Flow hydrogen carrier, method for producing flow hydrogen carrier, charge / discharge cell, secondary battery, hydrogen filling device, power generation device, hydrogen filling and power generation device,

Abstract

The mobile hydrogen carrier comprises a hydrogen absorbing alloy and an alkaline electrolyte.

Description

Technical Field

[0001] The present invention relates to a mobile hydrogen carrier, a method for manufacturing a mobile hydrogen carrier, a charge-discharge battery 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 transmission method. Background Art

[0002] In recent years, from the perspective of environmental issues, the introduction of power generation using renewable energy has been actively promoted. When transmitting electricity generated by power generation equipment such as solar panels and windmills, there will be a burden of cost for the construction and maintenance of the infrastructure required for power transmission, power transmission losses, etc. Therefore, research is being conducted on energy utilization methods that convert renewable energy into hydrogen and transport the converted hydrogen to batteries, etc. to generate electricity.

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

[0004] Patent Document 2 proposes a method of transporting liquefied hydrogen. In the method of Patent Document 2, liquid hydrogen has a high density and no shape, so the filling rate in the container is also high, and a large amount of transportation is easy.

[0005] Non-patent document 1 proposes a method for extracting hydrogen using an organic hydride method. The organic hydride method is, for example, a technique in which toluene is reacted with hydrogen to generate methylcyclohexane, the methylcyclohexane is transported by tanker, and hydrogen is extracted by a dehydrogenation process from methylcyclohexane to toluene. In the method of non-patent document 1, hydrogen can be transported in liquid form. Liquid hydrogen is high-density and has no shape, so the filling rate in the container is also high, and it can be transported in large quantities and efficiently.

[0006] Patent Document 3 proposes a method of transporting hydrogen by absorbing it in a tank containing a hydrogen absorbing alloy. In the method of Patent Document 3, hydrogen can be transported at a higher density using a pressure lower than that of a high-pressure tank method by absorbing hydrogen in a hydrogen absorbing alloy, thereby enabling large-scale transport.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2018-162851

[0010] Patent Document 2: Japanese Patent No. 7055667

[0011] Patent Document 3: Japanese Patent Application Laid-Open No. 63-125897

[0012] Non-patent literature

[0013] Non-patent document 1: “NEDO Hydrogen Energy White Paper”, New Energy and Industrial Technology Development Organization, February 2015, p.119 Summary of the invention

[0014] Problems to be solved by the invention

[0015] However, the technology of Patent Document 1 requires a large amount of energy to compress hydrogen to a high pressure, and therefore it is difficult to efficiently transport the hydrogen.

[0016] According to the technology of Patent Document 2, in order to liquefy hydrogen for transportation, an extremely low temperature environment of -253°C must be created, which requires a large amount of energy, and therefore makes it difficult to efficiently transport the hydrogen.

[0017] In the technology of Non-Patent Document 1, heating at 350° C. to 400° C. is required to desorb hydrogen from the organic hydride, which requires a large amount of energy. Therefore, it is difficult to operate efficiently from the perspective of transporting the hydrogen to utilizing the hydrogen.

[0018] In the technology of Patent Document 3, it is necessary to control the temperature or pressure when hydrogen is adsorbed and desorbed, so it is difficult to precisely control the amount of hydrogen supplied to the battery stack. Therefore, the pressure may rise to a level higher than expected, and the pressure-resistant design of the tank containing the hydrogen-absorbing alloy has to be increased, so there is a problem of increasing the weight of the tank itself. In addition, the tank is rigid, so there is a problem that the filling efficiency of the tank in a tanker or container during transportation is lower than that of a liquid.

[0019] One embodiment of the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluid hydrogen carrier capable of efficiently transporting a large amount of hydrogen at normal temperature and pressure.

[0020] Means for solving problems

[0021] One embodiment of the fluid hydrogen carrier according to the present invention includes a hydrogen storage alloy and an alkaline electrolyte.

[0022] One embodiment of the present invention is a fluid hydrogen carrier including a hydrogen storage alloy and an alkaline electrolyte.

[0023] Another aspect of the present invention is a method for producing a fluid hydrogen carrier using the fluid hydrogen carrier described above, wherein:

[0024] The above-mentioned production method includes a step of heating at 80° C. or higher.

[0025] Another aspect of the present invention is a method for producing a fluid hydrogen carrier using the fluid hydrogen carrier described above, wherein:

[0026] The production method includes the step of pulverizing the hydrogen storage alloy in a state where the hydrogen storage alloy and the alkaline solution are mixed.

[0027] Another embodiment of the present invention is a charge-discharge cell, which is a charge-discharge cell comprising a negative electrode current collector, a positive electrode current collector, an oxygen electrode catalyst and an ion permeable membrane.

[0028] A portion of the negative electrode current collector is electrically connected to the mobile hydrogen carrier.

[0029] A portion of the positive electrode current collector is electrically connected to the oxygen electrode catalyst.

[0030] A portion of the oxygen electrode catalyst is ionically connected to the ion permeable membrane.

[0031] The ion permeable membrane is arranged to separate the negative electrode current collector from the positive electrode current collector.

[0032] A portion of the mobile hydrogen carrier is ionically connected to the ion-permeable membrane.

[0033] Another aspect of the present invention is a secondary battery including the above-mentioned charge and discharge cell.

[0034] Another aspect of the present invention is a hydrogen filling device comprising a negative electrode current collector, a negative electrode void capable of being filled with the above-mentioned fluid hydrogen carrier, a positive electrode current collector, a positive electrode void, an oxygen generating electrode and an ion permeable membrane.

[0035] The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane.

[0036] The positive electrode gap is in contact with the oxygen generating catalyst.

[0037] A portion of the positive electrode current collector is electrically connected to the oxygen generating catalyst.

[0038] A portion of the oxygen generating catalyst is contacted with an alkaline aqueous solution,

[0039] A portion of the oxygen generating catalyst is ionically connected to the ion permeable membrane.

[0040] The ion permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

[0041] Another aspect of the present invention is a power generation device comprising a negative electrode current collector, a negative electrode void that can be filled with 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.

[0042] The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane.

[0043] The positive electrode gap is in contact with the oxygen reduction catalyst.

[0044] A portion of the positive electrode current collector is electrically connected to the oxygen reduction catalyst.

[0045] A portion of the oxygen reduction catalyst is ionically connected to the ion permeable membrane,

[0046] A portion of the oxygen reduction catalyst is contacted with air,

[0047] The ion permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

[0048] Another embodiment of the present invention is a hydrogen filling and power generation device, which comprises a negative electrode current collector, a negative electrode void capable of being filled with the above-mentioned fluid hydrogen carrier, a positive electrode current collector, a positive electrode void, a binary catalyst capable of achieving both oxygen generation and oxygen reduction, and an ion permeable membrane.

[0049] The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane.

[0050] The positive electrode gap is connected to the binary catalyst.

[0051] A portion of the positive electrode current collector is electrically connected to the binary catalyst.

[0052] A portion of the binary catalyst is contacted with air or an alkaline aqueous solution.

[0053] The ion permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

[0054] Another embodiment of the present invention is a hydrogen filling and power generation device, which comprises 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.

[0055] The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane.

[0056] The positive electrode gap is in contact with both the positive electrode current collector and the ion permeable membrane.

[0057] The ion permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

[0058] Another aspect of the present invention is a hydrogen filling system having a tank for storing the aforementioned fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte.

[0059] The tank is connected to the positive electrode or negative electrode of the hydrogen filling device according to claim 13.

[0060] The hydrogen filling system has a pressurizing / depressurizing device capable of filling / discharging a fluid hydrogen carrier, a fluid nickel hydroxide slurry, air, oxygen or an alkaline electrolyte into / from the gaps of the positive electrode or the negative electrode.

[0061] Another embodiment of the present invention is a power generation system having a tank for storing the aforementioned fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte.

[0062] The tank is connected to the positive electrode or negative electrode of the power generation device.

[0063] The power generation system has a pressurizing / depressurizing device capable of filling / discharging a fluid hydrogen carrier, a fluid nickel hydroxide slurry, air, oxygen or an alkaline electrolyte into / from the gaps of the positive electrode or the negative electrode.

[0064] Another embodiment of the present invention is a hydrogen filling and power generation system, which has a tank for storing the aforementioned fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte,

[0065] The tank is connected to the positive electrode or negative electrode of the hydrogen filling and power generation device.

[0066] The hydrogen filling and power generation system has a pressurizing / depressurizing device that can fill / discharge a fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the voids of the positive electrode or negative electrode.

[0067] Another embodiment of the present invention is an energy transfer method, wherein the aforementioned liquid hydrogen carrier filled with hydrogen, or the liquid hydrogen carrier and the liquid nickel hydroxide slurry are extracted from the above-mentioned power generation system and transported.

[0068] Another embodiment of the present invention is an energy transfer method, wherein the aforementioned liquid hydrogen carrier filled with hydrogen, or the liquid hydrogen carrier and the liquid nickel hydroxide slurry are extracted from the aforementioned hydrogen filling and power generation system, and the liquid hydrogen carrier filled with hydrogen, or the liquid hydrogen carrier and the liquid nickel hydroxide slurry are transported.

[0069] Effects of the Invention

[0070] One embodiment of the fluid hydrogen carrier according to the present invention is capable of transporting a large amount of hydrogen at a high efficiency at normal temperature and pressure. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] [ Figure 1 ] is a schematic cross-sectional view showing the structure of a fluid hydrogen carrier according to an embodiment of the present invention.

[0072] [ Figure 2 ] is a schematic diagram showing the structure of a charge-discharge cell to which a mobile hydrogen carrier according to an embodiment of the present invention is applied.

[0073] [ Figure 3 ] is a schematic diagram showing another structure of a charge and discharge battery.

[0074] [ Figure 4 ] is a schematic diagram showing the structure of a secondary battery having a charge and discharge cell according to an embodiment of the present invention.

[0075] [ Figure 5 ] is a schematic diagram showing another structure of a secondary battery.

[0076] [ Figure 6 ] is a hydrogen filling device for a liquid hydrogen carrier according to an embodiment of the present invention.

[0077] [ Figure 7 ] is a schematic cross-sectional view showing a method of filling a liquid hydrogen carrier according to an embodiment of the present invention with hydrogen.

[0078] [ Figure 8 ] is a schematic cross-sectional view showing a power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0079] [ Fig. 9 ] is a schematic cross-sectional view showing a method for power generation using a mobile hydrogen carrier according to an embodiment of the present invention.

[0080] [ Fig.10 ] is a schematic cross-sectional view showing a hydrogen filling and power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0081] [ Fig.11 ] is a schematic cross-sectional view showing a second hydrogen filling and power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0082] [ Fig.12 ] is a schematic cross-sectional view showing a second hydrogen filling method and a hydrogen filling method of a power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0083] [ Fig.13] is a schematic cross-sectional view showing a method for power generation using a second hydrogen filling and power generation device of a liquid hydrogen carrier according to an embodiment of the present invention.

[0084] [ Fig.14 ] is a schematic cross-sectional view showing a second hydrogen filling device of a fluid hydrogen carrier according to an embodiment of the present invention.

[0085] [ Fig.15 ] is a schematic cross-sectional view showing a second power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0086] [ Fig.16 ] is a schematic cross-sectional view showing a third hydrogen filling and power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0087] [ Fig.17 ] is a schematic cross-sectional view showing a fourth hydrogen filling and power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0088] [ Fig.18 ] is a schematic cross-sectional view showing a third hydrogen filling device of a fluid hydrogen carrier according to an embodiment of the present invention.

[0089] [ Fig.19 ] is a schematic cross-sectional view showing a third power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0090] [ Fig. 20 ] is a schematic cross-sectional view showing a fifth hydrogen filling and power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0091] [ Fig.21 ] is a schematic cross-sectional view showing a sixth hydrogen filling and power generation device using a liquid hydrogen carrier according to an embodiment of the present invention.

[0092] [ Fig. 22 ] is a schematic cross-sectional view showing a hydrogen filling and power generation system using a liquid hydrogen carrier according to an embodiment of the present invention.

[0093] [ Fig.23 ] is a schematic cross-sectional view showing a second hydrogen filling and power generation system using a liquid hydrogen carrier according to an embodiment of the present invention.

[0094] [ Fig.24 ] is a schematic cross-sectional view showing a third hydrogen filling and power generation system using a liquid hydrogen carrier according to an embodiment of the present invention.

[0095] [ Fig.25] is a schematic cross-sectional view showing a fourth hydrogen filling and power generation system using a liquid hydrogen carrier according to an embodiment of the present invention.

[0096] [ Fig.26 ] is the charging curve of Example 1-1.

[0097] [ Fig. 27 ] is the discharge curve of Example 1-1.

[0098] [ Fig.28 ] is a charging curve during hydrogen filling obtained in Example 1-2.

[0099] [ Fig.29 ] is the discharge curve during power generation obtained from Example 1-2.

[0100] [ Fig.30 ] is the situation after the static test of Comparative Example 6.

[0101] [ Fig.31 ] is the situation after the static test of Example 14. DETAILED DESCRIPTION

[0102] Hereinafter, the specific embodiments of the present invention will be described in detail based on the accompanying drawings. It should be noted that, in order to facilitate the understanding of the description, the same components are given the same reference numerals in each of the accompanying drawings, and repeated descriptions are omitted. In addition, the scales of the components in the accompanying drawings are sometimes different from the actual ones. As for the "to" indicating the numerical range in this specification, unless otherwise specified, it means that the numerical values ​​recorded before and after it are included as the lower limit and upper limit.

[0103] <Mobile hydrogen carrier>

[0104] The fluid hydrogen carrier according to this embodiment will be described. Figure 1 1 is a schematic cross-sectional view showing the structure of a mobile hydrogen carrier according to an embodiment of the present invention. Figure 1 As shown, the liquid hydrogen carrier 10 according to the embodiment of the present invention is a mixture including a hydrogen storage alloy 11 and an alkaline electrolyte 12, and may also contain additional components such as a dispersant, a thickener, a surfactant, and a conductive filler in any amount as appropriate. The liquid hydrogen carrier 10 includes the hydrogen storage alloy 11 in a state dispersed in the alkaline electrolyte 12.

[0105] It should be noted that the liquid hydrogen carrier 10 may have a low viscosity or a high viscosity, and the viscosity of the liquid hydrogen carrier 10 can be appropriately set by the ratio of the hydrogen absorbing alloy contained in the liquid hydrogen carrier 10 to the alkaline electrolyte. The liquid hydrogen carrier 10 may have a high viscosity to the extent of being creamy or foamy, for example. In the present embodiment, even if the liquid hydrogen carrier 10 has a high viscosity, for example, even if the liquid hydrogen carrier 10 is dropped on a flat plate and the plate is tilted, the liquid hydrogen carrier 10 is also included in the liquid hydrogen carrier 10 as long as it can be made to flow by a conveying device such as a pump.

[0106] (Hydrogen absorbing alloy)

[0107] The hydrogen storage alloy 11 included in the fluid hydrogen carrier according to the present embodiment has a function of reversibly storing and releasing hydrogen, and has a substantially particle-like shape.

[0108] The material of the hydrogen storage alloy 11 is not particularly limited as long as it is a material that can store and release hydrogen. As the hydrogen storage alloy 11, for example, La-Ni alloy, La-Nd-Ni alloy, La-Gd-Ni alloy, La-Y-Ni alloy, La-Co-Ni alloy, La-Ce-Ni alloy, La-Ni-Ag alloy, La-Ni-Fe alloy, La-Ni-Cr alloy, La-Ni-Pd alloy, La-Ni-Cu alloy, La-Ni-Al alloy, La-Ni-Mn alloy, La-Ni-In alloy, La-Ni-Sn alloy, La-Ni-Ga alloy, La-Ni-Si alloy, La-Ni-Ge alloy, La-Ni-Al-Co alloy, La-Ni-Al-Mn alloy, La-Ni-Al-Cr alloy, La-Ni-Al-Cu alloy, La-Ni-Al-Si alloy, La-Ni-Al-Ti alloy, 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 by a mixed rare earth metal (a mixture of rare earth elements with Ce and La as main components); alloys formed by a combination of two or more of the elements Ti, Fe, Mn, Al, Ce, Ca, Mg, Zr, Nb, V, Co, Ni, and Cr, such as Ti-Zr-Mn-Mo alloys, Zr-Fe-Mn alloys, and Mg-Ni alloys; metals that form hydrides (have hydrogen storage properties) of Ti, V, Zr, La, Pd, Pt, etc.; hydrides (substances that store hydrogen) of the above alloys or the above metals; and the like. These may be used alone or in combination of two or more.

[0109] 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, or the like.

[0110] The average particle size of the hydrogen absorbing alloy 11 is 50 μm or less. When it is larger than 50 μm, problems such as the hydrogen absorbing alloy 11 blocking the flow path and the rapid sedimentation rate may occur in the process of filling hydrogen into the liquid hydrogen carrier 10. The average particle size of the hydrogen absorbing alloy 11 can be appropriately set within the range of 50 μm or less, for example, preferably 1 μm to 50 μm, more preferably 5 μm to 40 μm, and further preferably 10 μm to 20 μm. If the average particle size is too small, the viscosity of the liquid hydrogen carrier 10 increases, thereby hindering fluidity. If the average particle size of the hydrogen absorbing alloy 11 is within the above-mentioned preferred range, the hydrogen absorbing alloy 11 can be well dispersed in the alkaline electrolyte 12 and maintain the contact area with the alkaline electrolyte 12.

[0111] It should be noted that the so-called average particle size refers to the volume average particle size based on the effective diameter, and the average particle size is measured, for example, by a laser diffraction scattering method or a dynamic light scattering method. The average particle size can be set as: in the particle size distribution curve obtained by measuring the particle size distribution of the hydrogen absorbing alloy 11, the particle size (median diameter) when the cumulative amount accounts for 50% on a volume basis, from the smallest to the largest particles.

[0112] The hydrogen storage alloy 11 may be a porous body or a non-porous body, and is appropriately selected according to the material used.

[0113] When the hydrogen storage alloy 11 is a porous body, the specific surface area is not particularly limited and can be set to any appropriate size depending on the type and size of the hydrogen storage alloy 11. The specific surface area can be measured by a specific surface area measuring device using a gas adsorption method, for example.

[0114] The content of the hydrogen absorbing alloy 11 is 15% by volume or more relative to the liquid hydrogen carrier 10. If it is lower than this value, the energy density of the liquid hydrogen carrier 10 is reduced. In addition, if it is lower than this value, the metal component ratio in the liquid hydrogen carrier 10 is reduced, the conductivity of the liquid hydrogen carrier 10 is reduced, and the electrochemical hydrogen filling and power generation cannot be fully performed. The content of the hydrogen absorbing alloy 11 can be 15% by volume or more relative to the liquid hydrogen carrier 10, for example, preferably 15% by volume to 50% by volume, and more preferably 20% by volume to 40% by volume.

[0115] (Alkaline electrolyte)

[0116] The alkaline electrolyte 12 includes a supporting electrolyte and water.

[0117] The supporting electrolyte is dissolved in water.

[0118] 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.

[0119] The alkaline electrolyte 12 preferably contains, for example, 1 mol / L to 12 mol / L, more preferably 5 mol / L to 10 mol / L, and still more preferably 6 mol / L to 8 mol / L of a supporting electrolyte. If the alkaline electrolyte 12 contains 1 mol / L to 20 mol / L of a supporting electrolyte, the ion conductivity of the alkaline electrolyte 12 is improved, and if the alkaline electrolyte 12 contains 5 mol / L to 8 mol / L of a supporting electrolyte, the ion conductivity of the alkaline electrolyte 12 is most improved.

[0120] (Thickener)

[0121] The fluid hydrogen carrier 10 contains a thickener.

[0122] Regarding the viscosity of the liquid hydrogen carrier 10, at a shear rate of 100 sec -1 The viscosity at 100 mPa·sec or more is preferably 100 mPa·sec or more. When the viscosity is lower than this, the sedimentation of the hydrogen storage alloy becomes significant and the fluidity becomes poor.

[0123] As the thickener, one kind alone or two or more kinds of organic polymers soluble in the alkaline electrolyte 12 can be used in combination. In order to further improve the thickening effect, a water-soluble organic polymer having a weight average molecular weight of 1500 or more is preferred. It is more preferred to use a polyacrylate as the water-soluble organic polymer, and it is further preferred to use sodium polyacrylate as the water-soluble organic polymer.

[0124] (Thixotropic agent)

[0125] The liquid hydrogen carrier 10 contains a thixotropic agent. The thixotropic agent is an additive that exhibits thixotropy when mixed in a liquid. Thixotropy is a property that viscosity decreases when shear stress is applied and increases when the liquid hydrogen carrier is left at rest. The addition of the thixotropic agent can suppress the sedimentation of the hydrogen storage alloy 11 in the liquid hydrogen carrier 10 at rest.

[0126] The thixotropic agent is not particularly limited as long as it is a material that can make the fluid hydrogen carrier 10 exhibit thixotropy.

[0127] As the thixotropic agent, for example, silica particles, bentonite, calcium carbonate, castor oil, fatty acid ester, polyether, glycol ether, carbon black, etc. can be used. They can be used alone or in combination of two or more. Carbon black is more preferably used. Among the above-mentioned thixotropic agents, carbon black itself has high conductivity. Therefore, it not only suppresses the sedimentation of the hydrogen absorbing alloy 11, but also has the effect of improving the conductivity of the fluid hydrogen carrier 10.

[0128] In order to exhibit thixotropy with a smaller addition amount, it is better to use fine particles of a thixotropic agent. By using smaller particles, a dense network is formed when left to stand, thereby increasing the effect of suppressing the sedimentation of the hydrogen storage alloy 11. The particle size is not particularly limited, but is preferably 1 μm or less.

[0129] (Method for producing a fluid hydrogen carrier)

[0130] The method for producing the liquid hydrogen carrier 10 is not particularly limited, and includes, for example, a step of heating the hydrogen storage alloy 11 and the alkaline electrolyte 12 to 80° C. or higher in a mixed state. This has the effect of removing the non-conductive oxide film on the surface of the hydrogen storage alloy 11 and forming a highly conductive nickel-rich layer on the surface of the hydrogen storage alloy 11.

[0131] When the raw material of the hydrogen absorbing alloy 11 contains coarse particles of 50 μm or more, it is necessary to pulverize. The hydrogen absorbing alloy 11 can be pulverized using a ball mill, a jet mill, etc., and the surface is oxidized by pulverizing in the atmosphere. The smaller the particle size, the larger the specific surface area. Therefore, when a large amount of hydrogen absorbing alloy 11 is pulverized, there is a risk of heat generation and explosion during oxidation. Therefore, when the hydrogen absorbing alloy is pulverized, the hydrogen absorbing alloy 11 and the alkaline electrolyte 12 are mixed. The equipment used for pulverization is not limited, and a ball mill, a jet mill, etc. can be used.

[0132] In this way, the liquid hydrogen carrier 10 contains the hydrogen storage alloy 11 in the alkaline electrolyte 12, and contains the hydrogen storage alloy 11 in a state dispersed in the alkaline electrolyte 12. In the liquid hydrogen carrier 10, the hydrogen storage alloy 11 is dispersed in the alkaline electrolyte 12, so that it can store hydrogen at a high density while having fluidity at normal temperature and pressure. In addition, the liquid hydrogen carrier 10 can generate electricity (discharge) simultaneously with the release of hydrogen.

[0133] Therefore, the liquid hydrogen carrier 10 is not restricted by shape when transported by a tanker or other transport vessel, and can efficiently transport a large amount of hydrogen at a high filling rate. In addition, the liquid hydrogen carrier 10 can repeatedly store and release hydrogen.

[0134] <Charge and discharge cells>

[0135] A charge-discharge cell to which the fluid hydrogen carrier according to the present embodiment is applied will be described. Figure 2 is a diagram showing the charging and discharging of a battery cell. Figure 2As shown, 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 seal 25, and a fluid hydrogen carrier 26 is filled in the space formed by the negative electrode current collector 21, the ion permeable membrane 24, and the seal 25. The fluid hydrogen carrier 26 is a mixture containing a hydrogen storage alloy 261 in an alkaline electrolyte 262. The fluid hydrogen carrier 26 is the fluid hydrogen carrier 10 involved in the present embodiment described above, so detailed description is omitted.

[0136] (Negative current collector)

[0137] The negative electrode current collector 21 can be manufactured by, for example, roughening the surface of a nickel plate, a steel plate, a stainless steel plate, etc. with nickel plating, or by etching the surface of a nickel plate or a nickel foil, or by using a nickel mesh, a nickel foam, or a nickel porous body, or by plating the surface of a steel plate or a stainless steel plate that has been roughened in advance by etching, etc., with nickel. In addition, the surface can be formed with irregularities, or it can be porous.

[0138] The negative electrode current collector 21 may be arranged so as to be electrically connected to the mobile hydrogen carrier 26 and ionically connected to the ion permeable membrane 24. It should be noted that the so-called ion connection means that ion conduction from the mobile hydrogen carrier 26 to the ion permeable membrane 24 is not blocked.

[0139] (Positive current collector)

[0140] The positive electrode current collector 22 is configured in a manner that a part of it is electrically connected to the oxygen electrode catalyst 23. The positive electrode current collector 22 can be made of any material or shape as long as it has conductivity. For example, it can be a nickel plate, a nickel mesh, a nickel porous body, a stainless steel mesh, a stainless steel porous body, a stainless steel felt, etc., a carbon felt, a carbon paper, and can be manufactured by roughening their surfaces with nickel plating, or by etching the surfaces of a nickel plate or a nickel foil, or by plating the surface of stainless steel that has been roughened in advance by etching, etc.

[0141] (Oxygen Catalyst)

[0142] The oxygen electrode catalyst 23 is disposed so that a part thereof is ionically connected to the ion permeable membrane 24. It should be noted that the so-called ion connection means that ion conduction from the oxygen electrode catalyst 23 to the ion permeable membrane 24 is not blocked.

[0143] The oxygen electrode catalyst 23 can be any substance that generates hydroxide ions from oxygen, a catalyst that generates hydroxide ions from oxygen, or both, and can be, for example, platinum, rhodium, palladium, iridium, osmium, ruthenium, rhenium, gold, silver, nickel, cobalt, molybdenum, lanthanum, strontium, yttrium, bismuth iridium oxide, azaphthalocyanine metal complex, etc. The catalyst can be used alone or in combination of two or more.

[0144] As for the oxygen electrode catalyst 23, a catalytic layer including a catalyst carrier supported on a carrier or without a carrier and an ion-conductive binder can also be coated on a substrate such as a titanium mesh, a titanium porous body, a nickel mesh, a nickel porous body, carbon paper, or a positive electrode current collector 22.

[0145] As a carrier, acetylene black, Ketjen black, carbon nanotubes, carbon nanohorns, graphene, graphene oxide, nickel particles, etc. can be used. As far as the catalyst is supported on the carrier, methods such as impregnation method can be used. In addition, not only can a structure with a catalyst supported on the carrier be used, but also a material mixed with catalyst particles and particles that can become a carrier can be used. In this case, the particles that can become a carrier can also but do not necessarily have a catalytic function. In addition, it is preferred to use a material with high conductivity to form particles that can become a carrier.

[0146] The oxygen electrode catalyst 23 is electrically connected to the positive electrode current collector 22. Here, the so-called electrically connected state is that the oxygen electrode catalyst 23 and the positive electrode current collector 22 are electrically connected, and a conductive material may be interposed therebetween. For example, the oxygen electrode catalyst 23 may also be formed on carbon paper, and the carbon paper is connected to the oxygen electrode catalyst 23.

[0147] The oxygen electrode catalyst 23 is arranged in an ionically connected state with the ion permeable membrane 24. Here, the ionically connected state means a state in which ion conduction between the oxygen electrode catalyst 23 and the ion permeable membrane 24 is not blocked. For example, an electrolyte or water may exist between the oxygen electrode catalyst 23 and the ion permeable membrane 24.

[0148] (Ion permeable membrane)

[0149] The ion permeable membrane 24 is disposed between the negative electrode current collector 21 and the positive electrode current collector 22 to separate the negative electrode current collector 21 from the positive electrode current collector 22. The shape of the ion permeable membrane 24 is not particularly limited, and may have any appropriate shape.

[0150] The ion permeable membrane 24 can use both anion exchange membrane, anion exchange membrane and cation exchange membrane. When using two sheets of anion exchange membrane and 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 can also be provided between the anion exchange membrane and the cation exchange membrane, or the anion exchange membrane can also be contacted with the cation exchange membrane.

[0151] (Seal)

[0152] A pair of seals 25 are provided at both ends of the ion permeable membrane 24 to connect the negative electrode current collector 21 and the ion permeable membrane 24. The seals 25 prevent leakage of the mobile hydrogen carrier 26 or the alkaline electrolyte 262. The material and shape of the seal 25 are not limited as long as they can prevent leakage of the mobile hydrogen carrier 26 or the alkaline electrolyte 262.

[0153] As the material of the seal 25, 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. One of them can be used alone, or two or more of them can be used in combination.

[0154] In the charge-discharge cell 20, when current flows through the positive current collector 22 during charging, since the positive current collector 22 and the oxygen electrode catalyst 23 are electrically connected, the electrons flowing in the positive current collector 22 flow to the outside through the positive current collector 22. In addition, the oxygen electrode catalyst 23 and the ion permeable membrane 24 are ionically connected, so the hydroxide ions (OH) generated during charging and required for the reaction described later are - ) is supplied from the mobile hydrogen carrier 26 filled in the space formed by the negative electrode current collector 21, the ion permeable membrane 24 and the seal 25 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 escape from the hydroxide ions to generate oxygen and water.

[0155] 4OH - -4e - →O2+2H2 ···(1)

[0156] In this embodiment, part of the negative electrode current collector 21 is electrically connected to the mobile hydrogen carrier 26, and part of the mobile hydrogen carrier 26 is ionically connected to the ion permeable membrane 24. Ionically connected means that ion conduction from the mobile hydrogen carrier 26 to the ion permeable membrane 24 is not blocked.

[0157] Therefore, when charging is performed, as shown in the following formula (2), hydrogen is stored in the hydrogen storage alloy 261 by the reaction between the water in the liquid hydrogen carrier 26 and the hydrogen storage alloy 261, and hydroxide ions (OH - ).

[0158] M+H2O+e - →MH+OH - (2)

[0159] (Wherein, M is a hydrogen-absorbing alloy.)

[0160] A portion of the negative electrode current collector 21 is electrically connected to the liquid hydrogen carrier 26, so that electron transfer can be achieved between the liquid hydrogen carrier 26. A portion of the liquid hydrogen carrier 26 is ionically connected to the ion permeable membrane 24, so the generated hydroxide ions can quickly move to the positive electrode side, that is, the positive electrode current collector 22. It should be noted that the opposite reaction occurs during discharge.

[0161] By connecting the charge and discharge cell 20 and the can 31 (see Figure 4 ) or pump 32 (see Figure 4 ) is connected, and the liquid hydrogen carrier 26 can be easily discharged to the outside of the charge-discharge cell 20, so that it is connected to the charge-discharge cell 20 and the tank 31 (see Figure 4 ) and pump 32 (see Figure 4 ) are circulated between. Thus, the charge-discharge cell 20 can store the charged (hydrogen-absorbed) mobile hydrogen carrier 26 in the tank 31 (see Figure 4 ). In addition, when the charge (hydrogen storage amount) of the charge / discharge cell 20 is insufficient, the liquid hydrogen carrier 26 can be circulated in the charge / discharge cell 20 again to perform additional charging. In the charge / discharge cell 20, hydrogen is electrochemically stored in the liquid hydrogen carrier 26 or released from the liquid hydrogen carrier 26.

[0162] 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 seal 25, and includes a mobile hydrogen carrier 26 in a space formed by the negative electrode current collector 21, the ion permeable membrane 24, and the seal 25. Thus, the charge-discharge cell 20 can electrochemically absorb and release hydrogen in the mobile hydrogen carrier 26 in the aforementioned space, so that more precise control can be performed compared to the case of controlling temperature and pressure.

[0163] In the charge-discharge cell 20, the liquid hydrogen carrier 26 includes a hydrogen storage alloy 261, and the hydrogen storage alloy 261 can reversibly store and release hydrogen, such as when used as a 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.

[0164] It should be noted that, in this embodiment, Figure 3 As shown, in the charge-discharge battery cell 20 , a connector 27 may be connected to a pair of seal members 25 .

[0165] The joint 27 may be formed in a tubular shape. The joint 27 may be configured to allow the liquid hydrogen carrier 26 to be injected into and discharged from the seal 25. The joint 27 may be connected to the seal 25 at any position, and the connection position of the joint 27 is not particularly limited.

[0166] The material of the connector 27 may be any material that does not corrode or dissolve in the alkaline electrolyte 262. Such a material may be selected from, for example, nickel, stainless steel, polyethylene, polypropylene, acrylic resin, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, etc., and only one type may be used or two or more types may be used in combination.

[0167] <Secondary battery>

[0168] A secondary battery including the charge-discharge cell according to the present embodiment will be described. Figure 4 1 is a diagram showing the structure of a secondary battery having a charge-discharge cell according to the present embodiment. Figure 4 As shown, the secondary battery 30A includes a charge-discharge cell 20 , a tank 31 , and a pump 32 , and allows a liquid hydrogen carrier 26 to circulate between the charge-discharge cell 20 , the tank 31 , and the pump 32 via a joint 27 .

[0169] The joint 27 may be configured so as to allow the mobile hydrogen carrier 26 to circulate between the charge / discharge cell 20, the tank 31, and the pump 32. In the present embodiment, the joint 27 includes a joint 27A for connecting one seal 25 to the tank 31, a joint 27B for connecting the tank 31 to the pump 32, and a joint 27C for connecting the other seal 25 to the pump 32. The joint 27A, the joint 27B, and the joint 27C may be provided with a flow regulating valve (not shown) to control the flow rate.

[0170] The tank 31 may be formed of a material that is not corroded or dissolved by the alkaline electrolyte 262 contained in the liquid hydrogen carrier 26. The material constituting the tank 31 is not particularly limited, and examples thereof include nickel, stainless steel, polyethylene, polypropylene, acrylic resin, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, etc. These materials may be used alone or in combination of two or more.

[0171] In addition, in order to improve the wear resistance of the inner wall of the tank 31, a coating layer can be formed on the inner wall of the tank 31 using 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. They can be used alone or in combination of two or more. In addition, since gas is generated during charging and discharging, in order to suppress the increase in the internal pressure in the tank 31 and the damage of the secondary battery 30A, a pressure regulating valve not shown in the figure can be provided in the tank 31.

[0172] The pump 32 can be used as long as it can deliver liquid to the liquid hydrogen carrier 26, for example, a centrifugal pump, a propeller pump, a reciprocating pump, a rotary pump, etc. As a centrifugal pump, for example, a vortex pump, a turbine pump, etc. can be mentioned. As a propeller pump, for example, an axial flow pump, a mixed flow pump, a cascade pump, etc. can be mentioned. As a reciprocating pump, for example, a piston pump, a plunger pump, a diaphragm pump, a tube pump, a wing pump, etc. can be mentioned. As a rotary pump, for example, a gear pump, an eccentric shaft pump, a screw pump, etc. can be mentioned. They can be used alone or in combination of two or more.

[0173] In the secondary battery 30A, by operating the pump 32, the liquid hydrogen carrier 26 can be injected from the tank 31 into the charge / discharge cell 20, and discharged from the charge / discharge cell 20 to the tank 31. Thus, the liquid hydrogen carrier 26 can be circulated between the charge / discharge cell 20, the tank 31, and the pump 32 via the joint 27. In addition, the liquid hydrogen carrier 26 can be stored in the tank 31 by closing the flow rate adjustment (not shown) provided at the joint 27B.

[0174] Thus, the secondary battery 30A can electrochemically store and release hydrogen because it has the charge-discharge cell 20, so that the charge and discharge (hydrogen storage and release) can be easily and simply controlled. In addition, since the liquid hydrogen carrier 26 has fluidity at normal temperature and pressure, the secondary battery 30A can be easily handled. Therefore, the secondary battery 30A can transport the liquid hydrogen carrier 26 with high efficiency.

[0175] Another configuration of the secondary battery 30A including the charge / discharge cell 20 according to the present embodiment will be described. Figure 5 FIG. 2 is a diagram showing another configuration of the secondary battery 30A. Figure 5 As shown, the secondary battery 30B is Figure 4 The secondary battery 30A shown in FIG. 1 has a seal 34, a partition wall 35, a joint 36, a tank 37, and a pump 38 on the side of the ion permeable membrane 24 opposite to the liquid hydrogen carrier 26. The secondary battery 30B has a space inside due to the positive electrode current collector 22, the seal 34, and the partition wall 35, and the alkaline electrolyte 262 is supplied to the above space.

[0176] On the surface of the positive current collector 22 opposite to the ion permeable membrane 24, a pair of seals 34 are provided at both ends of the partition wall 35 so as to connect the positive current collector 22 and the partition wall 35. The seals 34 prevent leakage of the alkaline electrolyte 262 supplied to the space formed by the positive current collector 22, the seals 34, and the partition wall 35. The seals 34 are the same as the seals 25, so the details are omitted.

[0177] The partition wall 35 is provided on the side of the seal 34 opposite to the positive electrode current collector 22 , and a space is formed inside by the positive electrode current collector 22 , the seal 34 , and the partition wall 35 .

[0178] The partition wall 35 may be formed of any material that does not corrode or dissolve in the alkaline electrolyte 262 , and the same material as the tab 27 and the like may be used.

[0179] The joint 36 is connected to a pair of seals 34, and is connected to a tank 37 and a pump 38. The joint 36 can be configured so that the alkaline electrolyte 262 circulates between the charge-discharge cell 20, the tank 37, and the pump 38. In the present embodiment, the joint 36 includes a joint 36A that connects one seal 34 to the tank 37, a joint 36B that connects the tank 37 to the pump 38, and a joint 36C that connects the other seal 34 to the pump 38. A flow regulating valve (not shown) may be provided in the joints 36A, 36B, and 36C to control the flow rate.

[0180] The joint 36 may be formed in a tubular shape. The joint 36 may be configured to inject and discharge the alkaline electrolyte 262 into the seal 34. The joint 27 may be provided at a position that can be connected to the seal 34, and the connection position of the joint 36 is not particularly limited. The joint 36 uses the same material as the joint 27, so the details are omitted.

[0181] The tank 37 and the pump 38 are connected to the joint 36, respectively, and are used as a tank and a pump for the positive electrode. The tank 37 and the pump 38 are the same as the tank 31 and the pump 32, and therefore, the details are omitted.

[0182] In the secondary battery 30B, the seal 34 and the partition 35 are provided to form a space formed by the positive electrode current collector 22 , the seal 34 and the partition 35 , so that the alkaline electrolyte 262 can be supplied during charge and air or oxygen can be supplied during discharge.

[0183] Therefore, in the secondary battery 30B, similarly to the secondary battery 30A, by including the charge / discharge cell 20 , the seal 34 , and the partition wall 35 , charge / discharge (storage and release of hydrogen) can be easily and simply controlled and efficiently transported.

[0184] <Hydrogen filling device for liquid hydrogen carrier>

[0185] A hydrogen filling device for a fluid hydrogen carrier according to the present embodiment will be described. Figure 6 : is a diagram showing a hydrogen filling device. Figure 6 As shown, the hydrogen filling device 100A includes a negative electrode current collector 101, a negative electrode gap 102 that can be filled with a liquid hydrogen carrier, a positive electrode current collector 103, a positive electrode gap 104, an oxygen generating electrode 105, an ion permeable membrane 106, a seal 107 and a joint 108. The hydrogen filling device 100A fills the liquid hydrogen carrier 10 with hydrogen.

[0186] (Negative current collector)

[0187] For the negative electrode current collector 101, for example, it can be manufactured by roughening the surface of a nickel plate, a steel plate, a stainless steel plate, etc. with nickel plating, or by etching the surface of a nickel plate or a nickel foil, or by using a nickel mesh, a nickel foam, or a nickel porous body, or by plating the surface of a steel plate or a stainless steel plate that has been roughened in advance by etching, etc. In addition, it is possible to form unevenness on the surface, or it can be porous.

[0188] The negative electrode current collector 101 only needs to be arranged in a manner that it is in contact with the negative electrode gap 102.

[0189] (Negative electrode gap)

[0190] The negative electrode gap 102 is provided for filling the mobile hydrogen carrier 10 during the hydrogen filling operation. When the negative electrode gap 102 is filled with the mobile hydrogen carrier 10, the mobile hydrogen carrier 10 only needs to be electrically connected to the negative electrode current collector and ionically connected to the ion exchange membrane. It should be noted that the so-called ion connection means that the ion conduction from the mobile hydrogen carrier 10 to the ion permeable membrane 106 is not blocked.

[0191] (Positive current collector)

[0192] The positive electrode current collector 103 is configured in such a way that a part of it is electrically connected to the oxygen generating electrode 105. The material and shape of the positive electrode current collector 103 are not particularly limited as long as it has conductivity. For example, it can be nickel, stainless steel, carbon, titanium, and can also be manufactured by roughening the surface of these surfaces with nickel plating, or by etching the surface of a nickel plate or nickel foil, or by plating the surface of stainless steel that has been roughened in advance by etching or the like.

[0193] (Oxygen generating electrode)

[0194] The oxygen generating electrode 105 only needs to have oxygen generating activity on the surface. The so-called oxygen generating activity is the action of oxidizing hydroxide ions to generate oxygen, and an oxygen generating catalyst can be used. As for the oxygen generating electrode 105, the oxygen generating catalyst can be used alone, or the oxygen generating catalyst can be supported on a substrate for use. A catalytic layer comprising an oxygen generating catalyst, an ion-conductive binder, and a conductive agent can also 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 a positive current collector 103.

[0195] As the catalyst having oxygen generating activity, for example, platinum, rhodium, palladium, iridium, osmium, ruthenium, rhenium, gold, silver, nickel, cobalt, molybdenum, lanthanum, strontium, yttrium, iron oxide, cobalt iron oxide, copper iron oxide, nickel iron oxide, calcium iron oxide, nickel oxide, nickel sulfide, double hydroxide of nickel and cobalt, iron nickel tungsten oxide, carbonitride, iridium oxide, bismuth iridium oxide, titanium dioxide, lithium-containing nickel oxide, cobalt lanthanum oxide, etc. can be used. The catalyst can be used alone or in combination of two or more.

[0196] The oxygen generating electrode 105 is configured so 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 connected to the positive electrode gap 104. It should be noted that the so-called ion connection means that the ion conduction from the oxygen generating electrode 105 to the ion permeable membrane 106 is not blocked.

[0197] With this structure, electrons migrate from the positive electrode current collector 103 to the oxygen generating electrode, and the electrons oxidize hydroxide ions supplied from the ion permeable membrane 106 to generate oxygen.

[0198] (Ion permeable membrane)

[0199] The ion permeable membrane 106 is disposed 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 generating electrode to separate the negative electrode current collector 101 from the positive electrode current collector 103 .

[0200] The shape of the ion permeable membrane 106 is not particularly limited, and may have any appropriate shape.

[0201] The ion permeable membrane 106 may be an anion exchange membrane, a bipolar membrane formed by laminating an anion exchange membrane and a cation exchange membrane, a nonwoven fabric, etc. When two sheets of an anion exchange membrane and a cation exchange membrane are used, 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 a nonwoven fabric is used, it is preferred that the pores are smaller than the particle size of the hydrogen storage alloy 11.

[0202] (Seal)

[0203] The seal 107 can be used to prevent leakage of the fluid hydrogen carrier 10 or the alkaline electrolyte 12. The material and shape of the seal 25 are not limited as long as they can prevent leakage of the fluid hydrogen carrier 10 or the alkaline electrolyte 12.

[0204] As the material of the seal 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. One of them can be used alone, or two or more of them can be used in combination.

[0205] (Connector)

[0206] A joint 108 may be provided in order to fill or discharge the liquid hydrogen carrier 10 and the alkaline electrolyte 12 into or from the negative electrode gap 102 and the positive electrode gap 104 .

[0207] The joint 108 can be used as long as it does not hinder the filling or discharge of the liquid hydrogen carrier 10 and the alkaline electrolyte 12 into the negative electrode gap 102 and the positive electrode gap 104. The material of the joint 108 can be any material that does not corrode or dissolve in the alkaline electrolyte 12. Such a material can be selected from nickel, stainless steel, polyethylene, polypropylene, acrylic resin, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, etc., and only one type can be used, or two or more types can be used in combination.

[0208] (Method of filling liquid hydrogen carrier with hydrogen)

[0209] A method of filling the fluid hydrogen carrier with hydrogen according to the present embodiment will be described. Figure 7 This is an explanatory diagram showing an example of filling hydrogen into a liquid hydrogen carrier using a hydrogen filling device. Figure 7 As shown, 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 gap 104, the oxygen generating electrode 105 and the ion permeable membrane 106, the seal 107, and the joint 108. Figure 6 The negative electrode gap 102 and the positive electrode gap 104 of the hydrogen filling device 100A are filled with a fluid hydrogen carrier 10 and an alkaline electrolyte 12, respectively.

[0210] In the hydrogen filling device 100A, when a negative potential voltage is applied to the negative current collector 101 and a positive potential voltage is applied to the positive current collector 103, the positive current collector 103 is electrically connected to the oxygen generating electrode 105. Therefore, in the oxygen generating electrode, as shown in the following formula (1), electrons are transferred from hydroxide ions (OH - ) escapes to produce oxygen and water.

[0211] 4OH - →O2+4e - +2H2O ···(1)

[0212] In addition, in this embodiment, a part of the negative electrode current collector 101 is electrically connected to the liquid hydrogen carrier 10. Therefore, when a negative potential voltage is applied to the negative electrode current collector 101 and a positive potential voltage is applied to the positive electrode current collector 103, as shown in the following formula (2), hydrogen is filled into the hydrogen storage alloy 11 by the reaction between the water in the liquid hydrogen carrier 10 and the hydrogen storage alloy 11, and hydroxide ions (OH - ).

[0213] 4M+4H2O+4e - →4MH+4OH - ···(2)

[0214] (Wherein, M is the hydrogen absorbing alloy 11.)

[0215] In addition, in this embodiment, a portion of the mobile hydrogen carrier 10 is ionically connected to the ion permeable membrane 106, and a portion of the oxygen generating electrode 105 is ionically connected to the ion permeable membrane 106, so the generated hydroxide ions can quickly move to the surface of the oxygen generating electrode 105. Therefore, the reactions of formula (1) and formula (2) can continuously occur.

[0216] According to the above method, in the hydrogen filling device 100A of the present embodiment, hydrogen can be filled into the hydrogen storage alloy 11 in the fluid hydrogen carrier 10 by applying a negative voltage to the negative current collector 101 and a positive voltage to the positive current collector 103 .

[0217] In this embodiment, the liquid hydrogen carriers 10 and the alkaline electrolyte 12 can be injected or discharged from the outside of the hydrogen filling device 100A by providing the joint 108. By performing the hydrogen filling operation while the liquid hydrogen carriers 10 and the alkaline electrolyte 12 flow, a large number of liquid hydrogen carriers 10 can be continuously filled with hydrogen.

[0218] In this way, the hydrogen filling device 100A has a negative current collector 101, a negative electrode gap 102, a positive electrode current collector 103, a positive electrode gap 104, an oxygen generating electrode 105 and an ion permeable membrane 106, and can fill hydrogen into the hydrogen absorption alloy 11 in the liquid hydrogen carrier 10 by applying a negative potential voltage to the negative current collector 101 and a positive potential voltage to the positive current collector 103.

[0219] <Power generation device using liquid hydrogen carrier>

[0220] A power generation device using the fluid hydrogen carrier according to this embodiment will be described. Figure 8 is a diagram showing a power generation device. Figure 8 As shown, the power generation device 200A using the mobile hydrogen carrier includes a negative electrode current collector 101, a negative electrode void 102 that can be filled with the mobile hydrogen carrier, a positive electrode current collector 103, a positive electrode void 104, an oxygen reduction electrode 201 and an ion permeable membrane 106, a seal 107 and a joint 108. The power generation device 200A generates electricity using the mobile hydrogen carrier.

[0221] (Oxygen reduction electrode)

[0222] The oxygen reduction electrode 201 only needs to have oxygen reduction activity on the surface. The so-called oxygen reduction activity is the effect of reducing oxygen to generate hydroxide ions, and an oxygen reduction catalyst can be used. As for the oxygen reduction electrode 201, the oxygen reduction catalyst can be used alone, or the oxygen reduction catalyst can be supported on a substrate for use. A catalytic layer containing an oxygen reduction catalyst and an ion-conductive binder can also 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 a positive current collector 103.

[0223] As a catalyst with oxygen reduction activity, for example, platinum, rhodium, palladium, iridium, osmium, ruthenium, rhenium, gold, silver, nickel, cobalt, molybdenum, lanthanum, strontium, yttrium, bismuth iridium oxide, nitrogen-containing metal complex, cobalt phthalocyanine, tetraazaannulene iron, a composite of carbon quantum dots and nanosheet graphene oxide, trioxotriadene compounds, bismuth chloride, boron nitride, zirconium oxide with oxygen vacancies, azaphthalocyanine metal complexes, etc. can be used. The catalyst can be used alone or in combination of two or more.

[0224] The oxygen reduction electrode 201 is configured so 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 in contact with the positive electrode gap 104. It should be noted that the so-called ion connection means that ion conduction from the oxygen reduction electrode 201 to the ion permeable membrane 106 is not blocked.

[0225] With this structure, electrons migrate from the positive electrode current collector to the oxygen reduction electrode 201 , and the electrons can reduce oxygen to generate hydroxide ions.

[0226] The other components are the same as those of the hydrogen filling device, and thus detailed descriptions thereof are omitted.

[0227] (Power generation method using liquid hydrogen carrier)

[0228] A method for generating electricity using the fluid hydrogen carrier according to the present embodiment will be described. Fig. 9 1 is a diagram showing a method for generating electricity using a mobile hydrogen carrier in a power generation device. Fig. 9 As shown, Figure 8 The power generation device 200A shown in FIG. 2 has a structure in which the negative electrode gap 102 and the positive electrode gap 104 are filled with the liquid hydrogen carrier 14 filled with hydrogen and the oxygen-containing material 202, respectively.

[0229] (oxygenated substances)

[0230] As long as the oxygen-containing substance 202 contains oxygen, air or a liquid containing a large amount of oxygen dissolved in a perfluorocarbon and a surfactant can be used. In addition, humidified oxygen or air can also be used. When using air, a device for removing or adsorbing carbon dioxide in the air can also be connected.

[0231] In the power generation device 200A, when a load is connected to the negative current collector 101 and the positive current collector 103, since the positive current collector 103 is electrically connected to the oxygen reduction electrode 201, the oxygen reduction electrode donates electrons to oxygen (reduction) and consumes water to generate hydroxide ions (OH) as shown in the following formula (3). - ).

[0232] O2+4e - +2H2O→4OH - ···(3)

[0233] In addition, in the present embodiment, a portion of the negative electrode current collector 101 is electrically connected to the liquid hydrogen carrier 14 filled with hydrogen. Therefore, when a load is connected to the negative electrode current collector 101 and the positive electrode current collector 103, hydrogen can be desorbed from the hydrogen storage alloy 13 filled with hydrogen in the liquid hydrogen carrier 14 filled with hydrogen, and electrons can be extracted as shown in the following formula (4).

[0234] 4MH+4OH - →4M+4H2O+4e - ···(4)

[0235] (Wherein, M is the hydrogen absorbing alloy 11.)

[0236] In addition, in the present embodiment, a portion of the liquid hydrogen carrier 14 filled with hydrogen is ionically connected to the ion permeable membrane 106, and a portion of the oxygen reduction electrode 201 is ionically connected to the ion permeable membrane 106, so that the hydroxide ions generated in the oxygen reduction electrode 201 can quickly move to the surface of the liquid hydrogen carrier 14 filled with hydrogen. Therefore, the reactions of formula (3) and formula (4) can continuously occur.

[0237] By the above method, in the power generation device 200A of the present embodiment, by connecting a load between the negative current collector 101 and the positive current collector 103 , hydrogen can be released from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled liquid hydrogen carrier 14 to generate electricity.

[0238] In addition, in this embodiment, the liquid hydrogen carrier 14 and the oxygenate 202 filled with hydrogen can be injected or discharged from the outside of the power generation device 200A by providing the interface 28. By performing power generation operation while flowing the liquid hydrogen carrier 14 and the oxygenate 202 filled with hydrogen, large-capacity power generation can be performed for a long time.

[0239] 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 released from the hydrogen-filled hydrogen absorption alloy 13 in the hydrogen-filled liquid hydrogen carrier 14 to generate electricity.

[0240] <Hydrogen filling and power generation device using liquid hydrogen carrier>

[0241] According to the present embodiment, a hydrogen filling and power generation device capable of performing hydrogen filling and power generation by a single device can be provided. A hydrogen filling and power generation device using the fluid hydrogen carrier according to the present embodiment will be described. Fig.10 : is a diagram showing a hydrogen filling and power generation device. Fig.10 As shown, the hydrogen filling and power generation device 300A using a liquid hydrogen carrier is composed of a negative electrode current collector 101, a negative electrode gap 102 that can be filled with a liquid hydrogen carrier, a positive electrode current collector 103, a positive electrode gap 104, a binary electrode 301 that can generate oxygen reduction, an ion permeable membrane 106, a seal 107, and a joint 108.

[0242] (Binary electrode capable of oxygen reduction and oxygen generation)

[0243] The binary electrode 301 only needs to have both oxygen reduction activity and oxygen generation activity on the surface. The binary electrode 301 can be composed of a catalyst having oxygen reduction activity and oxygen generation activity, or it can be composed of two or more different catalysts for oxygen reduction and oxygen generation. The catalyst can be used alone, or the catalyst can be supported on a substrate for use. The catalytic layer containing the catalyst and the binder having ion conductivity can also 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 a positive current collector 103.

[0244] As the catalyst having both oxygen reduction and oxygen generation activities, for example, nickel compounds, cobalt compounds, pyrochlore-type bismuth-iridium oxides, pyrochlore-type bismuth-ruthenium composite oxides, etc. The catalyst may be used alone or in combination of two or more.

[0245] The binary electrode 301 only needs to be configured so that a portion thereof is ionically connected to the ion permeable membrane 106 and a portion thereof is electrically connected to the positive electrode current collector 103 and in contact with the positive electrode gap 104. It should be noted that the so-called ion connection means that ion conduction from the oxygen reduction electrode 201 to the ion permeable membrane 106 is not blocked.

[0246] Through this structure, electrons migrate from the positive current collector 103 to the binary electrode 301, and through these electrons, oxygen is reduced to produce hydroxide ions. Electrons migrate from the positive current collector to the binary electrode 301, and through these electrons, the hydroxide ions supplied by the ion permeable membrane 106 can be oxidized to produce oxygen.

[0247] The other components are the same as those of the hydrogen filling device, and thus detailed descriptions thereof are omitted.

[0248] (Hydrogen filling and power generation method using a liquid hydrogen carrier)

[0249] The mechanism of the hydrogen filling and power generation method is the same as that of the hydrogen filling device and power generation device, and therefore detailed description is omitted.

[0250] Thus, the hydrogen filling and power generation device 300A includes the negative electrode current collector 101, the negative electrode gap 102, the positive electrode current collector 103, the positive electrode gap 104, the binary electrode 301, and the ion permeable membrane 106. The hydrogen filling and power generation device 300A can reduce oxygen to generate hydroxide ions by electrons after electrons migrate 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 after electrons migrate from the positive electrode current collector to the binary electrode 301 to generate oxygen.

[0251] <Second hydrogen filling and power generation device using liquid hydrogen carrier>

[0252] According to this embodiment, a hydrogen filling and power generation device can be provided which can perform hydrogen filling and power generation with one device without requiring oxygen generation and oxygen reduction. A second hydrogen filling and power generation device using the fluid hydrogen carrier according to this embodiment will be described. Fig.11 : is a diagram showing a second hydrogen filling and power generation device. Fig.11 As shown, the second hydrogen filling and power generation device 300B using a mobile hydrogen carrier is composed of a negative electrode current collector 101, a negative electrode gap 102 that can be filled with a mobile hydrogen carrier, a positive electrode current collector 103, a positive electrode gap 104, an ion permeable membrane 106, a seal 107 and a joint 108.

[0253] for Fig.10 The hydrogen filling and power generation device 300A shown in FIG. 1 is a structure in which the binary electrode 301 is removed. The other structures are the same as those of the hydrogen filling and power generation device 300A, and thus detailed description thereof is omitted.

[0254] (Second Hydrogen Filling and Power Generation Method Using Liquid Hydrogen Carrier)

[0255] The hydrogen filling and power generation method according to the present embodiment will be described. Fig.12 : is a diagram showing a hydrogen filling method. Fig.12 As shown, Fig.11 The second hydrogen filling and power generation device 300B shown in FIG. 1 has a structure in which the negative electrode gap 102 and the positive electrode gap 104 are filled with the fluid hydrogen carrier 10 and the slurry 302 containing nickel hydroxide, respectively. Fig.13 is a diagram showing a method of generating electricity. Fig.13 As shown, the following structure is shown, that is, Fig.11 The second hydrogen filling and power generation device 300B shown in FIG. 1 has a structure in which the negative electrode gap 102 and the positive electrode gap 104 are respectively filled with the liquid hydrogen carrier 14 filled with hydrogen and the slurry 304 containing nickel hydroxide and oxyhydroxide.

[0256] (Slurry containing nickel hydroxide)

[0257] The nickel hydroxide-containing slurry 302 according to the embodiment of the present invention is a mixture of a nickel hydroxide-containing substance 303 and an alkaline electrolyte 12, and may also contain additives such as a dispersant, a thickener, a surfactant, and a conductive filler in any amount. The nickel hydroxide-containing slurry 302 contains the nickel hydroxide-containing substance 303 in a state dispersed in the alkaline electrolyte 12.

[0258] (Nickel hydroxide containing substances)

[0259] The nickel hydroxide-containing material 303 included in the nickel hydroxide-containing slurry 302 according to the present embodiment can be reversibly oxidized and reduced by oxidizing to form nickel hydroxide oxide and reducing the nickel hydroxide oxide to form nickel hydroxide.

[0260] In addition, the nickel hydroxide-containing material 303 contained in the nickel hydroxide-containing slurry 302 according to the present embodiment preferably contains cobalt. The conductivity of nickel hydroxide is insufficient, and the conductivity is improved by adding cobalt.

[0261] The shape of the nickel hydroxide-containing material 303 is not particularly limited, and may be, for example, spherical, ellipsoidal, spindle-shaped, crushed, plate-shaped, columnar, or the like.

[0262] The average particle size of the nickel hydroxide-containing material 303 is 50 μm or less. When it is greater than 50 μm, in the process of filling the slurry 302 containing nickel hydroxide into hydrogen filling and power generation equipment, problems such as the nickel hydroxide-containing material 303 blocking the flow path and the fast sedimentation rate occur. The average particle size of the nickel hydroxide-containing material 303 can be appropriately set within the range of 50 μm or less, for example, preferably 10 nm to 50 μm, more preferably 20 nm to 25 μm, and further preferably 50 nm to 20 μm. If the average particle size is too small, the viscosity of the slurry 302 containing nickel hydroxide increases, hindering fluidity. If the average particle size of the nickel hydroxide-containing material 303 is within the above-mentioned preferred range, the nickel hydroxide-containing material 303 can be well dispersed in the alkaline electrolyte 12 and maintain the contact area with the alkaline electrolyte 12.

[0263] (Hydrogen filling method based on the second hydrogen filling and power generation device)

[0264] In the second hydrogen filling and power generation device 300B, when a negative potential voltage is applied to the negative current collector 101 and a positive potential voltage is applied to the positive current collector 103, since the positive current collector 103 is electrically connected to the slurry 302 containing nickel hydroxide, in the nickel hydroxide-containing material 303, electrons escape from the nickel hydroxide (Ni(OH)2) as shown in the following formula (5) to generate nickel hydroxide oxide (NiOOH) and water.

[0265] Ni(OH)2+OH - →NiOOH+H2O+e - ···(5)

[0266] In addition, in this embodiment, a part of the negative electrode current collector 101 is electrically connected to the liquid hydrogen carrier 10. Therefore, when a negative potential voltage is applied to the negative electrode current collector 101 and a positive potential voltage is applied to the positive electrode current collector 103, as shown in the following formula (2), hydrogen is filled into the hydrogen storage alloy 11 by the reaction between water in the liquid hydrogen carrier 14 filled with hydrogen and the hydrogen storage alloy 11, and hydroxide ions (OH - ).

[0267] 4M+4H2O+4e - →4MH+4OH - ···(2)

[0268] (Wherein, M is the hydrogen absorbing alloy 11.)

[0269] In addition, in this embodiment, a portion of the mobile hydrogen carrier 14 filled with hydrogen is ionically connected to the ion permeable membrane 106, and a portion of the oxygen generating electrode 105 is ionically connected to the ion permeable membrane 106, so 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 continuously occur.

[0270] By the above method, in the second hydrogen filling and power generation device 300B of the present embodiment, a negative potential voltage is applied to the negative current collector 101 and a positive potential voltage is applied to the positive current collector 103, so that hydrogen can be filled into the liquid hydrogen carrier 10 (see Figure 7 ) in the hydrogen absorbing alloy 11.

[0271] In addition, in this embodiment, the liquid hydrogen carrier 14 and the alkaline electrolyte 12 filled with hydrogen can be injected or discharged from the outside of the hydrogen filling device 100A by providing the joint 108. By performing the hydrogen filling operation while the liquid hydrogen carrier 10 and the alkaline electrolyte 12 flow, a large number of liquid hydrogen carriers 10 can be continuously filled with hydrogen.

[0272] Thus, the second hydrogen filling and power generation device 300B includes the negative electrode current collector 101, the negative electrode gap 102, the positive electrode current collector 103, the positive electrode gap 104 and the ion permeable membrane 106. By applying a negative potential voltage to the negative electrode current collector 101 and a positive potential voltage to the positive electrode current collector 103, hydrogen can be filled into the mobile hydrogen carrier 10 (see Figure 7 ) in the hydrogen storage alloy 11. Therefore, the second hydrogen filling and power generation device 300B does not have the binary electrode 301 in the hydrogen filling and power generation device 300A, and can perform hydrogen filling without performing oxygen generation and oxygen reduction.

[0273] (Electricity generation method using the second hydrogen filling and electricity generation device)

[0274] 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 is electrically connected to the slurry 304 containing nickel hydroxide, nickel hydroxide (Ni(OH)2) and hydroxide ions are generated by providing electrons to nickel hydroxide (NiOOH) and water as shown in the following formula (6).

[0275] NiOOH+H2O+e - →Ni(OH)2+OH - ···(6)

[0276] In addition, in the present embodiment, a portion of the negative electrode current collector 101 is electrically connected to the liquid hydrogen carrier 14 filled with hydrogen. Therefore, when a load is connected to the negative electrode current collector 101 and the positive electrode current collector 103, hydrogen can be desorbed from the hydrogen storage alloy 13 filled with hydrogen in the liquid hydrogen carrier 14 filled with hydrogen, and electrons can be extracted as shown in the following formula (4).

[0277] 4MH+4OH - →4M+4H2O+4e - ···(4)

[0278] (Wherein, M is the hydrogen absorbing alloy 11.)

[0279] In addition, in this embodiment, a portion of the liquid hydrogen carrier 14 filled with hydrogen is ionically connected to the ion permeable membrane 106, and a portion of the oxygen reduction electrode 201 is ionically connected to the ion permeable membrane 106, so the hydroxide ions generated in equation (6) can quickly move to the surface of the liquid hydrogen carrier 14 filled with hydrogen. Therefore, the reactions of equations (6) and (4) can continuously occur.

[0280] Through the above method, in the second hydrogen filling and power generation device 300B of this embodiment, by connecting a load between the negative current collector 101 and the positive current collector 103, hydrogen can be released from the hydrogen-filled hydrogen absorbing alloy 13 in the hydrogen-filled liquid hydrogen carrier 14 to generate electricity.

[0281] In addition, in this embodiment, the fluid hydrogen carrier 14 filled with hydrogen and the slurry 304 containing nickel hydroxide can be injected or discharged from the outside of the second hydrogen filling and power generation device 300B by providing the joint 108. By performing power generation operation while the fluid hydrogen carrier 14 filled with hydrogen and the slurry 304 containing nickel hydroxide flow, large-capacity power generation can be performed for a long time.

[0282] Thus, the second hydrogen filling and power generation device 300B has the negative electrode current collector 101, the negative electrode gap 102, the positive electrode current collector 103, the positive electrode gap 104 and the 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 released from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled liquid hydrogen carrier 14 to generate electricity. Therefore, the second hydrogen filling and power generation device 300B does not have the binary electrode 301 in the hydrogen filling and power generation device 300A, and can generate electricity without generating oxygen and reducing oxygen.

[0283] <Second hydrogen filling device for liquid hydrogen carrier>

[0284] The second hydrogen filling device for the fluid hydrogen carrier according to the present embodiment will be described. Fig.14 : is a diagram showing a second hydrogen filling device. Fig.14 As shown, the second hydrogen filling device 100B is composed of a negative electrode current collector 101, a negative electrode gap 102 that can be filled with a liquid hydrogen carrier, a positive electrode current collector 103, a positive electrode gap 104, an oxygen generating electrode 105, an ion permeable membrane 106, a seal 107, a joint 108, a porous negative electrode current collector 111 and a porous positive electrode current collector 112.

[0285] (Porous negative electrode current collector)

[0286] The porous negative electrode current collector 111 has through holes in the thickness direction and is configured in a manner of contacting the ion permeable membrane 106. By having through holes in the thickness direction, the hydroxyl ions generated when the liquid hydrogen carrier is filled with hydrogen can be mass transferred. In addition, by being configured in a manner of contacting the ion permeable membrane 106, the distance from the positive electrode collector can be shortened, and the cell resistance can be reduced. In addition, the deformation of the ion permeable membrane 106 during actual use can be suppressed.

[0287] The porous negative electrode current collector 111 only needs to be porous and conductive, for example, nickel mesh, nickel foam, nickel porous body, nickel nonwoven fabric, carbon nonwoven fabric, carbon paper, stainless steel mesh, stainless steel foam, stainless steel porous body, stainless steel nonwoven fabric, etc. can be used.

[0288] (Porous positive electrode current collector)

[0289] The porous positive electrode current collector 112 has through holes in the thickness direction and is configured in a manner of contacting the ion permeable membrane 106. By having through holes in the thickness direction, the hydroxyl ions generated when the liquid hydrogen carrier is filled with hydrogen can be mass transferred. In addition, by being configured in a manner of contacting the ion permeable membrane 106, the distance from the positive electrode collector can be shortened, and the cell resistance can be reduced. In addition, the deformation of the ion permeable membrane 106 during actual use can be suppressed.

[0290] The porous positive current collector 112 only needs to be porous and conductive, for example, nickel mesh, nickel foam, nickel porous body, nickel nonwoven fabric, carbon nonwoven fabric, carbon paper, stainless steel mesh, stainless steel foam, stainless steel porous body, stainless steel nonwoven fabric, etc. can be used.

[0291] The configuration is the same as that of the first hydrogen filling device except that a porous negative electrode current collector 111 and a porous positive electrode current collector 112 are used.

[0292] Thus, the second hydrogen filling device 100B is a hydrogen filling device 100A having a porous negative current collector 111 and a porous positive current collector 112. The second hydrogen filling device 100B, like the hydrogen filling device 100A, can fill hydrogen into the liquid hydrogen carrier 10 (see Figure 7 ) in the hydrogen absorbing alloy 11.

[0293] <Second power generation device using liquid hydrogen carrier>

[0294] The second power generation device of the fluid hydrogen carrier according to the present embodiment will be described. Fig.15 : is a diagram showing a second power generation device. Fig.15 As shown, the second power generation device 200B is composed of a negative electrode current collector 101, a negative electrode void 102 that can be filled with a mobile hydrogen carrier, a positive electrode current collector 103, a positive electrode void 104, an oxygen reduction electrode 201, an ion permeable membrane 106, a seal 107, a joint 108, a porous negative electrode current collector 111, and a porous positive electrode current collector 112.

[0295] The configuration is the same as that of the first power generating device except that a porous negative electrode current collector 111 and a porous positive electrode current collector 112 are used.

[0296] Thus, the second power generation device 200B has the porous negative electrode current collector 111 and the porous positive electrode current collector 112 in the power generation device 200A. Thus, the second power generation device 200B, like the power generation device 200A, can generate electricity by connecting a load between the negative electrode current collector 101 and the positive electrode current collector 103, thereby allowing hydrogen to escape from the hydrogen-filled hydrogen storage alloy 13 in the hydrogen-filled liquid hydrogen carrier 14.

[0297] <Third hydrogen filling and power generation device using liquid hydrogen carrier>

[0298] A third hydrogen filling and power generation device using the fluid hydrogen carrier according to the present embodiment will be described. Fig.16 : is a diagram showing a third hydrogen filling and power generation device. Fig.16 As shown, the third hydrogen filling and power generation device 300C is composed of a negative electrode current collector 101, a negative electrode void 102 that can be filled with a mobile hydrogen carrier, a positive electrode current collector 103, a positive electrode void 104, a binary electrode 301 and an ion permeable membrane 106, a seal 107, a joint 108, a porous negative electrode current collector 111, and a porous positive electrode current collector 112.

[0299] The device is the same as the first hydrogen filling and power generation device except that the porous negative electrode current collector 111 and the porous positive electrode current collector 112 are used.

[0300] 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. The third hydrogen filling and power generation device 300C can reduce oxygen to generate hydroxide ions by electrons after electrons migrate from the positive electrode current collector 103 to the binary electrode 301, and can oxidize hydroxide ions supplied from the ion permeable membrane 106 to generate oxygen by electrons after electrons migrate from the positive electrode current collector to the binary electrode 301, similarly to the hydrogen filling and power generation device 300A.

[0301] <Fourth hydrogen filling and power generation device using liquid hydrogen carrier>

[0302] A fourth hydrogen filling and power generation device using the fluid hydrogen carrier according to the present embodiment will be described. Fig.17 : is a diagram showing a fourth hydrogen filling and power generation device. Fig.17 As shown, the fourth hydrogen filling and power generation device 300D is composed of a negative electrode current collector 101, a negative electrode void 102 that can be filled with a mobile hydrogen carrier, a positive electrode current collector 103, a positive electrode void 104, an ion permeable membrane 106, a seal 107, a joint 108, a porous negative electrode current collector 111, and a porous positive electrode current collector 112.

[0303] The device is the same as the second hydrogen filling and power generation device except that the porous negative electrode current collector 111 and the porous positive electrode current collector 112 are used.

[0304] Therefore, the fourth hydrogen filling 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 filling and power generation device 300B. The fourth hydrogen filling and power generation device 300D is similar to the second hydrogen filling and power generation device 300B, and can fill hydrogen into the liquid hydrogen carrier 10 (see Figure 7 ) in the hydrogen storage alloy 11. In addition, the fourth hydrogen filling and power generation device 300D can generate electricity by connecting a load between the negative current collector 101 and the positive current collector 103, so that hydrogen can escape from the hydrogen storage alloy 13 filled with hydrogen in the liquid hydrogen carrier 14 filled with hydrogen. Therefore, the fourth hydrogen filling and power generation device 300D, like the second hydrogen filling and power generation device 300B, does not have a binary electrode 301, and can perform hydrogen filling and power generation without oxygen generation and oxygen reduction.

[0305] <Third hydrogen filling device for liquid hydrogen carrier>

[0306] A third hydrogen filling device for the fluid hydrogen carrier according to the present embodiment will be described. Fig.18 : is a diagram showing a third hydrogen filling device. Fig.18 As shown, the third hydrogen filling device 100C has a structure in which two second hydrogen filling devices are stacked with a bipolar plate 121 interposed therebetween, and has the same components as those of the second hydrogen filling device except for the bipolar plate 121 .

[0307] 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 more than two, and is not limited thereto. By connecting more than two hydrogen filling devices in series, a voltage multiple of the number of connected devices can be generated. That is, if the amount of energy is the same, the current flowing can be reduced, and heat generation can be suppressed.

[0308] (Bipolar Plate)

[0309] The bipolar plate 121 can also be used when two or more hydrogen filling devices are connected in series, and can function as both the negative current collector 101 and the positive current collector 103. That is, any material that can be used for the negative current collector 101 and the positive current collector 103 can be used without particular limitation.

[0310] Therefore, the third hydrogen filling device 100C includes a plurality of (in this embodiment, two) second hydrogen filling devices 100B via the bipolar plate 121. Similarly to the second hydrogen filling device 100B, hydrogen can be filled into the liquid hydrogen carrier 10 (see Figure 7 ) in the hydrogen absorbing alloy 11.

[0311] <Third power generation device using liquid hydrogen carrier>

[0312] A third power generation device using the fluid hydrogen carrier according to this embodiment will be described. Fig.19 : is a diagram showing a third power generation device. Fig.19 As shown, the third power generation device 200C has a structure in which two second power generation devices are stacked with a bipolar plate 121 interposed therebetween, and has the same components as the second power generation device except for the bipolar plate 121 .

[0313] 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 more than two, and is not limited thereto. By connecting more than two hydrogen filling devices in series, a voltage multiple of the number of connected devices can be generated. That is, if the amount of energy is the same, the current flowing can be reduced, and heat generation can be suppressed.

[0314] Therefore, the third power generation device 200C has multiple (in this embodiment, 2) second power generation devices 200B separated by the bipolar plate 121. Similar to the second power generation device 200B, by connecting a load between the negative current collector 101 and the positive current collector 103, hydrogen can be allowed to escape from the hydrogen-filled hydrogen absorption alloy 13 in the hydrogen-filled liquid hydrogen carrier 14 to generate electricity.

[0315] <Fifth hydrogen filling and power generation device using liquid hydrogen carrier>

[0316] A fifth hydrogen filling and power generation device using the fluid hydrogen carrier according to the present embodiment will be described. Fig. 20 : is a diagram showing a fifth hydrogen filling and power generation device. Fig. 20 As shown, the fifth hydrogen filling and power generation device 300E has a structure in which two third hydrogen filling and power generation devices are stacked with a bipolar plate 121 interposed therebetween, and has the same components as the third hydrogen filling and power generation device except for the bipolar plate 121 .

[0317] 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 more than two, and is not limited thereto. By connecting more than two hydrogen filling devices in series, a voltage multiple of the number of connected devices can be generated. That is, if the amount of energy is the same, the current flowing can be reduced, and heat generation can be suppressed.

[0318] Therefore, the fifth hydrogen filling and power generation device 300E includes a plurality of (in this embodiment, two) third hydrogen filling and power generation devices 300C in series through the bipolar plate 121, so that the same amount of energy can be used while suppressing heat generation: Figure 7 ) is filled with hydrogen into the hydrogen storage alloy 11, and hydrogen is released from the hydrogen storage alloy 13 filled with hydrogen in the liquid hydrogen carrier 14 filled with hydrogen, thereby generating power.

[0319] <Sixth hydrogen filling and power generation device using liquid hydrogen carrier>

[0320] A sixth hydrogen filling and power generation device using the fluid hydrogen carrier according to the present embodiment will be described. Fig.21 : is a diagram showing the sixth hydrogen filling and power generation device. Fig.21 As shown, the sixth hydrogen filling and power generation device 300E has a structure in which two fourth hydrogen filling and power generation devices are stacked with a bipolar plate 121 interposed therebetween, and has the same components as the fourth hydrogen filling and power generation device except for the bipolar plate 121 .

[0321] 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 more than two, and is not limited thereto. By connecting more than two hydrogen filling devices in series, a voltage multiple of the number of connected devices can be generated. That is, if the amount of energy is the same, the current flowing can be reduced, and heat generation can be suppressed.

[0322] <Hydrogen filling and power generation system>

[0323] A hydrogen filling and power generation system using the mobile hydrogen carrier 10 according to the present embodiment is described. 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 may be applied. In the present embodiment, the sixth hydrogen filling and power generation device 300E is used for description.

[0324] Fig. 22 : is a diagram showing a hydrogen filling and power generation system. Fig. 22 As shown, the hydrogen filling and power generation system 400A is composed of a sixth hydrogen filling and power generation device 300E formed by connecting four hydrogen filling and power generation devices in series, a negative electrode tank 410, a negative electrode pressurizing / depressurizing device 420, a positive electrode tank 430, a positive electrode pressurizing / depressurizing 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 can be provided outside the hydrogen filling and power generation device, or can be built into the hydrogen filling and power generation device.

[0325] (Negative electrode tank)

[0326] The negative electrode tank 410 is used to store the mobile hydrogen carrier 10. It can be formed of a material that is not corroded or dissolved by the alkaline electrolyte 12 contained in the mobile hydrogen carrier 10. The material constituting the negative electrode tank 410 is not particularly limited, and examples thereof include nickel, stainless steel, polyethylene, polypropylene, acrylic resin, polyvinyl chloride, ABS resin, polyoxymethylene, polycarbonate, polystyrene, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, etc. These can be used alone or in combination of two or more.

[0327] In addition, in order to improve the wear resistance of the inner wall of the negative electrode can 410, a coating layer can be formed on the inner wall of the negative electrode can 410 using 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. They can be used alone or in combination of two or more. In addition, gas is generated along with charging and discharging, so in order to suppress the increase in the internal pressure of the negative electrode can 410, hydrogen filling and damage to the power generation system 400A, a pressure regulating valve not shown in the figure can be provided in the negative electrode can 410. In addition, one or more unillustrated cocks that can discharge the liquid hydrogen carrier 10 in the negative electrode can 410 or inject the liquid hydrogen carrier 10 into the negative electrode can 410 can also be provided.

[0328] (Negative electrode pressurization / depressurization device)

[0329] The negative electrode pressurization / decompression device 420 can be used as long as it can deliver liquid to the liquid hydrogen carrier 10, for example, a centrifugal pump, a propeller pump, a reciprocating pump, a rotary pump, etc. can be cited. As a centrifugal pump, for example, a vortex pump, a turbine pump, etc. can be cited. As a propeller pump, for example, an axial flow pump, a mixed flow pump, a cascade pump, etc. can be cited. As a reciprocating pump, for example, a piston pump, a plunger pump, a diaphragm pump, a tubular pump, a wing pump, etc. can be cited. As a rotary pump, for example, a gear pump, an eccentric shaft pump, a screw pump, etc. can be cited. They can be used alone or in combination of two or more.

[0330] (Positive electrode tank)

[0331] 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 slurry 302 containing nickel hydroxide, or the slurry 304 containing nickel hydroxide oxide, it can be formed of a material that is not corroded or dissolved by the alkaline electrolyte 12. At this time, the material constituting the positive electrode tank 430 is not particularly limited, and examples thereof include nickel, stainless steel, polyethylene, polypropylene, acrylic resin, polyvinyl chloride, ABS resin, polyoxymethylene, polycarbonate, polystyrene, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, etc. These can be used alone or in combination of two or more.

[0332] (Positive electrode pressurization / depressurization device)

[0333] The positive electrode pressurization / decompression device 440 can transport alkaline electrolyte 12, slurry 302 containing nickel hydroxide, slurry 304 containing oxidized nickel hydroxide, and oxygen-containing material 202, for example, centrifugal pumps, propeller pumps, reciprocating pumps, rotary pumps, etc. can be cited. As a centrifugal pump, for example, a vortex pump, a turbine pump, etc. can be cited. As a propeller pump, for example, an axial flow pump, a mixed flow pump, a cascade pump, etc. can be cited. As a reciprocating pump, for example, a piston pump, a plunger pump, a diaphragm pump, a tubular pump, a wing pump, etc. can be cited. As a rotary pump, for example, a gear pump, an eccentric shaft pump, a screw pump, etc. can be cited. They can be used only one kind, or two or more kinds can be used in combination.

[0334] (Flow path between devices)

[0335] The inter-device flow path 450 is a flow path provided for conveying / distributing the mobile hydrogen carrier 10, the alkaline electrolyte 12, the nickel hydroxide-containing slurry 302, the nickel hydroxide oxyhydroxide-containing slurry 304, and the oxygen-containing material 202 to each device when a plurality of devices are connected in series.

[0336] The material constituting the inter-device flow path 450 is not particularly limited, and examples thereof include nickel, stainless steel, polyethylene, polypropylene, acrylic resin, polyvinyl chloride, ABS resin, polyoxymethylene, polycarbonate, polystyrene, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, stainless steel, nickel, carbon steel, etc. These materials may be used alone or in combination of two or more.

[0337] The shape of the inter-device flow path 450 is not particularly limited, and may be tubular, or may be formed as a member in a hydrogen filling or power generation device.

[0338] (Device flow path)

[0339] The device flow path 460 is a flow path branched from the inter-device flow path 450 for transporting the mobile hydrogen carrier 10, the alkaline electrolyte 12, the nickel hydroxide-containing slurry 302, the nickel hydroxide-containing slurry 304, and the oxygen-containing material 202 to the negative electrode gap 102 or the positive electrode gap 104 in the device.

[0340] The material constituting the device flow path 460 is not particularly limited, and examples thereof include nickel, stainless steel, polyethylene, polypropylene, acrylic resin, polyvinyl chloride, ABS resin, polyoxymethylene, polycarbonate, polystyrene, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, polyetheretherketone, stainless steel, nickel, carbon steel, etc. These materials may be used alone or in combination of two or more.

[0341] For the flow rate inside the device, in order to uniformly flow between stacked devices, As represented by the following formula (7) is preferably small: As<1 is preferred, As<0.1 is more preferred, and As<0.01 is further preferred.

[0342] As = [minimum cross-sectional area of ​​device flow path 460] / [maximum cross-sectional area of ​​inter-device flow path 450] (7)

[0343] The liquid 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 liquid hydrogen carrier 10 in the inter-device flow path 450 and the device flow path 460. This causes a decrease in energy efficiency.

[0344] That is, in the path of the short-circuit current path of the hydrogen filling and power generation system 400A according to the present embodiment, the continuous inter-device flow path 450 and the device flow path 460 between the adjacent hydrogen filling and power generation devices sandwiching the bipolar plate 121 ( Fig. 22 The dotted line in FIG. 1 has an area made of insulating material, and the shortest distance of the flow path made of the insulating material needs to be 50 cm or more. In this embodiment, only the conductivity of the mobile hydrogen carrier 10 is described in detail, but the slurry 302 containing nickel hydroxide and the slurry 304 containing nickel hydroxide also have conductivity, so a flow path made of insulating material is also required.

[0345] Thus, the hydrogen filling and power generation system 400A can reduce the short-circuit current by having the above-mentioned structure, and can perform hydrogen filling and power generation with high energy efficiency.

[0346] <Second Hydrogen Filling and Power Generation System>

[0347] The second hydrogen filling and power generation system using the mobile hydrogen carrier 10 involved in this embodiment is described. 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 can be applied. In this embodiment, the sixth hydrogen filling and power generation device 300E is used for description.

[0348] Fig.23 FIG. 2 is a diagram showing a second hydrogen filling and power generation system. Fig.23 As shown, 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 shutoff device 461 is provided in the device flow path 460 .

[0349] (Liquid cut-off device)

[0350] The liquid shutoff device 461 is provided in the device flow path 460 as the short-circuit current path, and is provided to cut off the continuity of the fluid hydrogen carrier 10 or the slurry 302 containing nickel hydroxide and the slurry 304 containing nickel hydroxide oxide, which are the cause of the short circuit. Here, the so-called cutoff means that the short-circuit path is blocked by mixing a gas such as air, nitrogen, and oxygen with low conductivity into the continuous path of the fluid hydrogen carrier 10 or the slurry 302 containing nickel hydroxide and the slurry 304 containing nickel hydroxide oxide. The means for mixing the gas to block the short-circuit path is not limited, for example, a structure for dripping the fluid hydrogen carrier 10 or the slurry 302 containing nickel hydroxide and the slurry 304 containing nickel hydroxide oxide can be used like a drip tube used in medical treatment. By dripping the conductive fluid, the short-circuit path is blocked and the short-circuit current does not flow.

[0351] Therefore, the second hydrogen filling and power generation system 400B has the above-described structure, and thus can reduce short-circuit current and perform hydrogen filling and power generation with high energy efficiency, similar to the hydrogen filling and power generation system 400A.

[0352] <Third Hydrogen Filling and Power Generation System>

[0353] A third hydrogen filling and power generation system using the mobile hydrogen carrier 10 according to the present embodiment is described. 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 are applicable. In the present embodiment, the sixth hydrogen filling and power generation device 300E is used for description.

[0354] Fig.24 FIG. 4 is a diagram showing a third hydrogen filling and power generation system. Fig.24 As shown, 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.

[0355] (Valve that can be opened and closed)

[0356] The valve 462 that can be opened and closed is provided in the device flow path 460 that is the short-circuit current path, and is provided to cut off the continuity of the mobile hydrogen carrier 10 or the slurry 302 containing nickel hydroxide and the slurry 304 containing nickel hydroxide oxide that are the cause of the short circuit. Here, the so-called cutoff means that the continuous path of the mobile hydrogen carrier 10 or the slurry 302 containing nickel hydroxide and the slurry 304 containing nickel hydroxide oxide that has conductivity is blocked by the valve. In addition, at the same time, among the devices connected in series, only the valve connected to one device can be opened at the same time.

[0357] Therefore, the third hydrogen filling and power generation system 400C has the above-described structure, and thus can reduce short-circuit current and perform hydrogen filling and power generation with high energy efficiency, similar to the hydrogen filling and power generation system 400A.

[0358] <Fourth Hydrogen Filling and Power Generation System>

[0359] A fourth hydrogen filling and power generation system using the mobile hydrogen carrier 10 according to the present embodiment is described. 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 are applicable. In the present embodiment, the sixth hydrogen filling and power generation device 300E is used for description.

[0360] Fig.25 FIG. 4 is a diagram showing a fourth hydrogen filling and power generation system. Fig.25 As shown, 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 mobile hydrogen carrier can be separated into the negative electrode tank for storing the mobile hydrogen carrier 14 filled with hydrogen and the mobile hydrogen carrier 10 before hydrogen filling for storage. In addition, according to this structure, the mobile hydrogen carrier can be separated into the positive electrode tank for storing the slurry 302 containing nickel hydroxide and the slurry 304 containing nickel hydroxide for storage.

[0361] (Second negative electrode tank)

[0362] The second negative electrode tank 470 has the same structure as the negative electrode tank 410, so detailed description is omitted. The sixth hydrogen filling and power generation device 300E is arranged between the second negative electrode tank 470 and the negative electrode tank 410. With this arrangement, the liquid hydrogen carriers 10 before hydrogen filling and the liquid hydrogen carriers 14 filled with hydrogen can be stored separately.

[0363] (Second positive electrode tank)

[0364] The second cathode tank 480 has the same structure as the cathode tank 430, so detailed description is omitted. The sixth hydrogen filling and power generation device 300E is arranged between the second cathode tank 480 and the cathode tank 430. With this arrangement, the slurry 302 containing nickel hydroxide and the slurry 304 containing nickel oxyhydroxide can be stored separately.

[0365] Therefore, the fourth hydrogen filling and power generation system 400D has the above-described structure, and when it is extracted as a hydrogen carrier in the form of a tank, the fluid hydrogen carrier before and after hydrogen filling is not mixed, and can be easily used as a hydrogen carrier.

[0366] As described above, each embodiment is described, but the above embodiments are presented as examples, and the present invention is not limited by the above embodiments. The above embodiments can be implemented in various other ways, and various combinations, omissions, substitutions, changes, etc. can be made within the scope of the invention without departing from the main idea of ​​the invention. These embodiments and their variations are included in the scope and main idea of ​​the invention, and are included in the invention described in the claims and their equivalents.

[0367] Example

[0368] The embodiment will be described in more detail below with reference to Examples and Comparative Examples, but the embodiment is not limited to these Examples and Comparative Examples.

[0369] <Example 1-1>

[0370] [Preparation of Liquid Hydrogen Carrier]

[0371] 0.2 wt% carboxymethyl cellulose (CMC) was mixed into a 6 mol / L potassium hydroxide aqueous solution and stirred overnight to dissolve the CMC. 8.125 g of the solution was mixed with 2.5 g of hydrogen absorbing alloy 261 and stirred at 2000 rpm for 3 minutes using a rotary and revolving stirrer. This operation was repeated 3 times to prepare a fluid hydrogen carrier.

[0372] [Manufacturing of charging and discharging battery cells]

[0373] Production Figure 5 The charge-discharge cell 20 of the secondary battery 30B shown in FIG. Carbon paper is used as the positive electrode current collector 22, nickel-plated stainless steel is used as the negative electrode current collector 21, platinum-supported carbon is used as the oxygen electrode catalyst 23, an anion exchange membrane is used as the ion permeable membrane 24, butyl rubber is used as the ion permeable membrane 24, stainless steel containers are used as the negative electrode side tank, i.e., tank 31, and the positive electrode side tank, i.e., tank 37, a single-axis eccentric screw pump is used as the negative electrode side pump, i.e., pump 32, and the positive electrode side pump, i.e., pump 38, and a nickel plate is used as the partition 35. The joints 27 and 36 are made of stainless steel piping, and the charge-discharge cell 20, tank 31, and pump 32 are connected, and the charge-discharge cell 20, tank 37, and pump 38 are connected.

[0374] [Charge]

[0375] 10 g of alkaline electrolyte 262 was put into tank 37, and 10 g of liquid hydrogen carrier 26 was put into tank 31, and charging was performed with a current of 10 mA. The flow rates of pumps 32 and 38 at this time were set to 5 mL / min at both the positive and negative electrodes. Fig.26 The charging curve at this time is shown in FIG. It should be noted that Fig.26 In the figure, the vertical axis represents voltage and the horizontal axis represents charging capacity.

[0376] like Fig.26 As shown, the electrochemical reaction was carried out at a constant voltage of about 1.55 V. This is considered to be due to oxygen generation in the positive electrode current collector 22 and hydrogen absorption into the hydrogen absorption alloy 261 in the negative electrode current collector 21, although there is also an overvoltage factor.

[0377] [Extraction of mobile hydrogen carriers]

[0378] A portion of the anode pipe is removed, and the anode-side pump is driven to extract the liquid hydrogen carrier 26 .

[0379] [Discharge]

[0380] 3 g of charged liquid hydrogen carrier 26 was injected into the tank of a cell different from the charge-discharge cell used in charging, and it was circulated at a flow rate of 5 mL / min using only the pump on the negative electrode side. The cell on the positive electrode side was filled with only air. In this state, discharge was performed at a current density of 10 mA.

[0381] Fig. 27 The discharge curve at this time is shown in FIG. It should be noted that, Fig. 27 In the figure, the vertical axis represents voltage and the horizontal axis represents discharge capacity.

[0382] like Fig. 27 As shown, the electrochemical reaction was carried out at a constant voltage of about 0.75 V. This is considered to be because oxygen reduction occurred in the positive electrode current collector 22 and hydrogen was released from the hydrogen storage alloy 261 in the negative electrode current collector 21 .

[0383] according to Fig.26 and Fig. 27 It was confirmed that by making the liquid hydrogen carrier 26 involved in the present embodiment fluid at normal temperature and pressure, the charge-discharge battery cell 20 involved in the present embodiment can easily extract and move the charged (hydrogen-occluded) liquid hydrogen carrier 26, and even thereafter, hydrogen can be released (discharged) from the liquid hydrogen carrier 26.

[0384] The mobile hydrogen carrier involved in this embodiment can make hydrogen high-density at room temperature and pressure, so it can transport a large amount of hydrogen. In addition, the mobile hydrogen carrier involved in this embodiment has fluidity at room temperature and pressure, so it can be easily handled and can be transported with high efficiency. The charge-discharge battery cell equipped with the mobile hydrogen carrier involved in this embodiment can electrochemically absorb and release hydrogen, so it can form a simple system that can easily control charging and discharging (absorption and release of hydrogen).

[0385] <Example 1-2>

[0386] [Preparation of Liquid Hydrogen Carrier]

[0387] Sodium polyacrylate (PAANa) with a weight average molecular weight of 2700 is mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 5 wt%, and stirred overnight to dissolve the PAANa. The solution is mixed with 20 volume % of a hydrogen absorbing alloy 11 with a median diameter of 15 μm, and stirred at 2000 rpm for 3 minutes using a rotary and revolving stirrer. The operation is repeated 3 times to prepare a slurry. It should be noted that the hydrogen absorbing alloy is obtained by pulverizing and classifying in an inert atmosphere. The slurry is heated at 100°C for 2 hours to prepare a fluid hydrogen carrier 10. The viscosity of the fluid hydrogen carrier 10 of Example 1-2 is measured using a rheometer manufactured by Anton Paar. As a result, the shear rate is 100sec. -1 The viscosity at this time is 450 mPa·sec.

[0388] [Production of Hydrogen Filling Device]

[0389] Production Figure 6 The hydrogen filling device 100A shown in FIG. Nickel-plated stainless steel is used as the positive electrode current collector 103, a nickel porous electrode with nickel sulfide formed on the surface is used as the oxygen generating electrode 105, nickel-plated stainless steel is used as the negative electrode current collector 21, an anion exchange membrane is used as the ion permeable membrane 106, and butyl rubber is used as the seal 107.

[0390] [Production of hydrogen filling system]

[0391] Make as Fig. 22 Such a hydrogen filling system is shown in FIG. A polypropylene tank is used as the negative electrode tank 410, a tube pump is used as the negative electrode pressurizing / depressurizing device 420, a polypropylene tank is used as the positive electrode tank 430, a tube pump is used as the positive electrode pressurizing / depressurizing device 440, and a device flow path 460 is used. In Example 1-2, the cells were not stacked, so no flow path between devices was used.

[0392] [Hydrogen filling into liquid hydrogen carrier]

[0393] 12 mL of the liquid hydrogen carrier 10 is added to the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is added to the positive electrode tank 430. The liquid hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0394] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density. Fig.28 2 shows the charging curve during hydrogen filling obtained in Example 1-2.

[0395] [Production of power generation device]

[0396] Production Figure 8 The power generation device 200A shown in FIG. Nickel-plated stainless steel is used as the positive electrode current collector 103, hydrophobic carbon paper coated with platinum-supported carbon on the surface is used as the oxygen reduction electrode 201, nickel-plated stainless steel is used as the negative electrode current collector 21, an anion exchange membrane is used as the ion permeable membrane 106, and butyl rubber is used as the seal 107.

[0397] [Production of power generation system]

[0398] Make as Fig. 22 The power generation system is shown in FIG. 4. A polypropylene can is used as the negative electrode can 410, a tube pump is used as the negative electrode pressurizing / depressurizing device 420, a tube pump is used as the positive electrode pressurizing / depressurizing device 440, and a device flow path 460 is used. In Example 1-2, no power generation devices are stacked, so no flow path between devices is used. In addition, in Example 1-2, since air is allowed to flow, the positive electrode can 430 is not used.

[0399] [Power generation using liquid hydrogen carriers]

[0400] The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0401] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 5.492Ah and the average discharge voltage is 0.77V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 1-2 is measured and the result is 10mL. That is, the discharge capacity density is equivalent to 549Ah / L. The Ah efficiency in Example 1-2 is 99.5%. Fig.292 shows the discharge curve during power generation obtained in Example 1-2.

[0402] In the power generation cell of the present invention, it was confirmed that the fluid hydrogen carrier comprising the hydrogen storage alloy of the present invention and an alkaline electrolyte is useful as a highly efficient hydrogen carrier.

[0403] Examples regarding the content of the hydrogen storage alloy in the fluid hydrogen carrier will be described below.

[0404] <Example 2>

[0405] The preparation of the fluid hydrogen carrier of Example 2 was the same as that of Example 1-2 except that 15 volume % of the hydrogen storage alloy 11 was mixed. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2.

[0406] [Hydrogen filling into liquid hydrogen carrier]

[0407] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 2 is described. 12 mL of the mobile hydrogen carrier 10 of Example 2 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0408] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 4.968 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 4.968 Ah was equivalent to 414 Ah / L in terms of capacity density.

[0409] [Power generation using liquid hydrogen carriers]

[0410] The power generation method according to Example 2 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0411] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 4.637Ah and the average discharge voltage is 0.71V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 2 was measured and the result was 11.2mL. That is, the discharge capacity density is equivalent to 412Ah / L. The Ah efficiency in Example 2 is 99.7%.

[0412] <Example 3>

[0413] The preparation of the fluid hydrogen carrier of Example 3 was the same as that of Example 1-2 except that 25 volume % of the hydrogen storage alloy 11 was mixed. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2.

[0414] [Hydrogen filling into liquid hydrogen carrier]

[0415] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 3 is described. 12 mL of the mobile hydrogen carrier 10 of Example 3 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0416] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 10000 until the capacity reached 8.280 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 8.280 Ah was equivalent to 690 Ah / L in terms of capacity density.

[0417] [Power generation using liquid hydrogen carriers]

[0418] The power generation method according to Example 3 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0419] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The discharge was carried out at a current value of 0.4V until the voltage reached 0.4V. The discharge capacity was 7.086Ah and the average discharge voltage was 0.80V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 3 was measured and the result was 10.3mL. That is, the discharge capacity density was equivalent to 687Ah / L. The Ah efficiency in Example 3 was 99.7%.

[0420] <Example 4>

[0421] The preparation of the fluid hydrogen carrier of Example 4 was the same as that of Example 1-2 except that 30 volume % of the hydrogen storage alloy 11 was mixed. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2.

[0422] [Hydrogen filling into liquid hydrogen carrier]

[0423] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 4 is described. 12 mL of the mobile hydrogen carrier 10 of Example 4 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0424] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 10000 until the capacity reached 9.936Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12mL, the capacity of 9.936Ah was equivalent to 828Ah / L in terms of capacity density.

[0425] [Power generation using liquid hydrogen carriers]

[0426] The power generation method according to Example 4 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0427] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 4.322Ah and the average discharge voltage is 0.82V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 4 was measured and the result was 6.0mL. That is, the discharge capacity density is equivalent to 720Ah / L. The Ah efficiency in Example 4 is 87.0%.

[0428] <Comparative Example 1>

[0429] The preparation of the fluid hydrogen carrier of Comparative Example 1 was the same as that of Example 1-2 except that 10 volume % of the hydrogen storage alloy 11 was mixed. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2.

[0430] [Hydrogen filling into liquid hydrogen carrier]

[0431] The method of filling hydrogen into the mobile hydrogen carrier involved in Comparative Example 1 is described. 12 mL of the mobile hydrogen carrier 10 of Comparative Example 1 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0432] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 3.312 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 3.312 Ah was equivalent to 276 Ah / L in terms of capacity density.

[0433] [Power generation using liquid hydrogen carriers]

[0434] The power generation method according to Comparative Example 1 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0435] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value was discharged until the voltage reached 0.4V. The discharge capacity was 2.390Ah and the average discharge voltage was 0.71V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Comparative Example 1 was measured and the result was 11.5mL. That is, the discharge capacity density was equivalent to 208Ah / L. The Ah efficiency in Comparative Example 1 was 75.3%.

[0436] In Examples 1-2, Examples 2 to 4, and Comparative Example 1, hydrogen filling and power generation characteristics of fluid hydrogen carriers with changed contents of the hydrogen storage alloy 11 were compared. The results are shown in Table 1.

[0437] [Table 1]

[0438]

[0439] The hydrogen absorption alloy content of Comparative Example 1 is 10% by volume, the Ah efficiency is low, and the average discharge voltage is also low. Based on the result of the low average discharge voltage, the resistance is predicted to be high. That is, it is believed that when the hydrogen absorption alloy content is 10% by volume, the amount of hydrogen absorption alloy with high conductivity is small, and the conductivity of the fluid hydrogen carrier itself is insufficient. At the level of Examples 1-2, Examples 2, and 3 in which the hydrogen absorption alloy content is more than 15% by volume, the Ah efficiency is more than 99%. It can be seen that the hydrogen absorption alloy content in the fluid hydrogen carrier is preferably more than 15% by volume. The hydrogen absorption alloy content of Example 4 is 30% by volume, and the discharge capacity density during power generation is high, but the Ah efficiency is lower than that of Examples 1-2, Examples 2, and 3. In addition, in Example 4, the volume of the fluid hydrogen carrier that can be extracted from the tank of the hydrogen filling device to the power generation device is smaller than other levels. This is because the viscosity of the fluid hydrogen carrier increases as the hydrogen absorption alloy content increases.

[0440] Hereinafter, examples concerning the particle size of the hydrogen storage alloy serving as a fluid hydrogen carrier will be described.

[0441] <Example 5>

[0442] The preparation of the fluid hydrogen carrier of Example 5 is the same as that of Example 1-2 except that the hydrogen storage alloy 11 with a median diameter of 5 μm is used. 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.

[0443] [Hydrogen filling into liquid hydrogen carrier]

[0444] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 5 is described. 12 mL of the mobile hydrogen carrier 10 of Example 5 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0445] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0446] [Power generation using liquid hydrogen carriers]

[0447] The power generation method according to Example 5 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0448] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 4.943Ah, and the average discharge voltage is 0.80V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 5 was measured and the result was 9.3mL. That is, the discharge capacity density is equivalent to 532Ah / L. The Ah efficiency in Example 5 is 96.3%.

[0449] <Example 6>

[0450] The preparation of the fluid hydrogen carrier of Example 6 is the same as that of Example 1-2 except that the hydrogen storage alloy 11 with a median diameter of 25 μm is used. 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.

[0451] [Hydrogen filling into liquid hydrogen carrier]

[0452] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 6 is described. 12 mL of the mobile hydrogen carrier 10 of Example 6 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0453] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0454] [Power generation using liquid hydrogen carriers]

[0455] The power generation method according to Example 6 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0456] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 5.646Ah and the average discharge voltage is 0.78V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 6 was measured and the result was 10.3mL. That is, the discharge capacity density is equivalent to 548Ah / L. The Ah efficiency in Example 6 is 99.3%.

[0457] <Example 7>

[0458] The preparation of the fluid hydrogen carrier of Example 7 is the same as that of Example 1-2 except that the hydrogen storage alloy 11 with a median diameter of 35 μm is used. 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.

[0459] [Hydrogen filling into liquid hydrogen carrier]

[0460] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 7 is described. 12 mL of the mobile hydrogen carrier 10 of Example 7 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0461] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0462] [Power generation using liquid hydrogen carriers]

[0463] The power generation method according to Example 7 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0464] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 5.744Ah and the average discharge voltage is 0.75V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 7 was measured and the result was 10.5mL. That is, the discharge capacity density is equivalent to 547Ah / L. The Ah efficiency in Example 7 is 99.1%.

[0465] <Example 8>

[0466] The preparation of the fluid hydrogen carrier of Example 8 was the same as that of Example 1-2 except that the hydrogen storage alloy 11 with a median diameter of 45 μm was used. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2.

[0467] [Hydrogen filling into liquid hydrogen carrier]

[0468] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 8 is described. 12 mL of the mobile hydrogen carrier 10 of Example 8 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0469] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0470] [Power generation using liquid hydrogen carriers]

[0471] The power generation method according to Example 8 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0472] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 5.841Ah and the average discharge voltage is 0.75V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 8 was measured and the result was 10.7mL. That is, the discharge capacity density is equivalent to 545Ah / L. The Ah efficiency in Example 8 is 98.9%.

[0473] <Comparative Example 2>

[0474] The preparation of the fluid hydrogen carrier of Comparative Example 2 was the same as that of Example 1-2 except that the hydrogen storage alloy 11 with a median diameter of 55 μm was used. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2.

[0475] [Hydrogen filling into liquid hydrogen carrier]

[0476] The method of filling hydrogen into the liquid hydrogen carrier 10 according to Comparative Example 2 is described. 12 mL of the liquid hydrogen carrier 10 according to Comparative Example 2 is put into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The liquid hydrogen carrier 10 is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the 6 mol / L potassium hydroxide aqueous solution is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0477] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of , and as a result, the flow of the liquid hydrogen carrier 10 stopped in the middle of the charge. The reason for the stop was the blockage of the flow path caused by the aggregation of the hydrogen storage alloy 11.

[0478] The hydrogen filling and power generation characteristics of the fluid hydrogen carriers when the median diameter of the hydrogen storage alloy 11 was changed were compared between Examples 1-2, Examples 5 to 8, and Comparative Example 2. The results are shown in Table 2.

[0479] [Table 2]

[0480]

[0481] In the liquid hydrogen carrier 10 using the hydrogen absorbing alloy 11 with a median diameter of 55 μm in Comparative Example 2, the hydrogen absorbing alloy 11 aggregates during the flow. In other embodiments, almost the same power generation characteristics are obtained. That is, the median diameter of the hydrogen absorbing alloy 11 involved in the present invention is preferably 50 μm or less. In addition, the liquid hydrogen carrier 10 using the hydrogen absorbing alloy 11 with a median diameter of 55 μm in Example 5 has an increased viscosity, so the amount of liquid hydrogen carrier that can be extracted to the power generation device is slightly less than other levels. That is, the median diameter is more preferably 10 μm or more and 50 μm or less, and further preferably 10 μm or more and 20 μm or less.

[0482] Examples of additives in alkaline electrolyte solutions related to mobile hydrogen carriers are described below.

[0483] <Example 9>

[0484] In the preparation of the mobile hydrogen carrier of Example 9, the same method as in Example 1-2 was used except that sodium polyacrylate (PAANa) with a weight average molecular weight of 2700 was mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 3 wt%. In addition, the configuration of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system was the same as in Example 1-2. The mobile hydrogen carrier of Example 9 was subjected to a shear rate of 100 sec. -1 The viscosity at this time is 150 mPa·sec.

[0485] [Hydrogen filling into liquid hydrogen carrier]

[0486] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 9 is described. 12 mL of the mobile hydrogen carrier 10 of Example 9 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0487] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0488] [Power generation using liquid hydrogen carriers]

[0489] The power generation method according to Example 9 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0490] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 5.191Ah and the average discharge voltage is 0.80V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 9 was measured and the result was 10.2mL. That is, the discharge capacity density is equivalent to 509Ah / L. The Ah efficiency in Example 9 is 92.2%.

[0491] <Example 10>

[0492] In the preparation of the mobile hydrogen carrier of Example 10, the same method as in Example 1-2 was used except that sodium polyacrylate (PAANa) with a weight average molecular weight of 2700 was mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 7 wt%. In addition, the configuration of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system was the same as in Example 1-2. The mobile hydrogen carrier of Example 10 was subjected to a shear rate of 100 sec. -1 The viscosity at this time is 750 mPa·sec.

[0493] [Hydrogen filling into liquid hydrogen carrier]

[0494] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 10 is described. 12 mL of the mobile hydrogen carrier 10 of Example 10 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0495] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0496] [Power generation using liquid hydrogen carriers]

[0497] The power generation method according to Example 10 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0498] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 5.669Ah and the average discharge voltage is 0.73V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 10 is measured and the result is 10.3mL. That is, the discharge capacity density is equivalent to 550Ah / L. The Ah efficiency in Example 10 is 99.7%.

[0499] <Comparative Example 3>

[0500] The preparation of the flowable hydrogen carrier of Comparative Example 3 was the same as that of Example 1-2 except that sodium polyacrylate (PAANa) with a weight average molecular weight of 1200 was mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 5 wt%. In addition, the configuration of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system was the same as that of Example 1-2. The flowable hydrogen carrier of Comparative Example 3 was -1 The viscosity at this time is 10 mPa·sec.

[0501] [Hydrogen filling into liquid hydrogen carrier]

[0502] The method of filling hydrogen into the liquid hydrogen carrier involved in Comparative Example 3 is described. 12 mL of the liquid hydrogen carrier 10 of Comparative Example 3 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The liquid hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0503] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0504] [Power generation using liquid hydrogen carriers]

[0505] The power generation method according to Comparative Example 3 is described. Liquid hydrogen carriers filled with hydrogen are extracted 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. Liquid hydrogen carriers 14 filled with hydrogen are flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0506] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 0.597Ah and the average discharge voltage is 0.47V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Comparative Example 3 is measured and the result is 10.5mL. That is, the discharge capacity density is equivalent to 57Ah / L. The Ah efficiency in Comparative Example 3 is 10.3%.

[0507] <Comparative Example 4>

[0508] The preparation of the flowable hydrogen carrier of Comparative Example 4 was the same as that of Example 1-2 except that sodium polyacrylate (PAANa) with a weight average molecular weight of 1200 was mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 10 wt %. In addition, the configuration of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system was the same as that of Example 1-2. The flowable hydrogen carrier of Comparative Example 4 was -1 The viscosity at this time is 30 mPa·sec.

[0509] [Hydrogen filling into liquid hydrogen carrier]

[0510] The method of filling hydrogen into the liquid hydrogen carrier involved in Comparative Example 4 is described. 12 mL of the liquid hydrogen carrier 10 of Comparative Example 4 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The liquid hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0511] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0512] [Power generation using liquid hydrogen carriers]

[0513] The power generation method according to Comparative Example 4 is described. Liquid hydrogen carriers filled with hydrogen are extracted 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. Liquid hydrogen carriers 14 filled with hydrogen are flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0514] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was discharged at a current value of 0.4 V until the voltage reached 0.4 V. The set voltage was reached immediately after the discharge started, and power generation failed in Example 12.

[0515] <Example 11>

[0516] In the preparation of the mobile hydrogen carrier of Example 11, the same method as in Example 1-2 was used except that sodium polyacrylate (PAANa) with a weight average molecular weight of 20,000 was mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 1 wt%. In addition, the configuration of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system was the same as in Example 1-2. The mobile hydrogen carrier of Example 11 was subjected to a shear rate of 100 sec. -1 The viscosity at this time is 270 mPa·sec.

[0517] [Hydrogen filling into liquid hydrogen carrier]

[0518] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 11 is described. 12 mL of the mobile hydrogen carrier 10 of Example 11 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0519] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0520] [Power generation using liquid hydrogen carriers]

[0521] The power generation method according to Example 11 is described. The liquid hydrogen carrier filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0522] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value was discharged until the voltage reached 0.4V. The discharge capacity was 5.436Ah and the average discharge voltage was 0.78V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 11 was measured and the result was 10.7mL. That is, the discharge capacity density was equivalent to 538Ah / L. The Ah efficiency in Example 11 was 97.5%.

[0523] <Example 12>

[0524] In the preparation of the flowable hydrogen carrier of Example 12, the same method as in Example 1-2 was used except that hydroxyethyl cellulose (HEC) was mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 5 wt%. In addition, the configuration of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system was the same as in Example 1-2. The flowable hydrogen carrier of Example 12 was subjected to a shear rate of 100 sec. -1 The viscosity at this time is 330 mPa·sec.

[0525] [Hydrogen filling into liquid hydrogen carrier]

[0526] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 12 is described. 12 mL of the mobile hydrogen carrier 10 of Example 12 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0527] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0528] [Power generation using liquid hydrogen carriers]

[0529] The power generation method according to Example 12 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0530] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2The current value was discharged until the voltage reached 0.4V. The discharge capacity was 4.787Ah and the average discharge voltage was 0.71V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 12 was measured and the result was 10.3mL. That is, the discharge capacity density was equivalent to 465Ah / L. The Ah efficiency in Example 12 was 84.2%.

[0531] <Comparative Example 5>

[0532] The preparation of the flowable hydrogen carrier of Comparative Example 5 was the same as that of Example 1-2 except that sodium lignin sulfonate (LSANa) was mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 5 wt%. In addition, the configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2. The flowable hydrogen carrier of Comparative Example 5 was subjected to a shear rate of 100 sec. -1 The viscosity at this time is 80 mPa·sec.

[0533] [Hydrogen filling into liquid hydrogen carrier]

[0534] The method of filling hydrogen into the liquid hydrogen carrier involved in Comparative Example 5 is described. 12 mL of the liquid hydrogen carrier 10 of Comparative Example 5 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The liquid hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0535] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0536] [Power generation using liquid hydrogen carriers]

[0537] The power generation method according to Comparative Example 5 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0538] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 0.205Ah and the average discharge voltage is 0.41V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Comparative Example 5 is measured and the result is 10.6mL. That is, the discharge capacity density is equivalent to 19Ah / L. The Ah efficiency in Comparative Example 5 is 3.5%.

[0539] <Example 13>

[0540] In the preparation of the liquid hydrogen carrier of Example 13, the same method as in Example 1-2 was used except that carboxymethyl cellulose (CMC) was mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 5 wt%. In addition, the configuration of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system was the same as in Example 1-2. The liquid hydrogen carrier of Example 13 was subjected to a shear rate of 100 sec. -1 The viscosity at this time is 500 mPa·sec.

[0541] [Hydrogen filling into liquid hydrogen carrier]

[0542] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 13 is described. 12 mL of the mobile hydrogen carrier 10 of Example 13 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0543] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0544] [Power generation using liquid hydrogen carriers]

[0545] The power generation method according to Example 13 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0546] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value was discharged until the voltage reached 0.4V. The discharge capacity was 5.586Ah and the average discharge voltage was 0.73V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 13 was measured and the result was 10.4mL. That is, the discharge capacity density was equivalent to 537Ah / L. The Ah efficiency in Example 13 was 97.3%.

[0547] The hydrogen filling and power generation characteristics of Examples 1-2, Examples 9 to 13, and Comparative Examples 3 to 5 were compared when the type and amount of the additive added to the alkaline electrolyte 12 contained in the fluid hydrogen carrier 10 were changed. The results are shown in Table 3.

[0548] [Table 3]

[0549]

[0550] According to Table 3, the shear rate is 100 sec. -1 Examples 1-2 and Examples 9 to 13, in which the viscosity at the time is 100 mPa·sec or more, have high Ah efficiency and high capacity density. That is, in order to achieve high Ah efficiency and high capacity density, a shear rate of 100 sec -1 The viscosity of the fluid hydrogen carrier 10 at this time is 100 mPa·sec or more.

[0551] In addition, from the difference in weight average molecular weight (Mw) of the same PAANa in Table 3, when Mw is 1500 or more, high Ah efficiency and high capacity density are obtained. That is, in order to achieve high Ah efficiency and high capacity density, an additive with Mw of 1500 or more can be used.

[0552] In addition, from the difference in the types of additives in Table 3, PAANa, HEC, and CMC have high Ah efficiency and high capacity density. That is, in order to achieve high Ah efficiency and high capacity density, additives such as PAANa, HEC, and CMC can be used.

[0553] Hereinafter, examples and comparative examples concerning a method for suppressing the precipitation of a hydrogen storage alloy in a fluid hydrogen carrier will be described.

[0554] <Comparative Example 6>

[0555] The fluid hydrogen carrier 10 of Comparative Example 6 was prepared by the same method as in Example 1-2.

[0556] [Static sedimentation test]

[0557] Depending on the purpose of the mobile hydrogen carrier 10, the hydrogen absorbing alloy 11 may not be allowed to settle. That is, a technique for suppressing the settling of the mobile hydrogen carrier 10 is required. The following is a description of the method of the static sedimentation test for evaluating the sedimentation. The mobile hydrogen carrier 10 of Comparative Example 6 is injected into a transparent glass container, the upper part of the container is sealed with a sealing film to prevent drying, and the container is left to stand for 30 days. After standing, the presence or absence of a clear layer as a supernatant is confirmed. Fig.30 2 shows the state after the standing test of Comparative Example 6. A growth layer was confirmed in Comparative Example 6. That is, it was confirmed that sedimentation occurred after standing for 30 days.

[0558] The hydrogen filling and power generation characteristics of the fluid hydrogen carrier of Comparative Example 6 are the same as those of Example 1-2.

[0559] <Example 14>

[0560] As a method of suppressing sedimentation, thixotropy was imparted to the fluid hydrogen carrier 10. Carbon black was studied as a thixotropic agent as an additive imparting thixotropy. The fluid hydrogen carrier 10 of Example 14 was prepared in the same manner as in Comparative Example 6 except that 0.5 wt % of carbon black was added to the fluid hydrogen carrier 10.

[0561] [Static sedimentation test]

[0562] Fig.31 2 shows the state after the standing test of Example 14. No growth layer was confirmed in Example 14. That is, it was confirmed that no sedimentation occurred after standing for 30 days.

[0563] [Hydrogen filling into liquid hydrogen carrier]

[0564] The method of filling hydrogen into the mobile hydrogen carrier 10 according to Example 14 is described. 12 mL of the mobile hydrogen carrier 10 according to Example 14 is put into the negative electrode tank 410 of the hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0565] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0566] [Power generation using liquid hydrogen carriers]

[0567] The power generation method according to Example 14 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0568] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value was discharged until the voltage reached 0.4V. The discharge capacity was 4.395Ah and the average discharge voltage was 0.82V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 14 was measured and the result was 8.2mL. That is, the discharge capacity density was equivalent to 535Ah / L. The Ah efficiency in Example 14 was 97.1%.

[0569] By adding carbon black as a thixotropic agent, the power generation efficiency is equivalent to that of Comparative Example 6 in which no carbon black is added, but the average discharge voltage is increased. It is believed that the main reason is that the conductivity of carbon black itself is high, which improves the conductivity of the fluid hydrogen carrier 10. In other words, it is confirmed that carbon black as a thixotropic agent has two effects of sedimentation suppression and voltage increase, and is useful as a thixotropic agent.

[0570] The following is a heat treatment method for the mobile hydrogen carrier:

[0571] <Comparative Example 7>

[0572] The preparation of the fluid hydrogen carrier of Comparative Example 7 was the same as that of Example 1-2 except that the mixture was not heated after being stirred with a hybrid mixer. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2.

[0573] [Hydrogen filling into liquid hydrogen carrier]

[0574] The method of filling hydrogen into the liquid hydrogen carrier involved in Comparative Example 7 is described. 12 mL of the liquid hydrogen carrier 10 of Comparative Example 7 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The liquid hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0575] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0576] [Power generation using liquid hydrogen carriers]

[0577] The power generation method according to Comparative Example 7 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0578] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value was discharged until the voltage reached 0.4V. The discharge capacity was 1.802Ah and the average discharge voltage was 0.43V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Comparative Example 7 was measured and the result was 10.2mL. That is, the discharge capacity density was equivalent to 177Ah / L. The Ah efficiency in Comparative Example 7 was 32.0%.

[0579] <Example 15>

[0580] The preparation of the fluid hydrogen carrier of Example 15 was the same as that of Example 1-2 except that the mixture was heated at 80° C. for 2 hours after stirring with a mixer. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2.

[0581] [Hydrogen filling into liquid hydrogen carrier]

[0582] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 15 is described. 12 mL of the mobile hydrogen carrier 10 of Example 15 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0583] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0584] [Power generation using liquid hydrogen carriers]

[0585] The power generation method according to Example 15 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0586] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The discharge was carried out at a current value of 0.4V until the voltage reached 0.4V. The discharge capacity was 5.877Ah and the average discharge voltage was 0.76V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 15 was measured and the result was 10.7mL. That is, the discharge capacity density was equivalent to 549Ah / L. The Ah efficiency in Example 15 was 99.5%.

[0587] <Example 16>

[0588] The preparation of the fluid hydrogen carrier of Example 16 was the same as that of Example 1-2 except that the mixture was heated at 120° C. for 2 hours after stirring with a mixer. The configurations of the hydrogen filling device, hydrogen filling system, power generation device, and power generation system were the same as those of Example 1-2.

[0589] [Hydrogen filling into liquid hydrogen carrier]

[0590] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 16 is described. 12 mL of the mobile hydrogen carrier 10 of Example 16 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0591] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0592] [Power generation using liquid hydrogen carriers]

[0593] The power generation method according to Example 16 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0594] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 5.669Ah and the average discharge voltage is 0.79V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 16 was measured and the result was 10.3mL. That is, the discharge capacity density is equivalent to 550Ah / L. The Ah efficiency in Example 16 is 99.7%.

[0595] The hydrogen filling and power generation characteristics when the heating temperature of the fluid hydrogen carrier 10 was changed were compared with Examples 1-2, Examples 15 to 16, and Comparative Example 7. The results are shown in Table 4.

[0596] [Table 4]

[0597]

[0598] According to Table 4, Examples 1-2 and Examples 15 to 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, the fluid hydrogen carrier 10 heated at 80° C. or higher can be used.

[0599] The following is a method for pulverizing hydrogen absorbing alloys.

[0600] <Example 17>

[0601] Sodium polyacrylate (PAANa) with a weight average molecular weight of 2700 is mixed with a 6 mol / L potassium hydroxide aqueous solution in a manner of 5 wt%, and stirred overnight to dissolve the PAANa. The solution is mixed with 20 volume % of a hydrogen absorbing alloy 11 with a median diameter of 500 μm or more, and pulverized using a ball mill in the atmosphere to prepare a slurry with a median diameter adjusted to 15 μm. The slurry is heated at 100°C for 2 hours to prepare a fluid hydrogen carrier 10. The viscosity of the fluid hydrogen carrier 10 of Example 17 is measured using a rheometer manufactured by Anton Paar. As a result, the shear rate is 100sec. -1 The viscosity at 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 of Example 1-2.

[0602] [Hydrogen filling into liquid hydrogen carrier]

[0603] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 17 is described. 12 mL of the mobile hydrogen carrier 10 of Example 17 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0604] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0605] [Power generation using liquid hydrogen carriers]

[0606] The power generation method according to Example 17 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0607] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 5.889Ah and the average discharge voltage is 0.78V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 17 was measured and the result was 10.7mL. That is, the discharge capacity density is equivalent to 550Ah / L. The Ah efficiency in Example 17 is 99.7%.

[0608] In Examples 1-2 and 17, the conditions for pulverizing the hydrogen storage alloy in the fluid hydrogen carrier 10 are different. The hydrogen filling and power generation characteristics of these are compared. The results are shown in Table 5.

[0609] [Table 5]

[0610]

[0611] According to Table 5, no difference was observed in the power generation characteristics between Example 17 in which the alloy was pulverized in the atmosphere while being mixed with the alkaline electrolyte and Example 1-2 in which the alloy was pulverized in an inert atmosphere. That is, it was confirmed that the pulverization can be performed simply without an inert atmosphere by mixing the alkaline electrolyte and the hydrogen storage alloy.

[0612] The following is implemented based on the structural differences between the hydrogen filling device and the power generation device.

[0613] <Example 18>

[0614] The mobile hydrogen carrier used in Example 18 is the same as that in Example 1-2. Fig.14 and Fig.16 The other parts except the second hydrogen filling device 100B and the second power generation device 200B are the same as those of the embodiment.

[0615] [Production of Hydrogen Filling Device]

[0616] Production Fig.14 The second hydrogen filling device 100B shown in FIG. Nickel-plated stainless steel is used as the positive electrode current collector 103, a nickel porous electrode with nickel sulfide formed on the surface is used as the oxygen generating electrode 105, a 100-mesh nickel metal mesh is used as the porous positive electrode current collector 112, nickel-plated stainless steel is used as the negative electrode current collector 21, a 60-mesh nickel metal mesh is used as the porous negative electrode current collector 111, an anion exchange membrane is used as the ion permeable membrane 106, and butyl rubber is used as the seal 107.

[0617] [Production of power generation device]

[0618] Production Fig.15 The second power generation device 200B shown in FIG. Nickel-plated stainless steel is used as the positive electrode current collector 130, hydrophobic carbon paper coated with platinum-supported carbon on the surface is used as the oxygen reduction electrode 201, a 100-mesh nickel metal mesh is used as the porous positive electrode current collector 112, nickel-plated stainless steel is used as the negative electrode current collector 21, a 60-mesh nickel metal mesh is used as the porous negative electrode current collector 111, an anion exchange membrane is used as the ion permeable membrane 106, and butyl rubber is used as the seal 107.

[0619] [Hydrogen filling into liquid hydrogen carrier]

[0620] The method of filling hydrogen into the mobile hydrogen carrier involved in Example 18 is described. 12 mL of the mobile hydrogen carrier 10 of Example 18 is put into the negative electrode tank 410 of the above-mentioned hydrogen filling system, and 10 mL of a 6 mol / L potassium hydroxide aqueous solution is put into the positive electrode tank 430. The mobile hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the 6 mol / L potassium hydroxide aqueous solution is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0621] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0622] [Power generation using liquid hydrogen carriers]

[0623] The power generation method according to Example 18 is described. The liquid hydrogen carrier 14 filled with hydrogen is extracted from the negative electrode tank 410 of the hydrogen filling system and is put into the negative electrode tank 410 of the power generation device 200A. The liquid hydrogen carrier 14 filled with hydrogen is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0624] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 5.669Ah and the average discharge voltage is 0.80V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 18 is measured and the result is 10.3mL. That is, the discharge capacity density is equivalent to 550Ah / L. The Ah efficiency in Example 18 is 99.6%.

[0625] <Example 19>

[0626] The liquid hydrogen carrier used in Example 19 is the same as that in Example 1-2. In Example 19, a liquid hydrogen carrier capable of performing hydrogen filling and power generation with one device is used. Fig.16 A third hydrogen filling and power generation device is shown.

[0627] [Manufacturing of hydrogen filling and power generation equipment]

[0628] The method for manufacturing the hydrogen filling and power generation device according to Example 19 is described below. Fig.16 The third hydrogen filling and power generation device 300C shown in FIG. Nickel-plated stainless steel is used as the positive electrode current collector 103, a nickel porous body coated with pyrochlore-type bismuth-iridium oxide on the surface is used as the binary electrode 301, a 100-mesh nickel metal mesh is used as the porous positive electrode current collector 112, nickel-plated stainless steel is used as the negative electrode current collector 21, a 60-mesh nickel metal mesh is used as the porous negative electrode current collector 111, an anion exchange membrane is used as the ion permeable membrane 106, and butyl rubber is used as the seal 107.

[0629] [Production of hydrogen filling and power generation system]

[0630] The method for manufacturing the hydrogen filling and power generation system according to Example 19 is described below. Fig. 22The hydrogen filling system is shown in FIG. 4. A polypropylene can is used as the negative electrode can 410, a tube pump is used as the negative electrode pressurizing / depressurizing device 420, a tube pump is used as the positive electrode pressurizing / depressurizing device 440, and a device flow path 460 is used. In Example 19, since the cells are not stacked, no inter-device flow path is used. In addition, in Example 19, since air is allowed to flow, the positive electrode can 430 is not used.

[0631] [Hydrogen filling into liquid hydrogen carrier]

[0632] The method of filling the liquid hydrogen carrier with hydrogen according to Example 19 is described. 12 mL of the liquid hydrogen carrier 10 is put into the negative electrode tank 410 of the hydrogen filling and power generation system 400A. The liquid hydrogen carrier 10 is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0633] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0634] [Power generation using liquid hydrogen carriers]

[0635] The power generation method according to Example 19 is described below. 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 a charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the relative ion permeable membrane 106 is 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 6.604Ah and the average discharge voltage is 0.70V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 19 was measured and the result was 12mL. This is because hydrogen filling / power generation can be performed with one device, so there is no need to extract and transfer the mobile hydrogen carrier. That is, the discharge capacity density is equivalent to 550Ah / L. The Ah efficiency in Example 19 is 99.8%.

[0636] <Example 20>

[0637] The mobile hydrogen carrier used in Example 20 is the same as that in Example 1-2. In Example 20, a device capable of performing hydrogen filling and power generation is used. Fig.17A fourth hydrogen filling and power generation device is shown.

[0638] [Manufacturing of hydrogen filling and power generation equipment]

[0639] The method for manufacturing the hydrogen filling and power generation device according to Example 20 is described below. Fig.17 The fourth hydrogen filling and power generation device 300D shown in FIG. Nickel-plated stainless steel is used as the positive electrode current collector 103, a 100-mesh nickel metal mesh is used as the porous positive electrode current collector 112, nickel-plated stainless steel is used as the negative electrode current collector 21, a 60-mesh nickel metal mesh is used as the porous negative electrode current collector 111, an anion exchange membrane is used as the ion permeable membrane 106, and butyl rubber is used as the seal 107.

[0640] [Production of hydrogen filling and power generation system]

[0641] The method for manufacturing the hydrogen filling and power generation system according to Example 20 is described below. Fig. 22 The hydrogen filling system is shown. A polypropylene tank is used as the negative electrode tank 410, a polypropylene tank is used as the positive electrode tank 430, a tube pump is used as the negative electrode pressurizing / depressurizing device 420, a tube pump is used as the positive electrode pressurizing / depressurizing device 440, and a device flow path 460 is used. In Example 20, the cells were not stacked, so no flow path between devices was used.

[0642] [Hydrogen filling into liquid hydrogen carrier]

[0643] The method of filling hydrogen into the liquid hydrogen carrier involved in Example 20 is described. 12 mL of the liquid hydrogen carrier 10 is put into the negative electrode tank 410 of the hydrogen filling and power generation system 400A, and 20 mL of the slurry containing nickel hydroxide is put into the positive electrode tank 430. The liquid hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the slurry containing nickel hydroxide is made to flow at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0644] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since 12 mL of the liquid hydrogen carrier was put in, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of the capacity density of the liquid hydrogen carrier.

[0645] [Power generation using liquid hydrogen carriers]

[0646] The power generation method according to Example 20 is described below. 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 a charging and discharging device manufactured by Hokuto Denko Co., Ltd., respectively, and the area of ​​the ion permeable membrane 106 is 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 4.789Ah, and the average discharge voltage is 1.2V. This is because the redox potential of nickel hydroxide as the positive electrode is high, so a higher voltage than that of Example 1-2 can be obtained. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 20 was measured, and the result was 12mL. This is because hydrogen filling / power generation can be performed with one device, so there is no need to extract and transfer the mobile hydrogen carrier. That is, the discharge capacity density is equivalent to 399Ah / L. The Ah efficiency in Example 20 is 72.3%. As the reason for the low Ah efficiency, it is believed that the Ah efficiency of the nickel hydroxide slurry is low, so hydrogen cannot be fully detached from the hydrogen absorbing alloy.

[0647] The results are shown in Table 6 for Examples 1-2 and 18 to 20, in which the hydrogen filling and power generation device structures were different.

[0648] [Table 6]

[0649]

[0650] According to Table 6, in Example 18 using a porous current collector, the voltage is higher than that of Example 1-2 in which a porous current collector is not used. It is believed that this is because the positive electrode and the negative electrode collect electricity in a closer state, so the resistance of the device is reduced. In addition, in the structure of Example 19 in which hydrogen filling and power generation can be performed with one battery cell, almost the same power generation characteristics as Example 18 in which hydrogen filling and power generation are performed separately with different devices are obtained. Among them, the discharge voltage is slightly low. It is believed that this is because the oxygen reduction overvoltage of the binary catalyst is high. In addition, in Example 20, which is not a structure of an air battery using oxygen, but a slurry containing nickel hydroxide is used in the positive electrode, when compared with other embodiments, although the Ah efficiency is low, a high voltage can be obtained. It is advantageous in terms of the product of the voltage V and the capacity Ah, that is, the amount of energy Wh. According to the above results, it is confirmed that the hydrogen filling device and the power generation device implemented in each embodiment are effective in hydrogen filling and power generation of the mobile hydrogen carrier of the present invention.

[0651] Hereinafter, embodiments in which the short-circuit suppression structure of the hydrogen filling device and the power generation device connected in series is different will be described.

[0652] <Comparative Example 8>

[0653] Comparative Example 8 is a bipolar structure in which a hydrogen filling device and a power generation device are connected in series.

[0654] [Preparation of Liquid Hydrogen Carrier]

[0655] The fluid hydrogen carrier used in Comparative Example 8 is the same as that in Example 1-2.

[0656] [Manufacturing of hydrogen filling and power generation equipment]

[0657] The method for manufacturing the hydrogen filling and power generation device according to Comparative Example 8 is described below. Fig. 20 The fifth hydrogen filling and power generation device 300E shown in FIG. Nickel-plated stainless steel is used as the positive electrode current collector 103, a nickel porous body coated with pyrochlore-type bismuth-iridium oxide on the surface is used as the binary electrode 301, a 100-mesh nickel metal mesh is used as the porous positive electrode current collector 112, nickel-plated stainless steel is used as the negative electrode current collector 21, a 60-mesh nickel metal mesh is used as the porous negative electrode current collector 111, an anion exchange membrane is used as the ion permeable membrane 106, butyl rubber is used as the seal 107, and nickel-plated stainless steel is used as the bipolar plate 121.

[0658] [Production of hydrogen filling and power generation system]

[0659] The method for manufacturing the hydrogen filling and power generation system according to Comparative Example 8 is described below. Fig. 22 The hydrogen filling system is shown in FIG. 4. A polypropylene can is used as the negative electrode can 410, a tube pump is used as the negative electrode pressurizing / depressurizing device 420, a tube pump is used as the positive electrode pressurizing / depressurizing device 440, and a device flow path 460 is used. Polypropylene tube, used as flow path 450 between devices In Comparative Example 8, since air is allowed to flow, the positive electrode tank 430 is not used. In Comparative Example 8, Fig. 22 The length of the short-circuit current path indicated by the dotted line in FIG. 1 (the path of the continuous inter-device flow path 450 and the device flow path 460 between the adjacent hydrogen filling and power generation devices sandwiching the bipolar plate 121) is set to 25 cm.

[0660] [Hydrogen filling into liquid hydrogen carrier]

[0661] The method of filling hydrogen into the liquid hydrogen carrier involved in Comparative Example 8 is described. 12 mL of the liquid hydrogen carrier 10 is put into the negative electrode tank 410 of the hydrogen filling and power generation system 400A. The liquid hydrogen carrier 10 is flowed at a flow rate of 5 mL / min by the negative electrode pressurization / depressurization device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurization / depressurization device 440.

[0662] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery is charged with a current value of 10000 until the capacity reaches 3.312Ah. It should be noted that since the amount of mobile hydrogen carrier put in is 12mL, the capacity of 3.312Ah is equivalent to 276Ah / L in terms of capacity density. Since two devices are connected in series, the voltage is doubled, and the amount of energy is the same as the previous embodiment.

[0663] [Power generation using liquid hydrogen carriers]

[0664] The power generation method according to Comparative Example 8 is described below. 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 a charging and discharging device manufactured by Hokuto Denko Co., Ltd., respectively, and the area of ​​the ion permeable membrane 106 is 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 1.411Ah, and the average discharge voltage is 0.66V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Comparative Example 8 was measured and the result was 12mL. This is because hydrogen filling / power generation can be performed with one device, so there is no need to extract and transfer the mobile hydrogen carrier. That is, the discharge capacity density is equivalent to 118Ah / L. The Ah efficiency in Comparative Example 8 is 42.6%. That is, the short circuit could not be suppressed, and in the structure of Comparative Example 8, the hydrogen filling was not fully carried out.

[0665] <Example 21>

[0666] Example 21 is a bipolar structure in which a hydrogen filling device and a power generation device are connected in series, and in order to suppress short circuit, the short circuit path is extended.

[0667] [Preparation of Liquid Hydrogen Carrier]

[0668] The mobile hydrogen carrier used in Example 21 is the same as that in Example 1-2.

[0669] [Manufacturing of hydrogen filling and power generation equipment]

[0670] The method for manufacturing the hydrogen filling and power generation device involved in Example 21 is the same as that of Comparative Example 8.

[0671] [Production of hydrogen filling and power generation system]

[0672] In the method for manufacturing the hydrogen filling and power generation system according to Example 21, except Fig. 22The same as 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 the adjacent hydrogen filling and power generation devices sandwiching the bipolar plate 121) indicated by the dotted line is set to 50 cm.

[0673] [Hydrogen filling into liquid hydrogen carrier]

[0674] The method of filling hydrogen into the liquid hydrogen carrier involved in Example 21 is described. 12 mL of the liquid hydrogen carrier 10 is put into the negative electrode tank 410 of the hydrogen filling and power generation system 400A. The liquid hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min using the negative electrode pressurization / depressurization device 420, and the air is made to flow at a flow rate of 5 mL / min using the positive electrode pressurization / depressurization device 440.

[0675] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery is charged with a current value of 10000 until the capacity reaches 3.312Ah. It should be noted that since the amount of mobile hydrogen carrier put in is 12mL, the capacity of 3.312Ah is equivalent to 276Ah / L in terms of capacity density. Since two devices are connected in series, the voltage is doubled, and the amount of energy is the same as the previous embodiment.

[0676] [Power generation using liquid hydrogen carriers]

[0677] The power generation method according to Example 21 is described below. 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 a charging and discharging device manufactured by Hokuto Denko Co., Ltd., respectively, and the area of ​​the relative ion permeable membrane 106 is 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 3.246Ah, and the average discharge voltage is 1.53V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 21 was measured and the result was 12mL. This is because hydrogen filling / power generation can be performed with one device, so there is no need to extract and transfer the mobile hydrogen carrier. That is, the discharge capacity density is equivalent to 270Ah / L. The Ah efficiency in the embodiment is 97.8%. Compared with Example 19 without stacking, about twice the voltage can be obtained in Example 21, which is a high Ah efficiency, so it is believed that the short-circuit current can be fully suppressed by the structure of Example 21.

[0678] <Example 22>

[0679] Example 22 is a bipolar structure in which a hydrogen filling device and a power generation device are connected in series, and a liquid shutoff device 461 is provided to suppress short circuit.

[0680] [Preparation of Liquid Hydrogen Carrier]

[0681] The mobile hydrogen carrier used in Example 22 is the same as that in Example 1-2.

[0682] [Manufacturing of hydrogen filling and power generation equipment]

[0683] The method for manufacturing the hydrogen filling and power generation device involved in Example 22 is the same as that of Comparative Example 8.

[0684] [Production of hydrogen filling and power generation system]

[0685] The method for manufacturing the hydrogen filling and power generation system according to Example 22 is described below. Fig.23 The second hydrogen filling and power generation system 400B is shown. A polypropylene can is used as the negative electrode tank 410, a tube pump is used as the negative electrode pressurizing / depressurizing device 420, a tube pump is used as the positive electrode pressurizing / depressurizing device 440, and a device flow path 460 is used. Polypropylene tube, used as flow path 450 between devices A polypropylene tube is used as a drip tube as the liquid cutoff device 151. In addition, in Example 22, since air is allowed to flow, the positive electrode tank 430 is not used. In addition, in Example 22, Fig. 22 The length of the short-circuit current path indicated by the dotted line in FIG. 1 (the path of the continuous inter-device flow path 450 and the device flow path 460 between the adjacent hydrogen filling and power generation devices sandwiching the bipolar plate 121) is set to 5 cm.

[0686] [Hydrogen filling into liquid hydrogen carrier]

[0687] The hydrogen filling method for the liquid hydrogen carrier involved in Example 22 is described. 12 mL of the liquid hydrogen carrier 10 is put into the negative electrode tank 410 of the second hydrogen filling and power generation system 400B. The liquid hydrogen carrier 10 is made to flow at a flow rate of 5 mL / min using the negative electrode pressurization / depressurization device 420, and the air is made to flow at a flow rate of 5 mL / min using the positive electrode pressurization / depressurization device 440.

[0688] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2The battery is charged with a current value of 2.500 until the capacity reaches 3.312Ah. It should be noted that since the amount of mobile hydrogen carrier put in is 12mL, the capacity of 3.312Ah is equivalent to 276Ah / L in terms of capacity density. Since two devices are connected in series, the voltage is doubled, and the energy (Wh) represented by capacity density × voltage is the same as in the previous embodiment.

[0689] [Power generation using liquid hydrogen carriers]

[0690] The power generation method according to Example 22 is described below. 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 a charging and discharging device manufactured by Hokuto Denko Co., Ltd., respectively, and the area of ​​the relative ion permeable membrane 106 is 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 3.213Ah, and the average discharge voltage is 1.54V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 22 was measured and the result was 12mL. This is because hydrogen filling / power generation can be performed with one device, so there is no need to extract and transfer the mobile hydrogen carrier. That is, the discharge capacity density is equivalent to 267Ah / L. The Ah efficiency in Example 22 is 96.7%. Compared with Example 19 without stacking, about twice the voltage can be obtained in Example 22, which is a high Ah efficiency. Therefore, it is believed that through the construction of Example 22, the short-circuit current can be fully suppressed even in the case of a short short-circuit path.

[0691] <Example 23>

[0692] Example 23 is 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 circuit.

[0693] [Preparation of Liquid Hydrogen Carrier]

[0694] The mobile hydrogen carrier used in Example 23 is the same as that in Example 1-2.

[0695] [Manufacturing of hydrogen filling and power generation equipment]

[0696] The method for manufacturing the hydrogen filling and power generation device involved in Example 23 is the same as that of Comparative Example 8.

[0697] [Production of hydrogen filling and power generation system]

[0698] The method for manufacturing the hydrogen filling and power generation system according to Example 23 is described below. Fig.24The third hydrogen filling and power generation system 400C is shown. A polypropylene tank is used as the negative electrode tank 410, a tube pump is used as the negative electrode pressurizing / depressurizing device 420, a tube pump is used as the positive electrode pressurizing / depressurizing device 440, and a device flow path 460 is used. Polypropylene tube, used as flow path 450 between devices A polypropylene tube is used, and an electromagnetic valve is used as the valve 462 that can be opened and closed. In Example 23, since air is allowed to flow, the positive electrode tank 430 is not used. In Example 23, Fig. 22 The length of the short-circuit current path indicated by the dotted line in FIG. 1 (the path of the continuous inter-device flow path 450 and the device flow path 460 between the adjacent hydrogen filling and power generation devices sandwiching the bipolar plate 121) is set to 5 cm.

[0699] [Hydrogen filling into liquid hydrogen carrier]

[0700] The hydrogen filling method of the liquid hydrogen carrier involved in Example 23 is described. 12mL of the liquid hydrogen carrier 10 is put into the negative electrode tank 410 of the third hydrogen filling and power generation system 400C. The liquid hydrogen carrier 10 is made to flow at a flow rate of 5mL / min using the negative electrode pressurization / decompression device 420. As a valve 462 that can be opened and closed, as for the aforementioned solenoid valve, at the same time, among the devices connected in series, the valve connected to one device is opened. At this time, the other valves are in a closed state. After 1 second, after closing the valve connected to one device, the valve connected to the adjacent device is opened for 1 second, and the operation is repeated. In addition, the positive electrode pressurization / decompression device 440 is used to make air flow at a flow rate of 5mL / min.

[0701] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery is charged with a current value of 10000 until the capacity reaches 3.312Ah. It should be noted that since the amount of mobile hydrogen carrier put in is 12mL, the capacity of 3.312Ah is equivalent to 276Ah / L in terms of capacity density. Since it is a two-series connected device, the voltage is doubled, and the amount of energy (Wh) represented by capacity density × voltage is the same as the previous embodiment.

[0702] [Power generation using liquid hydrogen carriers]

[0703] The power generation method according to Example 23 is described below. 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 a charging and discharging device manufactured by Hokuto Denko Co., Ltd., respectively, and the area of ​​the relative ion permeable membrane 106 is 30 mA / cm 2The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 3.252Ah, and the average discharge voltage is 1.54V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 23 was measured and the result was 12mL. This is because hydrogen filling / power generation can be performed with one device, so there is no need to extract and transfer the mobile hydrogen carrier. That is, the discharge capacity density is equivalent to 271Ah / L. The Ah efficiency in Example 23 is 98.1%. Compared with Example 19 without stacking, about twice the voltage can be obtained in Example 23, which is a high Ah efficiency. Therefore, it is believed that through the construction of Example 23, the short-circuit current can be fully suppressed even in the case of a short short-circuit path.

[0704] As described above, in Comparative Example 8 and Examples 21 to 23, the short circuit suppression structures of the hydrogen filling devices and power generation devices connected in series are different. The effects are shown in Table 7.

[0705] [Table 7]

[0706]

[0707] According to Table 7, in Comparative Example 8 where the short-circuit path distance is 25 cm, the voltage is not doubled despite the cells being connected in series. In addition, the Ah efficiency is also low. That is, the short circuit cannot be suppressed. On the other hand, in Example 21 where the short-circuit path distance is 50 cm, Example 22 using the liquid shutoff device 461, and Example 23 using the openable and closable valve 462, the voltage is doubled, which is a high Ah efficiency. That is, it is confirmed that Examples 21 to 23 of the present invention are effective as short-circuit suppression means for hydrogen filling devices and power generation devices connected in series for filling the liquid hydrogen carrier of the present invention and for power generation using the liquid hydrogen carrier.

[0708] Other embodiments of the present invention are described below.

[0709] <Example 24>

[0710] As for the liquid hydrogen carrier of the present invention, the liquid hydrogen carrier filled with hydrogen can also be extracted from the hydrogen filling device and transported. When extracting, in order to extract at a higher hydrogen filling depth, it is preferred that the liquid hydrogen carrier that has not been filled with hydrogen and the liquid hydrogen carrier that has been filled with hydrogen are not mixed. In Example 24, the negative electrode tank storing the liquid hydrogen carrier 14 filled with hydrogen and the liquid hydrogen carrier 10 before hydrogen filling can be stored separately by using the second negative electrode tank 470 and the second positive electrode tank 480.

[0711] [Preparation of Liquid Hydrogen Carrier]

[0712] The mobile hydrogen carrier used in Example 24 is the same as that in Example 1-2.

[0713] [Manufacturing of hydrogen filling and power generation equipment]

[0714] The method for manufacturing the hydrogen filling and power generation device involved in Example 24 is the same as that of Comparative Example 8.

[0715] [Production of hydrogen filling and power generation system]

[0716] The method for manufacturing the hydrogen filling and power generation system according to Example 24 is described below. Fig.25 The fourth hydrogen filling and power generation system 400D is shown. A polypropylene can is used as the negative electrode tank 410, a polypropylene can is used as the second negative electrode tank 171, a tube pump is used as the negative electrode pressurizing / depressurizing device 420, a tube pump is used as the positive electrode pressurizing / depressurizing device 440, and a device flow path 460 is used. Polypropylene tube, used as flow path 450 between devices In Example 24, since air is allowed to flow, the positive electrode tank 430 and the second positive electrode tank 172 are not used. In Example 24, Fig. 22 The length of the short-circuit current path indicated by the dotted line in FIG. 1 (the path of the continuous inter-device flow path 450 and the device flow path 460 between the adjacent hydrogen filling and power generation devices sandwiching the bipolar plate 121) is set to 25 cm.

[0717] [Hydrogen filling into liquid hydrogen carrier]

[0718] The hydrogen filling method for the liquid hydrogen carrier involved in Example 24 is described. 12 mL of the liquid hydrogen carrier 10 is put into the negative electrode tank 410 of the fourth hydrogen filling and power generation system 400D. The liquid hydrogen carrier 10 is made to flow at a flow rate of 1 mL / min using the negative electrode pressurization / depressurization device 420, and the air is made to flow at a flow rate of 5 mL / min using the positive electrode pressurization / depressurization device 440.

[0719] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2 The battery is charged with a current value of 1.656 Ah until it reaches a capacity of 1.656 Ah. This is equivalent to 50% of the capacity when it is fully filled with hydrogen.

[0720] It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 1.656 Ah was equivalent to 138 Ah / L in terms of capacity density. Since two devices were connected in series, the voltage was doubled.

[0721] [Power generation using liquid hydrogen carriers]

[0722] The power generation method according to Example 24 is described below. Liquid hydrogen carriers filled with hydrogen in the second anode tank 171 of the fourth hydrogen filling and power generation system 400D are extracted and put into the anode tank 410 .

[0723] The positive current collector 103 and the negative current collector 101 of the device were connected to the positive and negative electrodes of the charging and discharging device manufactured by Hokuto Electric, respectively, and the area of ​​the relative ion permeable membrane 106 was 30 mA / cm 2 The discharge was carried out at a current value of 0.4V until the voltage reached 0.4V. The discharge capacity was 1.431Ah and the average discharge voltage was 1.53V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 24 was measured and the result was 5mL. That is, the discharge capacity density was equivalent to 270Ah / L. The Ah efficiency in Example 24 was 97.8%.

[0724] That is, although 50% of the hydrogen was filled into the hydrogen filling device, only the liquid hydrogen carriers that were completely filled with hydrogen were stored in the second negative electrode tank, so the liquid hydrogen carriers extracted therefrom were in a state of 100% hydrogen filling, confirming that Example 24 was useful.

[0725] Other embodiments of the present invention are described below.

[0726] <Example 25>

[0727] Example 25 is the same hydrogen filling and power generation system as Example 19 except that liquid paraffin is added to the negative electrode tank. Liquid paraffin has a lower specific gravity than the liquid hydrogen carrier, so liquid paraffin is added to the upper layer of the tank in the negative electrode tank for the purpose of suppressing the evaporation of water in the liquid hydrogen carrier.

[0728] [Hydrogen filling into liquid hydrogen carrier]

[0729] The method of filling the liquid hydrogen carrier with hydrogen according to Example 25 is described. 12 mL of the liquid hydrogen carrier 10 is put into the negative electrode tank 410 of the hydrogen filling and power generation system 400A. The liquid hydrogen carrier 10 is flowed at a flow rate of 5 mL / min by the negative electrode pressurizing / depressurizing device 420, and the air is flowed at a flow rate of 5 mL / min by the positive electrode pressurizing / depressurizing device 440.

[0730] 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 charging and discharging device manufactured by Hokuto Denko, respectively, and the area of ​​the ion permeable membrane 106 was 30 mA / cm 2The battery was charged with a current value of 1.500 until the capacity reached 6.624 Ah. It should be noted that since the amount of liquid hydrogen carrier introduced was 12 mL, the capacity of 6.624 Ah was equivalent to 552 Ah / L in terms of capacity density.

[0731] [Power generation using liquid hydrogen carriers]

[0732] The power generation method according to Example 25 is described below. 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 a charging and discharging device manufactured by Hokuto Denko Co., Ltd., respectively, and the area of ​​the relative ion permeable membrane 106 is 30 mA / cm 2 The current value is discharged until the voltage reaches 0.4V. The discharge capacity is 6.604Ah and the average discharge voltage is 0.70V. The volume of the mobile hydrogen carrier 10 put into the power generation device of Example 25 was measured and the result was 12mL. This is because hydrogen filling / power generation can be performed with one device, so there is no need to extract and transfer the mobile hydrogen carrier. That is, the discharge capacity density is equivalent to 550Ah / L. The Ah efficiency in Example 25 is 99.8%.

[0733] [Determination of solid content after hydrogen filling and power generation cycle]

[0734] The above-mentioned hydrogen filling and power generation operation was repeated 50 times. 1.0 g of the liquid 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 in Example 25 was 75%.

[0735] <Comparative Example 9>

[0736] Comparative Example 9 is the same hydrogen filling and power generation system as Example 24, except that liquid paraffin is not added to the negative electrode tank.

[0737] [Determination of solid content after hydrogen filling and power generation cycle]

[0738] The above-mentioned hydrogen filling and power generation operation was repeated 50 times. 1.0 g of the liquid 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 in Comparative Example 9 was 79%.

[0739] According to the above results, by adding liquid paraffin, which is a hydrophobic liquid with a lower specific gravity than the liquid hydrogen carrier of the present invention, into the negative electrode can, the increase in the solid content of the liquid hydrogen carrier can be suppressed. In other words, it can be seen that the volatilization of water in the liquid hydrogen carrier can be suppressed by the configuration of each example.

[0740] It should be noted that the embodiments of the present invention are as follows, for example.

[0741] <1> A fluid hydrogen carrier comprising a hydrogen absorbing alloy and an alkaline electrolyte.

[0742] <2> The fluid hydrogen carrier according to <1>, wherein the hydrogen storage alloy is contained in an amount of 15 volume % or more of the entire fluid hydrogen carrier.

[0743] <3> The fluid hydrogen carrier according to <1> or <2>, wherein the median diameter of the hydrogen storage alloy is 50 μm or less.

[0744] <4> The fluid hydrogen carrier according to any one of <1> to <3>, which has a shear rate of 100 sec -1 The viscosity at this time is 100 mPa·sec or more.

[0745] <5> The fluid hydrogen carrier according to any one of <1> to <4>, comprising a water-soluble organic polymer having a weight average molecular weight of 1500 or more.

[0746] <6> The fluid hydrogen carrier according to <5>, wherein the water-soluble organic polymer is a polyacrylate.

[0747] <7> The fluid hydrogen carrier according to any one of <1> to <6>, comprising a thixotropic agent.

[0748] <8> The fluid hydrogen carrier according to any one of <1> to <7>, comprising carbon black having a median diameter of 1 μm or less.

[0749] <9> The method for producing a fluid hydrogen carrier according to any one of <1> to <8>, comprising the step of heating at 80° C. or higher.

[0750] <10> A method for producing a fluid hydrogen carrier using the fluid hydrogen carrier according to any one of <1> to <8>, comprising the step of pulverizing the hydrogen storage alloy in a state where the hydrogen storage alloy and an alkaline solution are mixed.

[0751] <11> A charge-discharge cell comprising a negative electrode current collector, a positive electrode current collector, an oxygen electrode catalyst and an ion permeable membrane,

[0752] A portion of the negative electrode current collector is electrically connected to the mobile hydrogen carrier described in any one of <1> to <8>,

[0753] A portion of the positive electrode current collector and the oxygen electrode catalyst,

[0754] A portion of the oxygen electrode catalyst is ionically connected to the ion permeable membrane.

[0755] The ion permeable membrane is arranged to separate the negative electrode current collector from the positive electrode current collector.

[0756] A portion of the mobile hydrogen carrier is ionically connected to the ion-permeable membrane.

[0757] <12> A secondary battery comprising the charge-discharge cell according to <11>.

[0758] <13> A hydrogen filling device comprising a negative electrode current collector, a negative electrode void capable of being filled with the fluid hydrogen carrier described in any one of <1> to <8>, a positive electrode current collector, a positive electrode void, an oxygen generating electrode, and an ion permeable membrane,

[0759] The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane.

[0760] The positive electrode gap is connected to the oxygen generating catalyst.

[0761] A portion of the positive electrode current collector is electrically connected to the oxygen generating catalyst.

[0762] A portion of the oxygen generating catalyst is contacted with an alkaline aqueous solution,

[0763] A portion of the oxygen generating catalyst is ionically connected to the ion permeable membrane.

[0764] The ion permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

[0765] <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 liquid hydrogen carriers are filled or flowed into a part or the entirety of the negative electrode voids, thereby filling the liquid hydrogen carriers with hydrogen.

[0766] <15> The hydrogen filling device as described in <13> or <14>, wherein hydrogen is filled into the liquid hydrogen carrier by applying a voltage between the negative electrode current collector and the positive electrode current collector in a state where an alkaline electrolyte is filled or flowed into a part or the whole of the positive electrode gap.

[0767] <16> A power generation device comprising a negative electrode current collector, a negative electrode void that can be filled with the fluid hydrogen carrier according to any one of <1> to <8> filled with hydrogen, a positive electrode current collector, a positive electrode void, an oxygen reduction catalyst, and an ion permeable membrane,

[0768] The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane.

[0769] The positive electrode gap is in contact with the oxygen reduction catalyst.

[0770] A portion of the positive electrode current collector is electrically connected to the oxygen reduction catalyst.

[0771] A portion of the oxygen reduction catalyst is ionically connected to the ion permeable membrane,

[0772] A portion of the oxygen reduction catalyst is contacted with air,

[0773] The ion permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

[0774] <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 entirety of the negative electrode void is filled with or flows with a fluid hydrogen carrier.

[0775] <18> The power generation device according to <16> or <17>, wherein power generation is performed by connecting a load between the negative electrode current collector and the positive electrode current collector while oxygen or air is flowing into a part or the entirety of the positive electrode gap.

[0776] <19> 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 as described in any one of <1> to <8>, a positive electrode current collector, a positive electrode void, a binary catalyst capable of achieving both oxygen generation and oxygen reduction, and an ion permeable membrane,

[0777] The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane.

[0778] The positive electrode gap is connected to the binary catalyst.

[0779] A portion of the positive electrode current collector is electrically connected to the binary catalyst.

[0780] A portion of the binary catalyst is contacted with air or an alkaline aqueous solution.

[0781] The ion permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

[0782] <20> A hydrogen filling and power generation device as described in <19>, wherein a voltage is applied between the negative electrode current collector and the positive electrode current collector in a state where a liquid hydrogen carrier is filled or flows into the negative electrode void so that hydrogen is filled in the liquid hydrogen carrier, and a load is connected between the negative electrode current collector and the positive electrode current collector to generate electricity.

[0783] <21> A hydrogen filling and power generation device as described in <19> or <20>, wherein a voltage is applied between the negative electrode current collector and the positive electrode current collector in a state where an alkaline electrolyte is filled or flows into a part or the whole of the positive electrode void so that hydrogen is filled in the liquid hydrogen carrier, and a load is connected between the negative electrode current collector and the positive electrode current collector in a state where oxygen or air flows into a part or the whole of the positive electrode void so as to generate electricity.

[0784] <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,

[0785] The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane.

[0786] The positive electrode gap is in contact with both the positive electrode current collector and the ion permeable membrane.

[0787] The ion permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

[0788] <23> A hydrogen filling and power generation device as described in <22>, wherein, in a state where a fluid hydrogen carrier is filled or flows into a part or the whole of the aforementioned negative electrode voids, and in a state where a fluid nickel hydroxide slurry is filled or flows into a part or the whole of the aforementioned positive electrode voids, a voltage is applied between the aforementioned negative electrode current collector and the aforementioned positive electrode current collector so that hydrogen is filled in the aforementioned fluid hydrogen carrier, and a load is connected between the aforementioned negative electrode current collector and the aforementioned positive electrode current collector to generate electricity.

[0789] <24> The hydrogen filling device as described in any one of <13> to <15>, wherein the positive electrode current collector or the negative electrode current collector or a part of both is formed of a porous conductor having through holes in the thickness direction and a part of it is in contact with the ion permeable membrane.

[0790] <25> The hydrogen filling device according to any one of <13> to <15>, wherein a plurality of the hydrogen filling devices are stacked with bipolar plates serving as both the negative electrode current collector and the positive electrode current collector interposed therebetween.

[0791] <26> The power generation device as described in any one of <16> to <18> is characterized in that the positive electrode current collector or the negative electrode current collector or a part of both is formed by a porous conductor having through holes in the thickness direction and a part of it is in contact with the ion permeable membrane.

[0792] <27> The power generation device according to any one of <16> to <18>, wherein the power generation device is stacked in plurality with bipolar plates serving as both the negative electrode current collector and the positive electrode current collector interposed therebetween.

[0793] <28> A hydrogen filling and power generation device as described in any one of <19> to <23>, wherein the positive electrode current collector or the negative electrode current collector or a portion of both is formed by a porous conductor having through holes in the thickness direction and a portion thereof is in contact with the ion permeable membrane.

[0794] <29> The hydrogen filling and power generation device according to any one of <19> to <23>, wherein the hydrogen filling and power generation device is stacked in plurality via bipolar plates serving as both the negative electrode current collector and the positive electrode current collector.

[0795] <30> A hydrogen filling system having a tank for storing the aforementioned fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte,

[0796] The tank is connected to the hydrogen filling device or the positive electrode gap or the negative electrode gap described in any one of <13> to <15>,

[0797] The hydrogen filling system has a pressurizing / depressurizing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the voids of the positive electrode or the voids of the negative electrode.

[0798] <31> The hydrogen filling system as described in <30>, wherein the flow path for filling / discharging the fluid hydrogen carrier, the fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps between the plurality of stacked hydrogen filling devices has a region made of an insulating material,

[0799] 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.

[0800] <32> The hydrogen filling system as described in <30>, wherein the flow path for filling / discharging the fluid hydrogen carrier, the fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps between the plurality of stacked hydrogen filling devices has a region made of an insulating material,

[0801] In the flow path formed of the insulating material, the fluid hydrogen carrier, the fluid nickel hydroxide slurry or the alkaline electrolyte is discontinuous.

[0802] <33> A hydrogen filling system as described in any one of <30> to <32>, wherein a valve that can be opened and closed is provided in a flow path for filling / discharging the aforementioned fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps between each of the stacked multiple hydrogen filling devices.

[0803] <34> The hydrogen filling system according to any one of <30> to <33>, wherein the tank for storing the liquid hydrogen carrier after hydrogen filling is separate from the tank for storing the liquid hydrogen carrier after power generation.

[0804] <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.

[0805] <36> A power generation system having a tank for storing the aforementioned fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte,

[0806] The tank is connected to the positive electrode gap or the negative electrode gap of the power generation device described in any one of <16> to <18>,

[0807] A pressurizing / depressurizing device is provided for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into the voids of the positive electrode or the voids of the negative electrode.

[0808] <37> The power generation system according to <36>, wherein the flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps between the plurality of stacked power generation devices has a region made of an insulating material,

[0809] 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.

[0810] <38> The power generation system according to <36>, wherein the flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps between the plurality of stacked power generation devices has a region made of an insulating material,

[0811] In the flow path formed of the insulating material, the fluid hydrogen carrier, the fluid nickel hydroxide slurry or the alkaline electrolyte is discontinuous.

[0812] <39> A power generation system as described in any one of <36> to <38>, wherein a valve that can be opened and closed is provided in a flow path for filling / discharging the aforementioned fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps between each of the stacked multiple power generation devices.

[0813] <40> The power generation system according to any one of <36> to <39>, wherein the tank for storing the liquid hydrogen carrier after being filled with hydrogen is separate from the tank for storing the liquid hydrogen carrier after power generation.

[0814] <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 more is mixed in the tank.

[0815] <42> A hydrogen filling and power generation system having a tank for storing the aforementioned fluid hydrogen carrier, fluid nickel hydroxide slurry, or alkaline electrolyte,

[0816] The tank is connected to the positive electrode gap or the negative electrode gap of the hydrogen filling and power generation device described in any one of <19> to <23>,

[0817] The hydrogen filling and power generation system has a pressurizing / depressurizing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the voids of the positive electrode or the voids of the negative electrode.

[0818] <43> A hydrogen filling and power generation system as described in <42>, wherein the flow path for filling / discharging the aforementioned fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into the gaps between each of the stacked multiple hydrogen filling and power generation devices has an area composed of insulating material, and the shortest length of the continuous flow path composed of the aforementioned insulating material from a bipolar plate to another bipolar plate is more than 20 cm.

[0819] <44> The hydrogen filling and power generation system as described in <42>, wherein the flow path for filling / discharging the aforementioned fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps between the stacked plurality of hydrogen filling and power generation devices has a region made of an insulating material,

[0820] In the flow path formed of the insulating material, the fluid hydrogen carrier, the fluid nickel hydroxide slurry or the alkaline electrolyte is discontinuous.

[0821] <45> A hydrogen filling and power generation system as described in any one of <42> to <44>, wherein a valve that can be opened and closed is provided in a flow path for filling / discharging the aforementioned fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps between the stacked multiple hydrogen filling devices / power generation devices.

[0822] <46> The hydrogen filling and power generation system according to any one of <42> to <45>, wherein the tank for storing the liquid hydrogen carrier after hydrogen filling is separate from the tank for storing the liquid hydrogen carrier after power generation.

[0823] <47> The 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.

[0824] <48> An energy transfer method, wherein the aforementioned liquid hydrogen carrier filled with hydrogen, or the liquid hydrogen carrier and the liquid nickel hydroxide slurry, is extracted from the power generation system described in any one of <36> to <41>, and the liquid hydrogen carrier filled with hydrogen, or the liquid hydrogen carrier and the liquid nickel hydroxide slurry is transported.

[0825] <49> An energy transfer method, wherein a liquid hydrogen carrier filled with hydrogen, or a liquid hydrogen carrier and a liquid nickel hydroxide slurry, is extracted from a hydrogen filling and power generation system as described in any one of <42> to <47>, and the liquid hydrogen carrier filled with hydrogen, or the liquid hydrogen carrier and the liquid nickel hydroxide slurry are transported.

[0826] Description of Reference Numerals

[0827] 10.26 Mobile hydrogen carrier

[0828] 11.261 Hydrogen Absorbing Alloy

[0829] 12.262 Alkaline electrolyte

[0830] 13 Hydrogen-absorbing alloy filled with hydrogen

[0831] 14 Liquid hydrogen carrier filled with hydrogen

[0832] 17, 27, 36, 108 connectors

[0833] 20 Charge and discharge cells

[0834] 21.101 Negative current collector

[0835] 22.103 Positive current collector

[0836] 23. Oxygen electrode catalyst

[0837] 24. Ion permeable membrane

[0838] 25, 34, 107 seals

[0839] 30A, 30B secondary battery

[0840] 31, 37 cans

[0841] 32, 38 Pumps

[0842] 35 Next Door

[0843] 53 Nickel oxide and hydroxide containing substances

[0844] 100A Hydrogen Filling Device

[0845] 100B Second hydrogen filling device

[0846] 100C Third hydrogen filling device

[0847] 102 Negative electrode gap

[0848] 104 positive electrode gap

[0849] 105 Oxygen generating electrode

[0850] 106 Ion permeable membrane

[0851] 111 Porous negative electrode current collector

[0852] 112 Porous positive electrode current collector

[0853] 121 Bipolar Plate

[0854] 200A generator

[0855] 200B Second power generation device

[0856] 200C Third power generation unit

[0857] 201 Oxygen reduction electrode

[0858] 202 Oxygenates

[0859] 300A Hydrogen filling and power generation device

[0860] 300B Second hydrogen filling and power generation device

[0861] 300C Third Hydrogen Filling and Power Generation Device

[0862] 300D Fourth Hydrogen Filling and Power Generation Device

[0863] 300E Fifth Hydrogen Filling and Power Generation Device

[0864] 300F Sixth Hydrogen Filling and Power Generation Device

[0865] 301 Binary Electrode

[0866] 302 Nickel hydroxide containing slurry

[0867] 303 Nickel hydroxide containing substances

[0868] 304 Nickel hydroxide slurry

[0869] 400A Hydrogen Filling and Power Generation System

[0870] 400B Second Hydrogen Filling and Power Generation System

[0871] 400C Third Hydrogen Filling and Power Generation System

[0872] 400D Fourth Hydrogen Filling and Power Generation System

[0873] 410 Negative electrode tank

[0874] 420 Negative electrode pressurization / decompression device

[0875] 430 positive electrode tank

[0876] 440 Positive electrode pressurization / decompression device

[0877] 450 Inter-device flow path

[0878] 460 device flow path

[0879] 461 Liquid cut-off device

[0880] 462 Valve that can be opened and closed

[0881] 470 Second negative electrode tank

[0882] 480 Second positive electrode tank

Claims

1. A mobile hydrogen carrier comprising a hydrogen absorbing alloy and an alkaline electrolyte.

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

3. The mobile hydrogen carrier according to claim 1 or 2, wherein: The hydrogen absorbing alloy has a median diameter of 50 μm or less.

4. The mobile hydrogen carrier according to any one of claims 1 to 3, which has a shear rate of 100 sec -1 The viscosity at this time is 100 mPa·sec or more. 5 . The fluid hydrogen carrier according to claim 1 , comprising a water-soluble organic polymer having a weight average molecular weight of 1500 or more.

6. The mobile hydrogen carrier according to claim 5, wherein: The water-soluble organic polymer is polyacrylate. 7 . The fluid hydrogen carrier according to claim 1 , comprising a thixotropic agent. 8 . The fluid hydrogen carrier according to claim 1 , comprising carbon black having a median diameter of 1 μm or less. 9 . The method for producing a fluid hydrogen carrier according to claim 1 , comprising a step of heating at 80° C. or higher. 10 . The method for producing a fluid hydrogen carrier according to claim 1 , comprising the 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 electrode current collector, a positive electrode current collector, an oxygen electrode catalyst and an ion permeable membrane. A portion of the negative electrode current collector is electrically connected to the mobile hydrogen carrier according to any one of claims 1 to 8, A portion of the positive electrode current collector is electrically connected to the oxygen electrode catalyst, A portion of the oxygen electrode catalyst is ionically connected to the ion permeable membrane, The ion permeable membrane is arranged in a manner to separate the negative electrode current collector from the positive electrode current collector. A portion of the mobile hydrogen carrier is ionically connected to the ion-permeable membrane.

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

13. A hydrogen filling 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 claims 1 to 8, a positive electrode current collector, a positive electrode void, an oxygen generating electrode and an ion permeable membrane, The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane. The positive electrode gap is connected to the oxygen generating catalyst, A portion of the positive electrode current collector is electrically connected to the oxygen generating catalyst, a portion of the oxygen generating catalyst is contacted with an alkaline aqueous solution, A portion of the oxygen generating catalyst is ionically connected to the ion permeable membrane, The ion-permeable membrane is provided so as to separate the negative electrode current collector from 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 the entirety of the negative electrode voids are filled or flowed with liquid hydrogen carriers, so that hydrogen is filled into the liquid hydrogen carriers.

15. The hydrogen filling device according to claim 13 or 14, wherein: A voltage is applied between the negative electrode current collector and the positive electrode current collector in a state where an alkaline electrolyte is filled or flowed into a part or the whole of the positive electrode gap, so that hydrogen is filled into the mobile hydrogen carrier.

16. A power generation device comprising a negative electrode current collector, a negative electrode void that can be filled with the mobile hydrogen carrier according to any one of claims 1 to 8 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 gap is in contact with both the negative electrode current collector and the ion permeable membrane. The positive electrode gap is in contact with the oxygen reduction catalyst, A portion of the positive electrode current collector is electrically connected to the oxygen reduction catalyst, A portion of the oxygen reduction catalyst is ionically connected to the ion permeable membrane, A portion of the oxygen reduction catalyst is in contact with air, The ion-permeable membrane is provided so as to separate the negative electrode current collector from 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 the entirety of the negative electrode voids are filled or flowed with a fluid hydrogen carrier.

18. The power generation device according to claim 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 flows into a part or the whole of the positive electrode gap to generate power.

19. A hydrogen filling and power generation device comprising a negative electrode current collector, a negative electrode void capable of being filled with a mobile hydrogen carrier according to any one of claims 1 to 8, a positive electrode current collector, a positive electrode void, a binary catalyst capable of achieving both oxygen generation and oxygen reduction, and an ion permeable membrane, The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane. The positive electrode gap is connected to the binary catalyst. A portion of the positive electrode current collector is electrically connected to the binary catalyst, A portion of the binary catalyst is contacted with air or an alkaline aqueous solution, The ion-permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

20. The hydrogen filling and power generation device according to claim 19, wherein: A voltage is applied between the negative electrode current collector and the positive electrode current collector while liquid hydrogen carriers are filled or flowed into the negative electrode gaps so that hydrogen is filled into the liquid hydrogen carriers, and a load is connected between the negative electrode current collector and the positive electrode current collector to generate electricity.

21. The hydrogen filling and power generation device according to claim 19 or 20, wherein: In a state where alkaline electrolyte is filled or flows into a part or the whole of the positive electrode void, a voltage is applied between the negative electrode current collector and the positive electrode current collector so that hydrogen is filled in the mobile hydrogen carrier, and in a state where oxygen or air flows into a part or the whole of the positive electrode void, a load is connected between the negative electrode current collector and the positive electrode current collector to generate electricity.

22. A hydrogen filling and power generation device comprising a negative electrode current collector, a negative electrode void capable of being filled with a mobile hydrogen carrier, a positive electrode current collector, a positive electrode void and an ion permeable membrane, The negative electrode gap is in contact with both the negative electrode current collector and the ion permeable membrane. The positive electrode gap is in contact with both the positive electrode current collector and the ion permeable membrane. The ion-permeable membrane is provided so as to separate the negative electrode current collector from the positive electrode current collector.

23. The hydrogen filling and power generation device according to claim 22, wherein: In a state where a fluid hydrogen carrier is filled or flowed into a part or the whole of the negative electrode voids, and in a state where a fluid nickel hydroxide slurry is filled or flowed into a part or the whole of the positive electrode voids, A voltage is applied between the negative electrode current collector and the positive electrode current collector to fill the liquid hydrogen carrier with hydrogen, and a load is connected between the negative electrode current collector and the positive electrode current collector to generate electricity.

24. The hydrogen filling device according to any one of claims 13 to 15, wherein: The positive electrode current collector or the negative electrode current collector or a part of both is formed of a porous conductor having through holes in the thickness direction, and a part of them is in contact with the ion permeable membrane.

25. The hydrogen filling device according to any one of claims 13 to 15, wherein: A plurality of the hydrogen filling devices are stacked with bipolar plates serving as both the negative electrode current collector and the positive electrode current collector interposed therebetween.

26. The power generation device according to any one of claims 16 to 18, characterized in that: The positive electrode current collector or the negative electrode current collector or a part of both is formed of a porous conductor having through holes in the thickness direction, and a part of them is in contact with the ion permeable membrane.

27. The power generation device according to any one of claims 16 to 18, wherein: The power generation device is formed by stacking a plurality of bipolar plates interposed therebetween, each serving as both the negative electrode current collector and the positive electrode current collector.

28. The hydrogen filling and power generation device according to any one of claims 19 to 23, wherein: The positive electrode current collector or the negative electrode current collector or a part of both is formed of a porous conductor having through holes in the thickness direction, and a part of them is in contact with the ion permeable membrane.

29. The hydrogen filling and power generation device according to any one of claims 19 to 23, wherein: The hydrogen filling and power generation device is stacked in plurality via bipolar plates serving as both the negative electrode current collector and the positive electrode current collector.

30. A hydrogen filling system 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 or the positive electrode gap or the negative electrode gap according to any one of claims 13 to 15, The hydrogen filling system has a pressurizing / depressurizing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the positive electrode gap or the negative electrode gap.

31. The hydrogen filling system of claim 30, wherein: The flow path for filling / discharging the fluid hydrogen carrier, the fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps of the stacked plurality of hydrogen filling devices has a region made of an insulating material. 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.

32. The hydrogen filling system of claim 30, wherein: The flow path for filling / discharging the fluid hydrogen carrier, the fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps of the stacked plurality of hydrogen filling devices has a region made of an insulating material. In the flow path formed of the insulating material, the fluid hydrogen carrier, the fluid nickel hydroxide slurry or the alkaline electrolyte is discontinuous.

33. The hydrogen filling system according to any one of claims 30 to 32, 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 each gap of the plurality of stacked hydrogen filling devices.

34. The hydrogen filling system according to any one of claims 30 to 33, wherein: The tank for storing the liquid hydrogen carrier after hydrogen filling is separate from the tank for storing the liquid hydrogen carrier after power generation.

35. The hydrogen filling system according to any one of claims 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. A power generation system having a tank for storing the mobile hydrogen carrier, the mobile nickel hydroxide slurry or the alkaline electrolyte, The tank is connected to the positive electrode gap or the negative electrode gap of the power generation device according to any one of claims 16 to 18, The power generation system includes a pressurizing / depressurizing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen, or alkaline electrolyte into / from the positive electrode gap or the negative electrode gap.

37. The power generation system of claim 36, wherein: The flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the gaps between the plurality of stacked power generation devices has a region made of an insulating material. 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.

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

39. The power generation system according to any one of claims 36 to 38, wherein: A valve capable of opening and closing is provided in a flow path for filling and discharging the fluid hydrogen carrier, nickel hydroxide slurry, air, oxygen or alkaline electrolyte into and from the gaps between the plurality of stacked power generation devices.

40. The power generation system according to any one of claims 36 to 39, wherein: The tank for storing the liquid hydrogen carrier after hydrogen filling is separate from the tank for storing the liquid hydrogen carrier after power generation.

41. The power generation system according to any one of claims 36 to 40, 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.

42. A hydrogen filling and power generation system having a tank for storing the mobile hydrogen carrier, the mobile nickel hydroxide slurry, or the alkaline electrolyte, The tank is connected to the positive electrode gap or the negative electrode gap of the hydrogen filling and power generation device according to any one of claims 19 to 23, The hydrogen filling and power generation system has a pressurizing / depressurizing device capable of filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into / from the positive electrode gap or the negative electrode gap.

43. The hydrogen filling and power generation system according to claim 42, wherein: The flow path for filling / discharging the fluid hydrogen carrier, fluid nickel hydroxide slurry, air, oxygen or alkaline electrolyte into the gaps between the stacked multiple hydrogen filling and power generation devices has an area composed of insulating material, and the shortest length of the continuous flow path composed of the insulating material from a bipolar plate to another bipolar plate is more than 20 cm.

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

45. The hydrogen filling and power generation system according to any one of claims 42 to 44, 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 the gaps between the plurality of stacked hydrogen filling devices / power generation devices.

46. ​​The hydrogen filling and power generation system according to any one of claims 42 to 45, wherein: The tank for storing the liquid hydrogen carrier after hydrogen filling is separate from the tank for storing the liquid hydrogen carrier after power generation.

47. The hydrogen filling and power generation system according to any one of claims 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. A method of energy delivery, wherein: The fluid hydrogen carrier filled with hydrogen, or the fluid hydrogen carrier and the fluid nickel hydroxide slurry, is extracted from the power generation system according to any one of claims 36 to 41, and the fluid hydrogen carrier filled with hydrogen, or the fluid hydrogen carrier and the fluid nickel hydroxide slurry is transported.

49. A method of energy delivery, wherein: A fluid hydrogen carrier filled with hydrogen, or a fluid hydrogen carrier and a fluid nickel hydroxide slurry, is extracted from the hydrogen filling and power generation system according to any one of claims 42 to 47, and the fluid hydrogen carrier filled with hydrogen, or the fluid hydrogen carrier and the fluid nickel hydroxide slurry is transported.

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