) were mixed. Also, the configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as in Examples 1-2. The viscosity of the fluid hydrogen carrier of Comparative Example 5 at a shear rate of 100 sec ―1 was 80 mPa·sec.

[0315] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into the fluid hydrogen carrier according to Comparative Example 5 will be described. 12 mL of the fluid hydrogen carrier 10 of Comparative Example 5 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurization / decompression device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurization / decompression device 440.

[0316] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and charged to a capacity of 6.624 Ah at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. 2 Note that since the volume of the introduced fluid hydrogen carrier was 12 mL, the capacity density corresponded to 552 Ah / L.

[0317] [Power generation using the fluid hydrogen carrier] A power generation method according to Comparative Example 5 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min with the negative electrode pressurization / decompression device 420, and air was flowed at a flow rate of 5 mL / min with the positive electrode pressurization / decompression device 440.

[0318] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and a current value of 30 mA / cm 2 is applied until a voltage of 0.4 V is reached. The discharge capacity is 0.205 Ah, and the average discharge voltage is 0.41 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Comparative Example 5 was measured, it was 10.6 mL. That is, the discharge capacity density corresponds to 19 Ah / L. The Ah efficiency in Comparative Example 5 was 3.5%.

[0319] <Example 13> In the preparation of the fluid hydrogen carrier of Example 13, it is the same as in Examples 1-2 except that a 6 mol / L aqueous potassium hydroxide solution and 5 wt% carboxymethyl cellulose (CMC) are mixed. Also, the configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system are the same as in Examples 1-2. The viscosity of the fluid hydrogen carrier of Example 13 at a shear rate of 100 sec ―1 was 500 mPa·sec.

[0320] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into the fluid hydrogen carrier according to Example 13 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 13 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative pressure / pressure reduction device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min by the positive pressure / pressure reduction device 440.

[0321] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and a current value of 30 mA / cm 2 is applied to charge up to a capacity of 6.624 Ah. Since the volume of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 552 Ah / L.

[0322] [Power Generation Using a Liquid Hydrogen Carrier] The power generation method according to Example 13 will be described. The hydrogen-filled liquid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled liquid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative electrode pressure increasing / decreasing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressure increasing / decreasing device 440.

[0323] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and a current of 30 mA / cm 2 was applied until a voltage of 0.4 V was reached with respect to the area of the ion permeable membrane 106. The discharge capacity was 5.586 Ah, and the average discharge voltage was 0.73 V. When the volume of the liquid hydrogen carrier 10 introduced into the power generation device of Example 13 was measured, it was 10.4 mL. That is, the discharge capacity density corresponded to 537 Ah / L. The Ah efficiency in Example 13 was 97.3%.

[0324] Examples 1-2, Examples 9-13, and Comparative Examples 3-5 compared the hydrogen filling and power generation characteristics when the type and amount of the additive to the alkaline electrolyte 12 contained in the liquid hydrogen carrier 10 were changed. The results are shown in Table 3.

[0325] [Table 3]

[0326] According to Table 3, Examples 1-2 and Examples 9-13 with a viscosity of 100 mPa·sec or more at a shear rate of 100 sec ―1 have a high Ah efficiency and a high capacity density. That is, in order to achieve a high Ah efficiency and a high capacity density, it is preferable to use the liquid hydrogen carrier 10 with a viscosity of 100 mPa·sec or more at a shear rate of 100 sec ―1 .

[0327] Also, looking at the difference in the weight average molecular weight (Mw) of the same PAANa in Table 3, when Mw is 1500 or more, it has a high Ah efficiency and a high volumetric density. That is, in order to achieve a high Ah efficiency and a high volumetric density, it is advisable to use an additive with Mw of 1500 or more.

[0328] Furthermore, looking at the difference in the types of additives in Table 3, PAANa, HEC, and CMC have a high Ah efficiency and a high volumetric density. That is, in order to achieve a high Ah efficiency and a high volumetric density, it is advisable to use additives such as PAANa, HEC, and CMC.

[0329] Hereinafter, examples and comparative examples of a method for suppressing sedimentation of a hydrogen storage alloy in a flowing hydrogen carrier will be described.

[0330] <Comparative Example 6> The flowing hydrogen carrier 10 of Comparative Example 6 was produced in the same manner as in Examples 1-2.

[0331] [Static sedimentation test] Depending on the use of the flowing hydrogen carrier 10, sedimentation of the hydrogen storage alloy 11 may not be allowed. That is, a technique for suppressing sedimentation of the flowing hydrogen carrier 10 is required. The method of the static sedimentation test for evaluating sedimentation will be described below. The flowing hydrogen carrier 10 of Comparative Example 6 was injected into a transparent glass container, and the upper part of the container was sealed with parafilm to prevent drying, and then left standing for 30 days. After standing, the presence or absence of a clear layer, which is the supernatant liquid, was confirmed. The state after the static test of Comparative Example 6 is shown in Fig. 30. A growth layer was confirmed in Comparative Example 6. That is, it was confirmed that sedimentation occurred after 30 days of standing.

[0332] The hydrogen filling and power generation characteristics of the flowing hydrogen carrier of Comparative Example 6 are the same as those of Examples 1-2.

[0333] <Example 14> As a method for suppressing sedimentation, thixotropic properties are imparted to the fluid hydrogen carrier 10. Carbon black was examined as a thixotropic agent, which is an additive for imparting thixotropic properties. The fluid hydrogen carrier 10 of Example 14 was produced in the same manner as Comparative Example 6, except that 0.5% by weight of carbon black was added to the fluid hydrogen carrier 10.

[0334] [Static sedimentation test] The state after the static test of Example 14 is shown in Fig. 31. No growth layer was confirmed in Example 14. That is, it was confirmed that there was no sedimentation after 30 days of standing.

[0335] [Hydrogen filling into the fluid hydrogen carrier] The method of filling hydrogen into the fluid hydrogen carrier 10 according to Example 14 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 14 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / decompressing device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / decompressing device 440.

[0336] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Charging was performed up to a capacity of 6.624 Ah at a current value of. Note that the capacity of 6.624 Ah corresponds to a capacity density of 552 Ah / L because the introduced fluid hydrogen carrier is 12 mL.

[0337] [Power generation using the fluid hydrogen carrier] The power generation method according to Example 14 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was caused to flow at a flow rate of 5 mL / min by the negative pressure booster / decompressor 420, and air was caused to flow at a flow rate of 5 mL / min by the positive pressure booster / decompressor 440.

[0338] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and discharge was performed until a voltage of 0.4 V was reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 4.395 Ah, and the average discharge voltage was 0.82 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 14 was measured, it was 8.2 mL. That is, the discharge capacity density corresponded to 535 Ah / L. The Ah efficiency in Example 14 was 97.1%.

[0339] By adding carbon black as a thixotropic agent, the power generation efficiency is equivalent to that of Comparative Example 6 without addition, but the average discharge voltage has increased. This is presumably because the carbon black itself has high electrical conductivity and has increased the electrical conductivity of the fluid hydrogen carrier 10. That is, it was confirmed that carbon black as a thixotropic agent has two effects of suppressing sedimentation and increasing the voltage, and is useful as a thixotropic agent.

[0340] The following is an implementation of the heat treatment method for the fluid hydrogen carrier.

[0341] <Comparative Example 7> In the production of the fluid hydrogen carrier of Comparative Example 7, it was the same as in Examples 1-2 except that it was not heated after stirring with a high-speed mixer. Also, the configurations of the hydrogen filling device, the hydrogen filling system, the power generation device, and the power generation system were the same as in Examples 1-2.

[0342] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into a fluid hydrogen carrier according to Comparative Example 7 will be described. 12 mL of the fluid hydrogen carrier 10 of Comparative Example 7 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and a current value of 30 mA / cm 2 was applied to charge up to a capacity of 6.624 Ah. Note that since the volume of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 552 Ah / L.

[0343] [Power Generation Using a Fluid Hydrogen Carrier] A power generation method according to Comparative Example 7 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440.

[0344] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and a current value of 30 mA / cm 2 was applied to discharge until a voltage of 0.4 V was reached. The discharge capacity was 1.802 Ah, and the average discharge voltage was 0.43 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Comparative Example 7 was measured, it was 10.2 mL. That is, the discharge capacity density corresponds to 177 Ah / L. The Ah efficiency in Comparative Example 7 was 32.0%.

[0345] <Example 15> In the production of the fluid hydrogen carrier of Example 15, it is the same as in Examples 1-2 except that it was heated at 80°C for 2 hours after stirring with a high-speed mixer. Also, the configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system are the same as in Examples 1-2.

[0346] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into the fluid hydrogen carrier according to Example 15 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 15 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / de-pressurizing device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / de-pressurizing device 440.

[0347] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and charged up to a capacity of 6.624 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the volume of the introduced fluid hydrogen carrier was 12 mL, the capacity density corresponds to 552 Ah / L.

[0348] [Power generation using the fluid hydrogen carrier] A power generation method according to Example 15 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min with the negative electrode pressurizing / de-pressurizing device 420, and air was flowed at a flow rate of 5 mL / min with the positive electrode pressurizing / de-pressurizing device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and 30 mA / cm 2Discharge was carried out until a voltage of 0.4 V was reached at the current value. The discharge capacity was 5.877 Ah, and the average discharge voltage was 0.76 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 15 was measured, it was 10.7 mL. That is, the discharge capacity density corresponded to 549 Ah / L. The Ah efficiency in Example 15 was 99.5%.

[0349] <Example 16> In the production of the fluid hydrogen carrier of Example 16, it was the same as in Examples 1-2 except that after stirring with a high-speed mixer, it was heated at 120 °C for 2 hours. Also, the configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as in Examples 1-2.

[0350] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into the fluid hydrogen carrier according to Example 16 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 16 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurization / decompression device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurization / decompression device 440.

[0351] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and 30 mA / cm with respect to the area of the ion permeable membrane 106 2 Charge was carried out up to a capacity of 6.624 Ah at the current value. Note that since the volume of the introduced fluid hydrogen carrier was 12 mL, the capacity density corresponded to 552 Ah / L.

[0352] [Power generation using the fluid hydrogen carrier] The power generation method according to Example 16 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was flowed at a flow rate of 5 mL / min by the negative electrode pressurization / decompression device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurization / decompression device 440.

[0353] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and a current of 30 mA / cm 2 was applied until a voltage of 0.4 V was reached with respect to the area of the ion permeable membrane 106. The discharge capacity was 5.669 Ah, and the average discharge voltage was 0.79 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 16 was measured, it was 10.3 mL. That is, the discharge capacity density corresponded to 550 Ah / L. The Ah efficiency in Example 16 was 99.7%.

[0354] Examples 1-2, Examples 15-16, and Comparative Example 7 compared the hydrogen filling and power generation characteristics when the heating temperature of the fluid hydrogen carrier 10 was changed. The results are shown in Table 4.

[0355]

Table 4

[0356] According to Table 4, Examples 1-2 and Examples 15-16 heated at 80°C or higher have high Ah efficiency and high capacity density. That is, in order to achieve high Ah efficiency and high capacity density, it is advisable to use the fluid hydrogen carrier 10 heated at a temperature of 80°C or higher.

[0357] The following describes the method for pulverizing the hydrogen storage alloy.

[0358] <Example 17> A 6 mol / L potassium hydroxide aqueous solution and 5 wt% of sodium polyacrylate (PAANa) with a weight average molecular weight of 2700 were mixed and stirred overnight to dissolve PAANa. This solution was mixed with 20 vol% of a hydrogen storage alloy 11 having a median diameter of 500 μm or more, and pulverized with a ball mill under the atmosphere to prepare a slurry adjusted to a median diameter of 15 μm. By heating this slurry at 100 °C for 2 hours, a fluid hydrogen carrier 10 was prepared. The viscosity of the fluid hydrogen carrier 10 of Example 17 was measured with a rheometer manufactured by Anton Paar. As a result, the viscosity at a shear rate of 100 sec ―1 was 450 mPa·sec. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system are the same as those in Examples 1-2.

[0359] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into the fluid hydrogen carrier according to Example 17 will be described. 12 mL of the fluid hydrogen carrier 10 of Example 17 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative electrode pressurization / decompression device 420, and the 6 mol / L potassium hydroxide aqueous solution was flowed at a flow rate of 5 mL / min with the positive electrode pressurization / decompression device 440.

[0360] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and charged to a capacity of 6.624 Ah at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. 2 The capacity of 6.624 Ah corresponds to a capacity density of 552 Ah / L because the introduced fluid hydrogen carrier was 12 mL.

[0361] [Power generation using the fluid hydrogen carrier] The power generation method according to Example 17 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was caused to flow at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and air was caused to flow at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440.

[0362] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and discharging was performed until a voltage of 0.4 V was reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 5.889 Ah, and the average discharge voltage was 0.78 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 17 was measured, it was 10.7 mL. That is, the discharge capacity density corresponded to 550 Ah / L. The Ah efficiency in Example 17 was 99.7%.

[0363] In Examples 1-2 and Example 17, the pulverization conditions of the hydrogen storage alloy in the fluid hydrogen carrier 10 were different. These hydrogen filling and power generation characteristics were compared. The results are shown in Table 5.

[0364]

Table 5

[0365] According to Table 5, no difference in power generation characteristics was observed between Example 17 in which pulverization was performed in the atmosphere in a state of being mixed with an alkaline electrolyte and Examples 1-2 in which pulverization was performed in an inert atmosphere. That is, it was confirmed that an inert atmosphere is not required by mixing an alkaline electrolyte and a hydrogen storage alloy, and pulverization can be easily performed.

[0366] The following was carried out regarding the structural differences between the hydrogen filling device and the power generation device.

[0367] <Example 18> The flowing hydrogen carrier used in Example 18 is the same as that in Examples 1-2. Example 18 is the same as the examples except that the second hydrogen filling device 100B and the second power generation device 200B shown in FIGS. 14 and 16 using a porous current collector are used.

[0368] [Fabrication of Hydrogen Filling Device] The second hydrogen filling device 100B shown in FIG. 14 was fabricated. Nickel-plated stainless steel was used as the positive current collector 103, a nickel porous electrode with nickel sulfide formed on the surface was used as the oxygen generation electrode 105, a 100-mesh nickel wire mesh was used as the porous positive current collector 112, nickel-plated stainless steel was used as the negative current collector 21, a 60-mesh nickel wire mesh was used as the porous negative current collector 111, an anion exchange membrane was used as the ion permeable membrane 106, and butyl rubber was used as the sealing material 107.

[0369] [Fabrication of Power Generation Device] The second power generation device 200B shown in FIG. 15 was fabricated. Nickel-plated stainless steel was used as the positive current collector 130, a water-repellent treated carbon paper coated with platinum-supported carbon on the surface was used as the oxygen reduction electrode 201, a 100-mesh nickel wire mesh was used as the porous positive current collector 112, nickel-plated stainless steel was used as the negative current collector 21, a 60-mesh nickel wire mesh was used as the porous negative current collector 111, an anion exchange membrane was used as the ion permeable membrane 106, and butyl rubber was used as the sealing material 107.

[0370] [Hydrogen Filling into Flowing Hydrogen Carrier] The method for filling hydrogen into the flowing hydrogen carrier according to Example 18 will be described. 12 mL of the flowing hydrogen carrier 10 of Example 18 was introduced into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L aqueous potassium hydroxide solution was introduced into the positive electrode tank 430. The flowing hydrogen carrier 10 was flowed at a flow rate of 5 mL / min with the negative pressure boosting / decompressing device 420, and the 6 mol / L aqueous potassium hydroxide solution was flowed at a flow rate of 5 mL / min with the positive pressure boosting / decompressing device 440.

[0371] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and charged up to a capacity of 6.624 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the amount of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 552 Ah / L.

[0372] [Power Generation Using Fluid Hydrogen Carrier] The power generation method according to Example 18 will be described. The hydrogen-filled fluid hydrogen carrier 14 was taken out from the negative electrode tank 410 of the hydrogen filling system and introduced into the negative electrode tank 410 of the power generation device 200A. The hydrogen-filled fluid hydrogen carrier 14 was caused to flow at a flow rate of 5 mL / min by the negative pressure increasing / decreasing device 420, and air was caused to flow at a flow rate of 5 mL / min by the positive pressure increasing / decreasing device 440.

[0373] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and discharged until a voltage of 0.4 V is reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 5.669 Ah, and the average discharge voltage was 0.80 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 18 was measured, it was 10.3 mL. That is, the discharge capacity density corresponds to 550 Ah / L. The Ah efficiency in Example 18 was 99.6%.

[0374] [Example 19] The fluid hydrogen carrier used in Example 19 is the same as that in Examples 1-2. In Example 19, the third hydrogen filling and power generation device shown in Fig. 16, which enables hydrogen filling and power generation in one device, is used.

[0375] [Fabrication of Hydrogen Filling and Power Generation Device] A method for manufacturing a hydrogen filling and power generation device according to Example 19 will be described. A third hydrogen filling and power generation device 300C shown in FIG. 16 was manufactured. As the positive current collector 103, nickel-plated stainless steel was used; as the binary electrode 301, a nickel porous body with a pyrochlore-type bismuth iridium oxide coated on its surface was used; as the porous positive current collector 112, a 100-mesh nickel wire mesh was used; as the negative current collector 21, nickel-plated stainless steel was used; as the porous negative current collector 111, a 60-mesh nickel wire mesh was used; as the ion permeable membrane 106, an anion exchange membrane was used; and as the sealing material 107, butyl rubber was used.

[0376] [Manufacture of Hydrogen Filling and Power Generation System] A method for manufacturing a hydrogen filling and power generation system according to Example 19 will be described. A hydrogen filling system as shown in FIG. 22 was manufactured. As the negative electrode tank 410, a polypropylene tank was used; as the negative electrode pressurization / decompression device 420, a tube pump was used; as the positive electrode pressurization / decompression device 440, a tube pump was used; and as the device flow path 460, a φ1.5 mm polypropylene tube was used. Since Example 19 is not a stacked cell, an inter-device flow path was not used. Also, in Example 19, since air was flowed, the positive electrode tank 430 was not used.

[0377] [Hydrogen Filling into Fluid Hydrogen Carrier] A method for filling hydrogen into a fluid hydrogen carrier according to Example 19 will be described. 12 mL of the fluid hydrogen carrier 10 was introduced into the negative electrode tank 410 of the hydrogen filling and power generation system 400A. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurization / decompression device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurization / decompression device 440.

[0378] In this state, the positive current collector 103 and the negative current collector 101 of the hydrogen filling device were connected to the positive and negative electrodes of a charge / discharge device manufactured by Hokuto Denko, respectively, and charging was performed up to a capacity of 6.624 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the introduced fluid hydrogen carrier was 12 mL, the capacity density corresponds to 552 Ah / L for the capacity of 6.624 Ah.

[0379] [Power Generation Using a Liquid Hydrogen Carrier] The power generation method according to Example 19 will be described. The positive current collector 103 and the negative current collector 101 of the hydrogen filling device were connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and discharged until a voltage of 0.4 V was reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 6.604 Ah, and the average discharge voltage was 0.70 V. When the volume of the liquid hydrogen carrier 10 introduced into the power generation device of Example 19 was measured, it was 12 mL. This is because hydrogen filling / power generation is possible with one device, and there is no need to extract and transfer the liquid hydrogen carrier. That is, the discharge capacity density corresponds to 550 Ah / L. The Ah efficiency in Example 19 was 99.8%.

[0380] [Example 20] The liquid hydrogen carrier used in Example 20 is the same as that in Examples 1-2. In Example 20, the fourth hydrogen filling and power generation device shown in FIG. 17, in which hydrogen filling and power generation are possible with one device, is used.

[0381] [Fabrication of Hydrogen Filling and Power Generation Device] The method for fabricating the hydrogen filling and power generation device according to Example 20 will be described. The fourth hydrogen filling and power generation device 300D shown in FIG. 17 was fabricated. Nickel-plated stainless steel was used as the positive current collector 103, 100-mesh nickel wire mesh was used as the porous positive current collector 112, nickel-plated stainless steel was used as the negative current collector 21, 60-mesh nickel wire mesh was used as the porous negative current collector 111, an anion exchange membrane was used as the ion permeable membrane 106, and butyl rubber was used as the sealing material 107.

[0382] [Fabrication of Hydrogen Filling and Power Generation System] A method for manufacturing a hydrogen filling and power generation system according to Example 20 will be described. A hydrogen filling system as shown in FIG. 22 was manufactured. A polypropylene tank was used as the negative electrode tank 410, a polypropylene tank was used as the positive electrode tank 430, a tube pump was used as the negative electrode pressurizing / decompressing device 420, a tube pump was used as the positive electrode pressurizing / decompressing device 440, and a φ1.5 mm polypropylene tube was used as the device flow path 460. Since Example 20 is not a laminated cell, an inter-device flow path was not used.

[0383] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into a fluid hydrogen carrier according to Example 20 will be described. 12 mL of the fluid hydrogen carrier 10 was introduced into the negative electrode tank 410 of the hydrogen filling and power generation system 400A, and 20 mL of a nickel hydroxide-containing slurry was introduced into the positive electrode tank 430. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and the nickel hydroxide-containing slurry was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440.

[0384] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and charged up to a capacity of 6.624 Ah at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. 2 Note that since the introduced fluid hydrogen carrier was 12 mL, the capacity of 6.624 Ah corresponds to a capacity density of the fluid hydrogen carrier of 552 Ah / L.

[0385] [Power generation using the fluid hydrogen carrier] A power generation method according to Example 20 will be described. The positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and 30 mA / cm 2Discharge was carried out until a voltage of 0.4 V was reached at the current value of . The discharge capacity was 4.789 Ah, and the average discharge voltage was 1.2 V. This was because the redox potential of nickel hydroxide, which is the positive electrode, was high, so a higher voltage could be obtained than in Example 1-2. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 20 was measured, it was 12 mL. This is because hydrogen filling / generation is possible with one device, so there is no need to extract and transfer the fluid hydrogen carrier. That is, the discharge capacity density corresponds to 399 Ah / L. The Ah efficiency in Example 20 was 72.3%. It is considered that the reason for the low Ah efficiency is that the Ah efficiency of the nickel hydroxide slurry was low, so hydrogen could not be sufficiently desorbed from the hydrogen storage alloy.

[0386] In Examples 1-2 and Examples 18 to 20, the structures of the hydrogen filling and power generation devices are different. The results are shown in Table 6.

[0387]

Table 6

[0388] According to Table 6, it can be seen that Example 18 using a porous current collector has a higher voltage than Example 1-2 that does not use it. This is presumably because the resistance of the device was reduced because the positive and negative electrodes collect current in a closer state. Also, in the structure of Example 19 where hydrogen filling and power generation are possible with one cell, power generation characteristics almost equivalent to those of Example 18 that requires different devices for hydrogen filling and power generation are obtained. However, the discharge voltage is slightly lower. This is presumably because the oxygen reduction overvoltage of the binary catalyst is high. Also, in Example 20 using a nickel hydroxide-containing slurry for the positive electrode instead of the structure of an air battery using oxygen, the Ah efficiency is low compared to other examples, but a high voltage can be obtained. It is advantageous in terms of the energy amount Wh, which is the product of the voltage V and the capacity Ah. From the above results, it was confirmed that the hydrogen filling device and power generation device implemented in each example are effective in hydrogen filling into the fluid hydrogen carrier of the present invention and power generation.

[0389] The following describes different embodiments of a short-circuit suppression structure for a hydrogen filling device and a power generation device connected in series.

[0390] <Comparative Example 8> Comparative Example 8 has a bipolar structure in which a hydrogen filling device and a power generation device are connected in series.

[0391] [Production of a Fluid Hydrogen Carrier] The fluid hydrogen carrier used in Comparative Example 8 is the same as in Examples 1-2.

[0392] [Production of a Hydrogen Filling and Power Generation Device] A method for producing a hydrogen filling and power generation device according to Comparative Example 8 will be described. The fifth hydrogen filling and power generation device 300E shown in FIG. 20 was produced. Nickel-plated stainless steel was used as the positive electrode current collector 103, a nickel porous body with a pyrochlore-type bismuth iridium oxide coated on the surface was used as the binary electrode 301, 100-mesh nickel wire mesh was used as the porous positive electrode current collector 112, nickel-plated stainless steel was used as the negative electrode current collector 21, 60-mesh nickel wire mesh was used as the porous negative electrode current collector 111, an anion exchange membrane was used as the ion permeation membrane 106, butyl rubber was used as the sealing material 107, and nickel-plated stainless steel was used as the bipolar plate 121.

[0393] [Production of a Hydrogen Filling and Power Generation System] A method for producing a hydrogen filling and power generation system according to Comparative Example 8 will be described. A hydrogen filling system as shown in FIG. 22 was produced. A polypropylene tank was used as the negative electrode tank 410, a tube pump was used as the negative electrode pressurization / decompression device 420, a tube pump was used as the positive electrode pressurization / decompression device 440, a φ1.5 mm polypropylene tube was used as the device flow path 460, and a φ1.5 mm polypropylene tube was used as the inter-device flow path 450. Also, in Comparative Example 8, the positive electrode tank 430 was not used because air was flowed. Also, in Comparative Example 8, the length of the short-circuit current path (the path of the continuous inter-device flow path 450 and the device flow path 460 between adjacent hydrogen filling and power generation devices sandwiching the bipolar plate 121), indicated by the broken line in FIG. 22, was set to 25 cm.

[0394] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into the fluid hydrogen carrier according to Comparative Example 8 will be described. 12 mL of the fluid hydrogen carrier 10 was introduced into the negative electrode tank 410 of the hydrogen filling and power generation system 400A. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and 30 mA / cm 2 charging was performed up to a capacity of 3.312 Ah at a current value of. Note that since the volume of the introduced fluid hydrogen carrier is 12 mL, the capacity density corresponds to 276 Ah / L. Since it is a two-series connection device, the voltage is doubled, and the amount of energy is the same as that of the previous examples.

[0395] [Power generation using the fluid hydrogen carrier] A power generation method according to Comparative Example 8 will be described. The positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and 30 mA / cm 2 discharging was performed until a voltage of 0.4 V was reached at a current value of. The discharge capacity was 1.411 Ah, and the average discharge voltage was 0.66 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Comparative Example 8 was measured, it was 12 mL. This is because hydrogen filling / generation is possible with one device, and there is no need to extract and transfer the fluid hydrogen carrier. That is, the discharge capacity density corresponds to 118 Ah / L. The Ah efficiency in Comparative Example 8 was 42.6%. That is, short-circuit suppression could not be achieved, and sufficient hydrogen filling could not be performed with the configuration of Comparative Example 8.

[0396] [Example 21] Example 21 has a bipolar structure in which a hydrogen filling device and a power generation device are connected in series, and the short-circuit path was extended to suppress short circuits.

[0397] [Preparation of Liquid Hydrogen Carrier] The liquid hydrogen carrier used in Example 21 is the same as that in Examples 1-2.

[0398] [Preparation of Hydrogen-Filled and Power Generation Device] The method for manufacturing the hydrogen-filled and power generation device according to Example 21 is the same as that in Comparative Example 8.

[0399] [Preparation of Hydrogen-Filled and Power Generation System] The method for manufacturing the hydrogen-filled and power generation system according to Example 21 is the same as that in Comparative Example 8, except that the length of the short-circuit current path (the path of the continuous inter-device flow path 450 and the device flow path 460 between adjacent hydrogen-filled and power generation devices across the bipolar plate 121) indicated by the dashed line in FIG. 22 is 50 cm.

[0400] [Hydrogen Filling into Liquid Hydrogen Carrier] The method for filling hydrogen into the liquid hydrogen carrier according to Example 21 will be described. 12 mL of the liquid hydrogen carrier 10 was introduced into the negative electrode tank 410 of the hydrogen-filled and power generation system 400A. The liquid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurization / decompression device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurization / decompression device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and charged to a capacity of 3.312 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the volume of the introduced liquid hydrogen carrier is 12 mL, the capacity density corresponds to 276 Ah / L. Since it is a two-series connection device, the voltage is doubled, and the energy amount is the same as that of the previous examples.

[0401] [Power Generation Using Liquid Hydrogen Carrier] The power generation method according to Example 21 will be described. The positive current collector 103 and the negative current collector 101 of the hydrogen filling device are respectively connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, and discharging is performed until a voltage of 0.4 V is reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 3.246 Ah, and the average discharge voltage was 1.53 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 21 was measured, it was 12 mL. This is because hydrogen filling / power generation is possible with one device, and there is no need to extract and transfer the fluid hydrogen carrier. That is, the discharge capacity density corresponds to 270 Ah / L. The Ah efficiency in the example was 97.8%. Compared with Example 19 which was not laminated, in Example 21, a voltage about twice as high can be obtained, and since the Ah efficiency is high, it is considered that the short current can be sufficiently suppressed by the configuration of Example 21.

[0402] <Example 22> Example 22 has a bipolar structure in which a hydrogen filling device and a power generation device are connected in series, and a liquid separation device 461 is provided to suppress short circuits.

[0403] [Production of Fluid Hydrogen Carrier] The fluid hydrogen carrier used in Example 22 is the same as in Examples 1-2.

[0404] [Production of Hydrogen Filling and Power Generation Device] The method for producing the hydrogen filling and power generation device according to Example 22 is the same as in Comparative Example 8.

[0405] [Production of Hydrogen Filling and Power Generation System] A method for manufacturing a hydrogen filling and power generation system according to Example 22 will be described. A second hydrogen filling and power generation system 400B as shown in FIG. 23 was manufactured. A polypropylene tank was used as the negative electrode tank 410, a tube pump was used as the negative electrode pressurizing / de-pressurizing device 420, a tube pump was used as the positive electrode pressurizing / de-pressurizing device 440, a φ1.5 mm polypropylene tube was used as the device flow path 460, a φ1.5 mm polypropylene tube was used as the inter-device flow path 450, and a drip chamber was used as the liquid separation device 151. Also, in Example 22, the positive electrode tank 430 was not used to allow air to flow. Further, in Example 22, the length of the short-circuit current path (the path of the continuous inter-device flow path 450 and device flow path 460 between the hydrogen filling and power generation devices adjacent to each other with the bipolar plate 121 in between), indicated by the broken line in FIG. 22, was set to 5 cm.

[0406] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into a fluid hydrogen carrier according to Example 22 will be described. 12 mL of the fluid hydrogen carrier 10 was introduced into the negative electrode tank 410 of the second hydrogen filling and power generation system 400B. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / de-pressurizing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / de-pressurizing device 440.

[0407] In this state, the positive electrode current collector 103 and negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and charging was performed up to a capacity of 3.312 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. Note that since the amount of the introduced fluid hydrogen carrier was 12 mL, the capacity density corresponded to 276 Ah / L. Since it was a two-series connection device, the voltage was doubled, and the amount of energy (Wh) represented by the capacity density × voltage was the same as that of the previous examples.

[0408] [Power generation using the fluid hydrogen carrier] The power generation method according to Example 22 will be described. The positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge-discharge device manufactured by Hokuto Electric Works, respectively, and a discharge is performed at a current value of 30 mA / cm 2 until a voltage of 0.4 V is reached. The discharge capacity is 3.213 Ah, and the average discharge voltage is 1.54 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 22 was measured, it was 12 mL. This is because hydrogen filling / power generation is possible with one device, and there is no need to extract and transfer the fluid hydrogen carrier. That is, the discharge capacity density corresponds to 267 Ah / L. The Ah efficiency in Example 22 was 96.7%. Compared with Example 19 which was not laminated, in Example 22, a voltage approximately twice as high can be obtained, and since the Ah efficiency is high, it is considered that the configuration of Example 22 can sufficiently suppress the short-circuit current even in a short short-circuit path.

[0409] [Example 23] Example 23 has a bipolar structure in which a hydrogen filling device and a power generation device are connected in series, and a valve that can be opened and closed is provided to suppress short circuits.

[0410] [Production of Fluid Hydrogen Carrier] The fluid hydrogen carrier used in Example 23 is the same as in Examples 1-2.

[0411] [Production of Hydrogen Filling and Power Generation Device] The method for producing the hydrogen filling and power generation device according to Example 23 is the same as in Comparative Example 8.

[0412] [Production of Hydrogen Filling and Power Generation System] A method for manufacturing a hydrogen filling and power generation system according to Example 23 will be described. A third hydrogen filling and power generation system 400C as shown in FIG. 24 was manufactured. A polypropylene tank was used as the negative electrode tank 410, a tube pump was used as the negative electrode pressurizing / decompressing device 420, a tube pump was used as the positive electrode pressurizing / decompressing device 440, a φ1.5 mm polypropylene tube was used as the device flow path 460, a φ1.5 mm polypropylene tube was used as the inter-device flow path 450, and a solenoid valve was used as the openable / closable valve 462. Also, in Example 23, the positive electrode tank 430 was not used to flow air. Further, in Example 23, the length of the short-circuit current path (the path of the continuous inter-device flow path 450 and the device flow path 460 between the hydrogen filling and power generation devices adjacent to each other across the bipolar plate 121) indicated by the broken line in FIG. 22 was set to 5 cm.

[0413] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into a fluid hydrogen carrier according to Example 23 will be described. 12 mL of the fluid hydrogen carrier 10 was introduced into the negative electrode tank 410 of the third hydrogen filling and power generation system 400C. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / decompressing device 420. As the openable / closable valve 462, the solenoid valve opened the valve connected to one device among the devices connected in series at the same time. At that time, the other valves were in a closed waiting state. After 1 second, after closing the valve connected to that one device, the operation of opening the valve connected to the adjacent device for 1 second was repeated. Also, air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440.

[0414] In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and charging was performed up to a capacity of 3.312 Ah at a current value of 30 mA / cm with respect to the area of the ion permeable membrane 106. 2 Note that since the amount of the introduced fluid hydrogen carrier was 12 mL, the capacity of 3.312 Ah corresponds to a capacity density of 276 Ah / L. Since it is a two-series-connected device, the voltage is doubled, and the amount of energy (Wh) represented by the capacity density × voltage is the same as that of the previous examples.

[0415] [Power Generation Using a Liquid Hydrogen Carrier] A power generation method according to Example 23 will be described. The positive current collector 103 and the negative current collector 101 of the hydrogen filling device are connected to the positive and negative electrodes of the charge / discharge device manufactured by Hokuto Electric Works, respectively, and a current of 30 mA / cm 2 is applied until a voltage of 0.4 V is reached. The discharge capacity is 3.252 Ah, and the average discharge voltage is 1.54 V. When the volume of the liquid hydrogen carrier 10 introduced into the power generation device of Example 23 was measured, it was 12 mL. This is because hydrogen filling / power generation is possible with a single device, and there is no need to extract and transfer the liquid hydrogen carrier. That is, the discharge capacity density corresponds to 271 Ah / L. The Ah efficiency in Example 23 was 98.1%. Compared with Example 19 which was not stacked, a voltage approximately twice as high can be obtained in Example 23, and since the Ah efficiency is high, it is considered that the short-circuit current can be sufficiently suppressed even in a short short-circuit path with the configuration of Example 23.

[0416] As described above, Comparative Example 8 and Examples 21 to 23 have different short-circuit suppression structures for the hydrogen filling device and the power generation device connected in series. The effects are shown in Table 7.

[0417]

Table 7

[0418] According to Table 7, Comparative Example 8 with a short-circuit path distance of 25 cm, although it is a series-connected cell, the voltage has not doubled. And the Ah efficiency is also low. That is, short-circuit suppression has not been achieved. On the other hand, in Example 21 with a short-circuit path distance of 50 cm, Example 22 using the liquid separation device 461, and Example 23 using the openable and closable valve 462, the voltage has doubled and the Ah efficiency is high. That is, it was confirmed that Examples 21 to 23 of the present invention are effective as short-circuit suppression means for the series-connected hydrogen filling device and power generation device for filling hydrogen into the fluid hydrogen carrier of the present invention and for power generation using the fluid hydrogen carrier.

[0419] Other embodiments according to the present invention will be described below.

[0420] <Example 24> The fluid hydrogen carrier of the present invention may extract the hydrogen-filled fluid hydrogen carrier from the hydrogen filling device and transport it. When extracting, in order to extract in a state with a higher hydrogen filling depth, it is better that the non-hydrogen-filled fluid hydrogen carrier and the hydrogen-filled fluid hydrogen carrier do not mix. In Example 24, the second negative electrode tank 470, the second positive electrode tank 480, the negative electrode tank for storing the hydrogen-filled fluid hydrogen carrier 14, and the fluid hydrogen carrier 10 before hydrogen filling can be stored separately.

[0421] [Production of Fluid Hydrogen Carrier] The fluid hydrogen carrier used in Example 24 is the same as in Examples 1-2.

[0422] [Production of Hydrogen Filling and Power Generation Device] The method for producing the hydrogen filling and power generation device according to Example 24 is the same as that of Comparative Example 8.

[0423] [Production of Hydrogen Filling and Power Generation System] A method for manufacturing a hydrogen filling and power generation system according to Example 24 will be described. A fourth hydrogen filling and power generation system 400D as shown in FIG. 25 was manufactured. A polypropylene tank was used as the negative electrode tank 410, a polypropylene tank was used as the second negative electrode tank 171, a tube pump was used as the negative electrode pressurizing / decompressing device 420, a tube pump was used as the positive electrode pressurizing / decompressing device 440, a φ1.5 mm polypropylene tube was used as the device flow path 460, and a φ1.5 mm polypropylene tube was used as the inter-device flow path 450. Also, in Example 24, the positive electrode tank 430 and the second positive electrode tank 172 were not used for flowing air. Further, in Example 24, the length of the short-circuit current path (the path of the continuous inter-device flow path 450 and the device flow path 460 between the hydrogen filling and power generation devices adjacent to each other with the bipolar plate 121 interposed therebetween), indicated by the broken line in FIG. 22, was set to 25 cm.

[0424] [Hydrogen filling into the fluid hydrogen carrier] A method for filling hydrogen into a fluid hydrogen carrier according to Example 24 will be described. 12 mL of the fluid hydrogen carrier 10 was introduced into the negative electrode tank 410 of the fourth hydrogen filling and power generation system 400D. The fluid hydrogen carrier 10 was flowed at a flow rate of 1 mL / min by the negative electrode pressurizing / decompressing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / decompressing device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and charging was performed up to a capacity of 1.656 Ah at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. This corresponds to 50% of the capacity when completely filled with hydrogen.

[0425] Note that since the introduced fluid hydrogen carrier is 12 mL, the capacity of 1.656 Ah corresponds to a capacity density of 138 Ah / L. Since it is a two-series connection device, the voltage is doubled.

[0426] [Power generation using the fluid hydrogen carrier] The power generation method according to Example 24 will be described. The hydrogen-filled fluid hydrogen carrier in the second negative electrode tank 171 of the fourth hydrogen filling and power generation system 400D was extracted and put into the negative electrode tank 410.

[0427] The positive current collector 103 and the negative current collector 101 of the device were connected to the positive and negative electrodes of the charge and discharge device manufactured by Hokuto Electric Works, respectively, and discharged until a voltage of 0.4 V was reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 1.431 Ah, and the average discharge voltage was 1.53 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 24 was measured, it was 5 mL. That is, the discharge capacity density corresponded to 270 Ah / L. The Ah efficiency in Example 24 was 97.8%.

[0428] That is, although 50% hydrogen filling was performed into the hydrogen filling device, only the fluid hydrogen carrier completely filled with hydrogen was stored in the second negative electrode tank. Therefore, the fluid hydrogen carrier extracted therefrom was in a state of 100% hydrogen filling, and it was confirmed that Example 24 was useful.

[0429] Other embodiments according to the present invention will be described below.

[0430] <Example 25> Example 25 is the same hydrogen filling and power generation system as Example 19, except that liquid paraffin was introduced into the negative electrode tank. Since the liquid paraffin is lighter than the specific gravity of the fluid hydrogen carrier, it was introduced into the upper layer of the tank in the negative electrode tank for the purpose of suppressing the evaporation of water in the fluid hydrogen carrier.

[0431] [Hydrogen filling into the fluid hydrogen carrier] The method for filling hydrogen into the fluid hydrogen carrier according to Example 25 will be described. 12 mL of the fluid hydrogen carrier 10 was introduced into the negative electrode tank 410 of the hydrogen filling and power generation system 400A. The fluid hydrogen carrier 10 was flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / de-pressurizing device 420, and air was flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / de-pressurizing device 440. In this state, the positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and a current value of 30 mA / cm 2 was applied for charging up to a capacity of 6.624 Ah. Note that since the volume of the introduced fluid hydrogen carrier was 12 mL, the capacity density corresponds to 552 Ah / L.

[0432] [Power Generation Using Fluid Hydrogen Carrier] The power generation method according to Example 25 will be described. The positive electrode current collector 103 and the negative electrode current collector 101 of the hydrogen filling device were connected to the positive electrode and the negative electrode of the charge / discharge device manufactured by Hokuto Denko, respectively, and discharging was performed until a voltage of 0.4 V was reached at a current value of 30 mA / cm 2 with respect to the area of the ion permeable membrane 106. The discharge capacity was 6.604 Ah, and the average discharge voltage was 0.70 V. When the volume of the fluid hydrogen carrier 10 introduced into the power generation device of Example 25 was measured, it was 12 mL. This is because hydrogen filling / power generation is possible with one device, and there is no need to extract and transfer the fluid hydrogen carrier. That is, the discharge capacity density corresponds to 550 Ah / L. The Ah efficiency in Example 25 was 99.8%.

[0433] [Measurement of Solid Content Ratio after Hydrogen Filling and Power Generation Cycles] The above hydrogen filling and power generation operations were repeated 50 times. 1.0 g of the fluid hydrogen carrier after the 50th power generation was extracted and vacuum dried at 80 °C for 12 hours. The weight after vacuum drying was 0.75 g. That is, the solid content ratio in Example 25 was 75%.

[0434] [Comparative Example 9] Comparative Example 9 is the same hydrogen filling and power generation system as Example 24, except that liquid paraffin is not introduced into the negative electrode tank.

[0435] [Measurement of solid content ratio after hydrogen filling and power generation cycle] The operations of hydrogen filling and power generation were repeated 50 times. 1.0 g of the fluid hydrogen carrier after the 50th power generation was extracted and vacuum dried at 80 °C for 12 hours. The weight after vacuum drying was 0.79 g. That is, the solid content ratio in Comparative Example 9 was 79%.

[0436] From the above results, it can be seen that by introducing liquid paraffin, which has a lower specific gravity and is a hydrophobic liquid, than the fluid hydrogen carrier of the present invention into the negative electrode tank, an increase in the solid content ratio of the fluid hydrogen carrier can be suppressed. That is, it can be understood that the evaporation of water in the fluid hydrogen carrier can be suppressed by the configuration of each example.

[0437] Incidentally, aspects of embodiments of the present invention are as follows, for example. <1> A fluid hydrogen carrier containing a hydrogen storage alloy and an alkaline electrolyte. <2> The fluid hydrogen carrier according to <1>, wherein the hydrogen storage alloy is contained in an amount of 15% by volume or more of the entire fluid hydrogen carrier. <3> The fluid hydrogen carrier according to <1> or <2>, wherein the median diameter of the hydrogen storage alloy is 50 μm or less. <4> The fluid hydrogen carrier according to any one of <1> to <3>, wherein the viscosity at a shear rate of 100 sec ―1 is 100 mPa·sec or more. <5> The fluid hydrogen carrier according to any one of <1> to <4>, containing a water-soluble organic polymer having a weight average molecular weight of 1500 or more. <6> The fluid hydrogen carrier according to <5>, wherein the water-soluble organic polymer is a polyacrylate. <7> The fluid hydrogen carrier according to any one of <1> to <6>, containing a thixotropic agent. <8> The fluid hydrogen carrier according to any one of <1> to <7>, containing carbon black having a median diameter of 1 μm or less. <9> A method for producing a fluid hydrogen carrier according to any one of <1> to <8>, comprising: A method for producing a fluid hydrogen carrier, comprising a step of heating at 80 °C or higher. <10> A method for producing a fluid hydrogen carrier using the fluid hydrogen carrier according to any one of <1> to <8>, comprising: A method for producing a fluid hydrogen carrier, comprising a step of pulverizing the hydrogen storage alloy in a state where the hydrogen storage alloy and an alkaline solution are mixed. <11> A charge and discharge cell including a negative current collector, a positive current collector, an oxygen electrode catalyst, and an ion permeable membrane, A part of the negative current collector is electrically connected to the fluid hydrogen carrier according to any one of <1> to <8>, A part of the positive current collector is electrically connected to the oxygen electrode catalyst, A part of the oxygen electrode catalyst is ionically connected to the ion permeable membrane, The ion permeable membrane is provided so as to isolate the negative current collector and the positive current collector, A charge and discharge cell in which a part of the fluid hydrogen carrier is ionically connected to the ion permeable membrane. <12> A secondary battery including the charge and discharge cell according to <11>. <13> A hydrogen filling device including a negative current collector, a negative electrode void capable of filling the fluid hydrogen carrier according to any one of <1> to <8>, a positive current collector, a positive electrode void, an oxygen generation electrode, and an ion permeable membrane, The negative electrode void is in contact with both the negative current collector and the ion permeable membrane, The positive electrode void is in contact with an oxygen generation catalyst, A part of the positive current collector is electrically connected to the oxygen generation catalyst, A part of the oxygen generation catalyst is in contact with an alkaline aqueous solution, A part of the oxygen generation catalyst is ionically connected to the ion permeable membrane, The ion permeable membrane is provided so as to isolate the negative current collector and the positive current collector. <14> The hydrogen filling device according to <13>, wherein a voltage is applied between the negative electrode current collector and the positive electrode current collector in a state where a part or the whole of the negative electrode void is filled with or flowed with a fluid hydrogen carrier to fill the fluid hydrogen carrier with hydrogen. <15> The hydrogen filling device according to <13> or <14>, wherein a voltage is applied between the negative electrode current collector and the positive electrode current collector in a state where a part or the whole of the positive electrode void is filled with or flowed with an alkaline electrolyte to fill the fluid hydrogen carrier with hydrogen. <16> A power generation device comprising a negative electrode current collector, a negative electrode void capable of being filled with the fluid hydrogen carrier according to any one of <1> to <8>, a positive electrode current collector, a positive electrode void, an oxygen reduction catalyst, and an ion permeable membrane, wherein the negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane, wherein the positive electrode void is in contact with the oxygen reduction catalyst, wherein a part of the positive electrode current collector is electrically connected to the oxygen reduction catalyst, wherein a part of the oxygen reduction catalyst is ionically connected to the ion permeable membrane, wherein a part of the oxygen reduction catalyst is in contact with air, wherein the ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector. <17> The power generation device according to <16>, wherein a load is connected between the negative electrode current collector and the positive electrode current collector in a state where a part or the whole of the negative electrode void is filled with or flowed with a fluid hydrogen carrier. <18> The power generation device according to <16> or <17>, wherein a load is connected between the negative electrode current collector and the positive electrode current collector in a state where oxygen or air is flowed through a part or the whole of the positive electrode void to generate power. <19> A power generation device comprising a negative electrode current collector, a negative electrode void capable of being filled with the fluid hydrogen carrier according to any one of <1> to <8>, a positive electrode current collector, a positive electrode void, a dual catalyst capable of both oxygen generation and oxygen reduction, and an ion permeable membrane, wherein the negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane, The positive electrode void is in contact with the binary catalyst, A part of the positive electrode current collector is electrically connected to the binary catalyst, A part of the binary catalyst is in contact with air or an alkaline aqueous solution, A hydrogen filling and power generation device in which the ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector. <20> The hydrogen filling and power generation device according to <19>, wherein hydrogen is filled into the fluid hydrogen carrier by applying a voltage between the negative electrode current collector and the positive electrode current collector in a state where the negative electrode void is filled with or flowing with a fluid hydrogen carrier, and power generation is performed by connecting a load between the negative electrode current collector and the positive electrode current collector. <21> The hydrogen filling and power generation device according to <19> or <20>, wherein hydrogen is filled into the fluid hydrogen carrier by applying a voltage between the negative electrode current collector and the positive electrode current collector in a state where a part or the whole of the positive electrode void is filled with or flowing with an alkaline electrolyte solution, and power generation is performed by connecting a load between the negative electrode current collector and the positive electrode current collector in a state where oxygen or air is flowing through a part or the whole of the positive electrode void. <22> A hydrogen filling and power generation device comprising a negative electrode current collector, a negative electrode void capable of being filled with a fluid hydrogen carrier, a positive electrode current collector, a positive electrode void, and an ion permeable membrane, The negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane, The positive electrode void is in contact with both the positive electrode current collector and the ion permeable membrane, A hydrogen filling and power generation device in which the ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector. <23> In a state where a part or the whole of the negative electrode void is filled with or flowing with a fluid hydrogen carrier, and in a state where a part or the whole of the positive electrode void is filled with or flowing with a fluid nickel hydroxide slurry, A hydrogen filling and power generation device according to <22>, wherein hydrogen is filled into the mobile hydrogen carrier by applying a voltage between the negative current collector and the positive current collector, and power is generated by connecting a load between the negative current collector and the positive current collector. <24> The hydrogen filling device according to any one of <13> to <15>, wherein a part of the positive current collector, the negative current collector, or both is made of a porous conductor having through holes in the thickness direction, and a part thereof is in contact with the ion permeable membrane. <25> The hydrogen filling device according to any one of <13> to <15>, wherein a plurality of the hydrogen filling devices are stacked via a bipolar plate that also serves as the negative current collector and the positive current collector. <26> The power generation device according to any one of <16> to <18>, characterized in that a part of the positive current collector, the negative current collector, or both is made of a porous conductor having through holes in the thickness direction, and a part thereof is in contact with the ion permeable membrane. <27> The power generation device according to any one of <16> to <18>, wherein a plurality of the power generation devices are stacked via a bipolar plate that also serves as the negative current collector and the positive current collector. <28> The hydrogen filling and power generation device according to any one of <19> to <23>, wherein a part of the positive current collector, the negative current collector, or both is made of a porous conductor having through holes in the thickness direction, and a part thereof is in contact with the ion permeable membrane. <29> The hydrogen filling and power generation device according to any one of <19> to <23>, wherein a plurality of the hydrogen filling and power generation devices are stacked via a bipolar plate that also serves as the negative current collector and the positive current collector. <30> having a tank for storing the mobile hydrogen carrier, the mobile nickel hydroxide slurry, or the alkaline electrolyte, the tank is connected to the hydrogen filling device according to any one of <13> to <15> or the positive electrode void or the negative electrode void, A hydrogen filling system having a pressurizing / decompressing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the positive electrode void or the negative electrode void. <31> A region where a flow path for filling / discharging the fluid hydrogen carrier, the fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of the plurality of stacked hydrogen filling devices is composed of an insulating material, The hydrogen filling system according to <30>, wherein the shortest length of the continuous flow path composed of the insulating material from one bipolar plate to another bipolar plate is 20 cm or more. <32> A region where a flow path for filling / discharging the fluid hydrogen carrier, the fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of the plurality of stacked hydrogen filling devices is composed of an insulating material, The hydrogen filling system according to <30>, wherein the fluid hydrogen carrier, the fluid nickel hydroxide slurry, or the alkaline electrolyte is discontinuous in the flow path composed of the insulating material. <33> The hydrogen filling system according to any one of <30> to <32>, wherein an openable / closable valve is provided in a flow path for filling / discharging the fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of the plurality of stacked hydrogen filling devices. <34> The hydrogen filling system according to any one of <30> to <33>, wherein a tank for storing the fluid hydrogen carrier after hydrogen filling and a tank for storing the fluid hydrogen carrier after power generation are separated. <35> The hydrogen filling system according to any one of <30> to <34>, wherein a hydrophobic liquid having a specific gravity of 1.5 or less and a boiling point of 150°C or more is mixed in the tank. <36> Having a tank for storing the fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte, The tank is connected to the positive electrode void or the negative electrode void of the power generation device according to any one of <16> to <18>, It has a pressurizing / decompressing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the positive electrode void or the negative electrode void. <37> A flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of the plurality of stacked power generation devices has a region made of an insulating material. The power generation system according to <36>, wherein the shortest length of the flow path made of the continuous insulating material from one bipolar plate to another bipolar plate is 20 cm or more. <38> A flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of the plurality of stacked power generation devices has a region made of an insulating material. The power generation system according to <36>, wherein the fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte is discontinuous within the flow path made of the insulating material. <39> The power generation system according to any one of <36> to <38>, wherein an openable / closable valve is provided in a flow path for filling / discharging the fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of the plurality of stacked power generation devices. <40> The power generation system according to any one of <36> to <39>, wherein a tank for storing the fluid hydrogen carrier after hydrogen filling and a tank for storing the fluid hydrogen carrier after power generation are separated. <41> The power generation system according to any one of <36> to <40>, wherein a hydrophobic liquid having a specific gravity of 1.5 or less and a boiling point of 150°C or higher is mixed in the tank. <42> It has a tank for storing the fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte. The tank is connected to the positive electrode void or the negative electrode void of the hydrogen filling and power generation device according to any one of <19> to <23>. A hydrogen filling and power generation system having a pressurizing / decompressing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the positive electrode void or the negative electrode void. <43>The flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of the plurality of stacked hydrogen filling and power generation devices has a region made of an insulating material, and the shortest length of the continuous flow path made of the insulating material from one bipolar plate to another bipolar plate is 20 cm or more. The hydrogen filling and power generation system according to <42>. <44>The flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of the plurality of stacked hydrogen filling and power generation devices has a region made of an insulating material. In the flow path made of the insulating material, the fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte is discontinuous. The hydrogen filling and power generation system according to <42>. <45>A hydrogen filling and power generation system according to any one of <42> to <44>, wherein an openable / closable valve is provided in the flow path for filling / discharging the fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of the plurality of stacked hydrogen filling devices / power generation devices. <46>A hydrogen filling and power generation system according to any one of <42> to <45>, wherein a tank for storing the fluid hydrogen carrier after hydrogen filling and a tank for storing the fluid hydrogen carrier after power generation are separated. <47>A hydrogen filling and power generation system according to any one of <42> to <46>, wherein a hydrophobic liquid having a specific gravity of 1.5 or less and a boiling point of 150°C or more is mixed in the tank. <48> Extract the hydrogen-filled fluid hydrogen carrier or the fluid hydrogen carrier and the fluid nickel hydroxide slurry from the power generation system according to any one of <36> to <41>, and an energy transportation method for transporting the hydrogen-filled fluid hydrogen carrier or the fluid hydrogen carrier and the fluid nickel hydroxide slurry. <49> Extract the hydrogen-filled fluid hydrogen carrier or the fluid hydrogen carrier and the fluid nickel hydroxide slurry from the hydrogen filling and power generation system according to any one of <42> to <47>, and an energy transportation method for transporting the hydrogen-filled fluid hydrogen carrier or the fluid hydrogen carrier and the fluid nickel hydroxide slurry.

Explanation of Signs

[0438] 10, 26 Fluid hydrogen carrier 11, 261 Hydrogen storage alloy 12, 262 Alkaline electrolyte 13 Hydrogen-filled hydrogen storage alloy 14 Hydrogen-filled fluid hydrogen carrier 17, 27, 36, 108 Joint 20 Charge and discharge cell 21, 101 Negative electrode current collector 22, 103 Positive electrode current collector 23, Oxygen electrode catalyst 24, Ion permeable membrane 25, 34, 107 Sealing material 30A, 30B Secondary battery 31, 37 Tank 32, 38 Pump 35 Partition 53 Nickel oxyhydroxide-containing substance 100A Hydrogen filling device 100B Second hydrogen filling device 100C Third hydrogen filling device 102 Negative electrode void 104 Positive electrode void 105 Oxygen generation electrode 106 Ion permeable membrane 111 Porous negative electrode current collector 112 Porous positive electrode current collector 121 Bipolar plate 200A Power generation device 200B Second power generation device 200C Third power generation device 201 Oxygen reduction electrode 202 Oxygen-containing substance 300A Hydrogen filling and power generation device 300B Second hydrogen filling and power generation device 300C Third hydrogen filling and power generation device 300D Fourth hydrogen filling and power generation device 300E Fifth hydrogen filling and power generation device 300F Sixth hydrogen filling and power generation device 301 Binary electrode 302 Nickel hydroxide-containing slurry 303 Nickel hydroxide-containing substance 304 Nickel oxyhydroxide-containing slurry 400A Hydrogen filling and power generation system 400B Second hydrogen filling and power generation system 400C Third hydrogen filling and power generation system 400D Fourth hydrogen filling and power generation system 410 Negative electrode tank 420 Negative electrode pressurizing / decompressing device 430 Positive electrode tank 440 Positive electrode pressurizing / decompressing device 450 Inter-device flow path 460 Device flow path 461 Liquid separation device 462 Openable / closable valve 470 Second negative electrode tank 480 Second positive electrode tank

Claims

1. A fluid hydrogen carrier comprising a hydrogen storage alloy and an alkaline electrolyte.

2. The fluid hydrogen carrier according to claim 1, wherein the hydrogen storage alloy is contained in an amount of 15% by volume or more of the entire fluid hydrogen carrier.

3. The fluid hydrogen carrier according to claim 1 or 2, wherein the median diameter of the hydrogen storage alloy is 50 μm or less.

4. Shearing rate: 100 sec ―１ The fluid hydrogen carrier according to claim 1 or 2, wherein the viscosity at this time is 100 mPa·sec or more.

5. The fluid hydrogen carrier according to claim 1 or 2, comprising a water-soluble organic polymer having a weight average molecular weight of 1500 or more.

6. The fluid hydrogen carrier according to claim 5, wherein the water-soluble organic polymer is a polyacrylate.

7. The fluid hydrogen carrier according to claim 1 or 2, comprising a thixotropic agent.

8. The fluid hydrogen carrier according to claim 1 or 2, comprising carbon black having a median diameter of 1 μm or less.

9. A method for producing the fluid hydrogen carrier according to claim 1 or 2, The method for producing a fluid hydrogen carrier, comprising a step of heating at 80 °C or higher.

10. A method for producing the fluid hydrogen carrier according to claim 1 or 2, The method for producing a fluid hydrogen carrier, comprising a step of pulverizing the hydrogen storage alloy in a state where the hydrogen storage alloy and an alkaline solution are mixed.

11. A charge-discharge cell comprising a negative current collector, a positive current collector, an oxygen electrode catalyst, and an ion permeable membrane, wherein a part of the negative current collector is electrically connected to the fluid hydrogen carrier according to claim 1 or 2, a part of the positive current collector is electrically connected to the oxygen electrode catalyst, a part of the oxygen electrode catalyst is ionically connected to the ion permeable membrane, the ion permeable membrane is provided so as to isolate the negative current collector and the positive current collector, and a part of the fluid hydrogen carrier is ionically connected to the ion permeable membrane.

12. A secondary battery comprising the charge-discharge cell according to claim 11.

13. Comprising a negative current collector, a negative electrode void capable of being filled with the fluid hydrogen carrier according to claim 1 or 2, a positive current collector, a positive electrode void, an oxygen generation electrode, and an ion permeable membrane, wherein the negative electrode void is in contact with both the negative current collector and the ion permeable membrane, the positive electrode void is in contact with an oxygen generation catalyst, a part of the positive current collector is electrically connected to the oxygen generation catalyst, and a part of the oxygen generation catalyst is in contact with an alkaline aqueous solution. A part of the oxygen generation catalyst is ionically connected to the ion permeable membrane. A hydrogen filling device in which the ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector.

14. The hydrogen filling device according to claim 13, wherein a voltage is applied between the negative electrode current collector and the positive electrode current collector in a state where a part or all of the negative electrode void is filled or flowed with a fluid hydrogen carrier to fill the fluid hydrogen carrier with hydrogen.

15. The hydrogen filling device according to claim 13, wherein a voltage is applied between the negative electrode current collector and the positive electrode current collector in a state where a part or all of the positive electrode void is filled or flowed with an alkaline electrolyte to fill the fluid hydrogen carrier with hydrogen.

16. A power generation device comprising a negative electrode current collector, a negative electrode void capable of being filled with the fluid hydrogen carrier according to claim 1 or 2 that has been filled with hydrogen, a positive electrode current collector, a positive electrode void, an oxygen reduction catalyst, and an ion permeable membrane. The negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane. The positive electrode void is in contact with the oxygen reduction catalyst. A part of the positive electrode current collector is electrically connected to the oxygen reduction catalyst. A part of the oxygen reduction catalyst is ionically connected to the ion permeable membrane. A part of the oxygen reduction catalyst is in contact with air. The ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector.

17. The power generation device according to claim 16, wherein a load is connected between the negative electrode current collector and the positive electrode current collector in a state where a part or all of the negative electrode void is filled or flowed with a fluid hydrogen carrier.

18. The power generation device according to claim 16, wherein a load is connected between the negative electrode current collector and the positive electrode current collector in a state where oxygen or air is flowed through a part or all of the positive electrode void to generate power.

19. A negative electrode current collector, a negative electrode void capable of being filled with the fluid hydrogen carrier according to claim 1 or 2, a positive electrode current collector, a positive electrode void, a dual catalyst capable of both oxygen generation and oxygen reduction, and an ion permeable membrane. The negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane. The positive electrode void is in contact with the dual catalyst. A part of the positive electrode current collector is electrically connected to the dual catalyst. A part of the dual catalyst is in contact with air or an alkaline aqueous solution. A hydrogen filling and power generation device in which the ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector.

20. The hydrogen filling and power generation device according to claim 19, wherein hydrogen is filled into the fluid hydrogen carrier by applying a voltage between the negative electrode current collector and the positive electrode current collector in a state where the negative electrode void is filled with or flowing with a fluid hydrogen carrier, and power is generated by connecting a load between the negative electrode current collector and the positive electrode current collector.

21. The hydrogen filling and power generation device according to claim 19, wherein hydrogen is filled into the fluid hydrogen carrier by applying a voltage between the negative electrode current collector and the positive electrode current collector in a state where a part or the whole of the positive electrode void is filled with or flowing with an alkaline electrolyte, and power is generated by connecting a load between the negative electrode current collector and the positive electrode current collector in a state where oxygen or air is flowing through a part or the whole of the positive electrode void.

22. A hydrogen filling and power generation device comprising a negative electrode current collector, a negative electrode void capable of being filled with the fluid hydrogen carrier according to claim 1 or 2, a positive electrode current collector, a positive electrode void, and an ion permeable membrane, wherein the negative electrode void is in contact with both the negative electrode current collector and the ion permeable membrane, the positive electrode void is in contact with both the positive electrode current collector and the ion permeable membrane, and the ion permeable membrane is provided so as to isolate the negative electrode current collector and the positive electrode current collector.

23. In a state where a part or the whole of the negative electrode void is filled with or flowing with a fluid hydrogen carrier, and in a state where a part or the whole of the positive electrode void is filled with or flowing with a fluid nickel hydroxide slurry, The hydrogen filling and power generation device according to claim 22, wherein hydrogen is filled into the fluid hydrogen carrier by applying a voltage between the negative electrode current collector and the positive electrode current collector, and power is generated by connecting a load between the negative electrode current collector and the positive electrode current collector.

24. The hydrogen filling device according to claim 13, wherein a part of the positive electrode current collector or the negative electrode current collector or both is made of a porous conductor having through holes in the thickness direction, and a part thereof is in contact with the ion permeable membrane.

25. The hydrogen filling device according to claim 13, wherein a plurality of the hydrogen filling devices are stacked via a bipolar plate in which the negative electrode current collector and the positive electrode current collector are combined.

26. The power generation device according to claim 16, wherein a part of the positive current collector, the negative current collector, or both of them is made of a porous conductor having through holes in the thickness direction, and a part of it is in contact with the ion permeable membrane.

27. The power generation device according to claim 16, wherein a plurality of the power generation devices are stacked via a bipolar plate that also serves as the negative current collector and the positive current collector.

28. The hydrogen filling and power generation device according to claim 19, wherein a part of the positive current collector, the negative current collector, or both of them is made of a porous conductor having through holes in the thickness direction, and a part of it is in contact with the ion permeable membrane.

29. The hydrogen filling and power generation device according to claim 19, wherein a plurality of the hydrogen filling and power generation devices are stacked via a bipolar plate that also serves as the negative current collector and the positive current collector.

30. Having a tank for storing the fluid hydrogen carrier, the fluid nickel hydroxide slurry, or the alkaline electrolyte, The tank is connected to the hydrogen filling device according to claim 13, or the positive electrode void or the negative electrode void, A hydrogen filling system having a pressurizing / decompressing device capable of filling / discharging the fluid hydrogen carrier, the fluid nickel hydroxide slurry, air, oxygen, or the alkaline electrolyte into / from the positive electrode void or the negative electrode void.

31. Having a region where a flow path for filling / discharging the fluid hydrogen carrier, the fluid nickel hydroxide slurry, air, oxygen, or the alkaline electrolyte into / from the voids of each of the plurality of stacked hydrogen filling devices is composed of an insulating material, The hydrogen filling system according to claim 30, wherein the shortest length of the continuous flow path composed of the insulating material from one bipolar plate to another bipolar plate is 20 cm or more.

32. Having a region where a flow path for filling / discharging the fluid hydrogen carrier, the fluid nickel hydroxide slurry, air, oxygen, or the alkaline electrolyte into / from the voids of each of the plurality of stacked hydrogen filling devices is composed of an insulating material, The hydrogen filling system according to claim 30, wherein the fluid hydrogen carrier, the fluid nickel hydroxide slurry, or the alkaline electrolyte is discontinuous within the flow path composed of the insulating material.

33. The hydrogen filling system according to claim 30, wherein an openable and closable valve is provided in a flow path for filling / discharging the fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from voids of each of the plurality of stacked hydrogen filling devices.

34. The hydrogen filling system according to claim 30, wherein a tank for storing the fluid hydrogen carrier after hydrogen filling and a tank for storing the fluid hydrogen carrier after power generation are separated.

35. The hydrogen filling system according to claim 30, wherein a hydrophobic liquid having a specific gravity of 1.5 or less and a boiling point of 150 °C or higher is mixed in the tank.

36. It has a tank for storing the fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte, the tank is connected to the positive electrode void or the negative electrode void of the power generation device according to claim 16, A power generation system having a pressurizing / decompressing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the positive electrode void or the negative electrode void.

37. A flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from voids of each of the plurality of stacked power generation devices has a region made of an insulating material, The shortest length of the flow path made of the insulating material continuously from one bipolar plate to another bipolar plate is 20 cm or more. The power generation system according to claim 36.

38. A flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from voids of each of the plurality of stacked power generation devices has a region made of an insulating material, In the flow path made of the insulating material, the fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte is discontinuous. The power generation system according to claim 36.

39. The power generation system according to claim 36, wherein an openable and closable valve is provided in a flow path for filling / discharging the fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from voids of each of the plurality of stacked power generation devices.

40. The power generation system according to claim 36, wherein a tank for storing the fluid hydrogen carrier after hydrogen filling and a tank for storing the fluid hydrogen carrier after power generation are separated.

41. The power generation system according to claim 36, wherein a hydrophobic liquid having a specific gravity of 1.5 or less and a boiling point of 150°C or higher is mixed in the tank.

42. It has a tank for storing the fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte, The tank is connected to the positive electrode void or the negative electrode void of the hydrogen filling and power generation device according to claim 19, A hydrogen filling and power generation system having a pressurizing / decompressing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the positive electrode void or the negative electrode void.

43. A flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of a plurality of stacked hydrogen filling and power generation devices has a region made of an insulating material, and the shortest length of the continuous flow path made of the insulating material from one bipolar plate to another bipolar plate is 20 cm or more. The hydrogen filling and power generation system according to claim 42.

44. A flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of a plurality of stacked hydrogen filling and power generation devices has a region made of an insulating material, In the flow path made of the insulating material, the fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte is discontinuous. The hydrogen filling and power generation system according to claim 42.

45. The hydrogen filling and power generation system according to claim 42, wherein an openable / closable valve is provided in a flow path for filling / discharging the fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the voids of each of a plurality of stacked hydrogen filling devices / power generation devices.

46. The hydrogen filling and power generation system according to claim 42, wherein a tank for storing the fluid hydrogen carrier after hydrogen filling and a tank for storing the fluid hydrogen carrier after power generation are separated.

47. The hydrogen filling and power generation system according to claim 42, wherein a hydrophobic liquid having a specific gravity of 1.5 or less and a boiling point of 150°C or higher is mixed in the tank.

48. An energy transportation method of extracting the hydrogen-filled fluid hydrogen carrier, or the fluid hydrogen carrier and the fluid nickel hydroxide slurry from the power generation system according to claim 36, and transporting the hydrogen-filled fluid hydrogen carrier, or the fluid hydrogen carrier and the fluid nickel hydroxide slurry.

49. An energy transportation method of extracting the hydrogen-filled fluid hydrogen carrier, or the fluid hydrogen carrier and the fluid nickel hydroxide slurry from the hydrogen filling and power generation system according to claim 42, and transporting the hydrogen-filled fluid hydrogen carrier, or the fluid hydrogen carrier and the fluid nickel hydroxide slurry.

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