JP2009221072A - Cartridge for hydrogen supply and fuel cell power generation system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cartridge for hydrogen supply which supplies hydrogen to equipment using hydrogen such as a fuel cell and quickly processes excess hydrogen present in the stoppage of the operation of the equipment, and to provide a fuel cell power generation system using the cartridge for hydrogen supply. <P>SOLUTION: The cartridge for hydrogen supply can be connected to the equipment using hydrogen and has a housing container for housing a hydrogen producing material producing hydrogen by reaction and a hydrogen removing apparatus for removing excessive portion of produced hydrogen to prevent the dissipation thereof to the outside. The fuel cell power generation system is provided with: a fuel cell body provided with an electrode-electrolyte integrated substance having a positive electrode for reducing oxygen, a negative electrode for oxidizing hydrogen and a solid electrolyte membrane arranged between the positive electrode and the negative electrode; and the cartridge for hydrogen supply. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  [Technical Field] The present invention relates to a hydrogen supply cartridge that can be used in a power generator for a mobile object such as a consumer cogeneration system or an automobile, a solid polymer fuel cell useful as a portable power source, and the hydrogen The present invention relates to a fuel cell power generation system including a supply cartridge.

  Solid polymer fuel cells operate at low temperatures from room temperature to 100 ° C or less, and have features such as quick start / stop and high output density, so mobile bodies for consumer cogeneration, automobiles, etc. It is expected to be used as a power generator and portable power source.

  A polymer electrolyte fuel cell (PEMFC) is a hydrogen ion conductive polymer electrolyte membrane as an electrolyte membrane layer, a catalyst layer disposed on both sides thereof, and a gas disposed on both sides thereof. It has an electrode / electrolyte integrated body (MEA: Membrane electrode assembly) composed of a porous electrode base material serving as a diffusion layer.

  The fuel used for PEMFC includes hydrogen, which is a flammable gas. As a method for producing such hydrogen, for example, a hydrogen generating substance such as aluminum, magnesium, silicon, and zinc is chemically reacted with water. Methods for generating hydrogen are known. Specifically, for example, Patent Document 1 discloses a method for stably maintaining an exothermic reaction by controlling the supplied water by using an exothermic reaction between a hydrogen generating substance and water, and a hydrogen generating substance or water. It has been proposed to easily proceed the reaction by heating either or both.

  By the way, according to FIG. 3 of Patent Document 1, when the supply of water or the like to the hydrogen generating substance is reduced or stopped, a phenomenon that hydrogen generation does not stop immediately but continues for a while is confirmed. This is because, for example, when aluminum powder is used as a hydrogen generating substance, the film (oxide film) formed on the surface of the aluminum powder is first dissolved by alkali or the like, and then the supplied water penetrates into the aluminum powder. This is because hydrogen generation is continued, but even after the supply of water is stopped, the hydrogen generation continues for a while due to the reaction with the water remaining in the system.

  Therefore, for example, in a hydrogen supply cartridge that is applied to a device that uses hydrogen, such as a fuel cell, when the method described in Patent Document 1 is used to secure hydrogen, the hydrogen generating material is simultaneously released when the operation of the device is stopped. Even if the supply of water is stopped, hydrogen generation continues in the hydrogen supply cartridge for a while. Therefore, when removing the hydrogen supply cartridge from the equipment, it is necessary to allow a considerable amount of time from the stoppage of water supply to the hydrogen generating material to the removal of the hydrogen supply cartridge to prevent leakage of hydrogen to the outside of the system. There is.

  As a technique for solving the above problems, for example, a stack case storing a fuel cell is filled with a cooling liquid, gas leaking into the cooling liquid is collected, and the gas is catalytically burned after gas-liquid separation. A fuel cell system including a catalytic combustor has been proposed (Patent Document 2).

JP 2007-45646 A JP 2002-134138 A

  However, in the technique of Patent Document 2, it is necessary to enclose a coolant in a stack case in which the fuel cell system is stored. However, especially in the case of portable device applications, the device is not always oriented in a certain direction. It is difficult to efficiently collect leaking gas. In addition, the fuel cell power generation system including a configuration for collecting and removing hydrogen may be increased in size.

  The present invention has been made in view of the above circumstances, and an object thereof is a hydrogen supply cartridge for supplying hydrogen to a device using hydrogen, such as a fuel cell, and is present when the operation of the device is stopped. An object of the present invention is to provide a hydrogen supply cartridge capable of quickly processing surplus hydrogen and a fuel cell power generation system using the hydrogen supply cartridge.

  The hydrogen supply cartridge of the present invention that has achieved the above object is a hydrogen supply cartridge that can be connected to an apparatus that uses hydrogen, and a storage container that can store a hydrogen generating substance that generates hydrogen by a reaction; It has a hydrogen removing device for removing surplus generated hydrogen and preventing dissipation to the outside.

  The fuel cell power generation system of the present invention includes an electrode / electrolyte integrated product having a positive electrode for reducing oxygen, a negative electrode for oxidizing hydrogen, and a solid electrolyte membrane disposed between the positive electrode and the negative electrode. The fuel cell main body and the hydrogen supply cartridge of the present invention are provided.

  ADVANTAGE OF THE INVENTION According to this invention, when removing from the apparatus after a stop of operation, the cartridge for hydrogen supply which can remove excess hydrogen rapidly by simple operation can be provided. Therefore, in the fuel cell power generation system of the present invention using the hydrogen supply cartridge of the present invention, for example, hydrogen can be prevented from leaking out of the system when the hydrogen supply cartridge is replaced.

  FIG. 1 shows a schematic diagram of a configuration example of a fuel cell power generation system of the present invention. Reference numeral 1 denotes a fuel cell, which has a plurality of electrode / electrolyte integrated bodies (MEA) 100 electrically connected in series, and is connected to an external load 6 (such as an electronic device to which the fuel cell power generation system is applied). Has been. Reference numeral 2 denotes a hydrogen production apparatus for supplying hydrogen as a fuel to the fuel cell 1. For example, the hydrogen production apparatus 2 may have the hydrogen supply cartridge of the present invention. However, it may be constituted only by the hydrogen supply cartridge of the present invention. A fuel flow path 4 is formed between the fuel cell 1 and the hydrogen production apparatus 2. Reference numeral 5 denotes a ventilation path. Furthermore, the arrow next to the fuel flow path 4 indicates the direction of hydrogen flow (the same applies to each drawing described later).

  3 is a stop valve, which is closed when the fuel cell 1 is stopped, shuts off the supply of hydrogen from the hydrogen production device 2 to the fuel cell 1, and is opened when the fuel cell 1 is operated. This is to enable supply of hydrogen from the hydrogen production apparatus 2 to the fuel cell 1.

  In the fuel cell power generation system of the present invention, a stop valve is not essential, but when a stop valve is provided, it is disposed between the hydrogen production apparatus 2 and the fuel cell 1 as shown in FIG. Is preferred. Further, FIG. 1 shows a configuration in which the external load 6 is connected to the fuel cell 1 in a switchable manner, but the external load 6 may be configured to be always connected to the fuel cell 1.

  FIG. 2 schematically shows an example of the hydrogen supply cartridge of the present invention. In FIG. 2, the hydrogen supply cartridge 20 is removed from the fuel cell power generation system and the hydrogen removing device 20b is operated. However, in order to facilitate understanding of each component, some components are illustrated. Is not hatched indicating that it is a cross section (the same applies to FIG. 3 described later).

  As shown in FIG. 2, the hydrogen supply cartridge 20 of the present invention includes a hydrogen generating substance storage container 20 a for storing a hydrogen generating substance and a hydrogen removing device 20 b. The hydrogen generating substance storage container 20a is supplied with water to react the hydrogen generating substance and water to generate hydrogen. Therefore, the hydrogen generating substance storage container 20a also plays a role as a reaction container.

  The hydrogen removing device 20b is operated when the fuel cell power generation system is stopped, that is, when the hydrogen supply cartridge 20 is removed from the combustion cell power generation system after the hydrogen generation speed of the hydrogen supply cartridge 20 is reduced.

  The hydrogen supply cartridge 20 shown in FIG. 2 is removed from the fuel cell power generation system, and then the hydrogen lead-out pipe 29 and the hydrogen removal device 20b of the hydrogen generating material container 20a are fixed by a screw structure to remove the hydrogen. It has the structure which operates the apparatus 20b. By adopting such a configuration, it is possible to join the hydrogen generating substance storage container 20a and the hydrogen removal device 20b while more reliably preventing hydrogen leakage from the hydrogen generating substance storage container 20a.

  A hydrogen removal apparatus 20b according to the hydrogen supply cartridge 20 shown in FIG. 2 has an MEA 200 that allows a positive electrode and a negative electrode to be conductive. The MEA 200 includes a positive electrode catalyst layer 202 that reduces oxygen and a negative electrode catalyst layer 204 that oxidizes hydrogen, and further includes a solid electrolyte membrane 203 between the positive electrode catalyst layer 202 and the negative electrode catalyst layer 204. Yes. Further, the positive electrode catalyst layer 202 has a stacked positive electrode diffusion layer 201 on the surface opposite to the surface on the solid electrolyte membrane 203 side, and the negative electrode catalyst layer 204 on the surface opposite to the surface on the solid electrolyte membrane 203 side. The negative electrode diffusion layer 205 is stacked.

  The positive electrode diffusion layer 201 and the negative electrode diffusion layer 205 are made of a porous electron conductive material or the like, and for example, a porous carbon sheet subjected to a water repellent treatment is used. In addition, on the catalyst layer side of the positive electrode diffusion layer 201 and the negative electrode diffusion layer 205, fluororesin particles [polytetrafluoroethylene (PTFE) resin particles, etc.] are provided for the purpose of further improving water repellency and improving contact with the catalyst layer. In some cases, a carbon powder paste is applied.

  The negative electrode catalyst layer 204 has a function of oxidizing hydrogen diffused through the negative electrode diffusion layer 205. The negative electrode catalyst layer 204 contains, for example, a carbon powder carrying a catalyst (catalyst carrying carbon powder) and a proton conductive material. Moreover, you may further contain the resin binder as needed.

  The catalyst contained in the negative electrode catalyst layer 204 is not particularly limited as long as it can oxidize hydrogen, and examples thereof include platinum fine particles. The catalyst may be an alloy of platinum and at least one metal element selected from the group consisting of iron, nickel, cobalt, tin, ruthenium and gold.

  Further, when a platinum alloy is used as the metal fine particles constituting the catalyst used in the negative electrode catalyst layer 204, the platinum alloy is composed of ruthenium, rhodium, palladium, osmium, iridium, cobalt, nickel, chromium, gold, iron, molybdenum and tin. Fine particles composed of an alloy of platinum and at least one metal selected from the group consisting of:

  Furthermore, the average particle diameter of the metal fine particles constituting the catalyst of the negative electrode catalyst layer 204 is preferably 2 to 5 nm from the viewpoint of increasing the surface area of the metal fine particles and further enhancing the hydrogen oxidation reaction activity.

As the carbon powder as the catalyst carrier, for example, carbon black having a BET specific surface area of 10 to 2000 m ² / g and an average particle diameter of 20 to 100 nm is used. The catalyst can be supported on the carbon powder by, for example, a colloid method.

  As a content ratio of the carbon powder and the catalyst, for example, the catalyst is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the carbon powder. This is because such a content ratio can constitute a positive electrode catalyst layer having sufficient catalytic activity. Further, for example, when the catalyst-supported carbon powder is produced by a method of depositing the catalyst on the carbon powder (for example, a colloid method), the catalyst diameter is as long as the carbon powder and the catalyst have the above-mentioned content ratio. This is because it does not become too large and sufficient catalytic activity is obtained.

  The proton conductive material contained in the negative electrode catalyst layer 204 is not particularly limited. For example, a resin having a sulfonic acid group such as a polyperfluorosulfonic acid resin, a sulfonated polyether sulfonic acid resin, or a sulfonated polyimide resin is used. Can be used. Specific examples of the polyperfluorosulfonic acid resin include “Nafion (registered trademark)” manufactured by DuPont, “Flemion (registered trademark)” manufactured by Asahi Glass, and “Aciplex (trade name) manufactured by Asahi Kasei Kogyo Co., Ltd. Or the like.

  The content of the proton conductive material in the negative electrode catalyst layer 204 is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the catalyst-supporting carbon powder. If the proton conductive material is contained in the above amount, sufficient proton conductivity is obtained in the negative electrode catalyst layer, and the electric resistance value does not become too large, and a fuel cell with good battery performance can be obtained. It is.

  The binder for the negative electrode catalyst layer 204 is not particularly limited. For example, PTFE, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetra Fluoropolymers such as fluoroethylene-ethylene copolymer (E / TFE), polyvinylidene fluoride (PVDF) and polychlorotrifluoroethylene (PCTFE), polyethylene, polypropylene, nylon, polystyrene, polyester, ionomer, butyl rubber, ethylene -Non-fluorinated resins such as vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, and ethylene / acrylic acid copolymer can be used.

  The binder content in the negative electrode catalyst layer 204 is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the catalyst-supporting carbon powder. This is because if the binder is contained in the above-described amount, sufficient binding properties can be obtained for the negative electrode catalyst layer, and the electric resistance value does not become too large, and a fuel cell with good battery performance can be obtained.

  The positive electrode catalyst layer 202 has a function of reducing oxygen diffused through the positive electrode diffusion layer 201. The positive electrode catalyst layer 202 contains, for example, carbon powder carrying a catalyst (catalyst carrying carbon powder) and a proton conductive material. Moreover, you may further contain the resin binder as needed.

  The catalyst contained in the positive electrode catalyst layer 202 is not particularly limited as long as oxygen can be reduced. For example, the above-described catalysts exemplified as the catalyst related to the negative electrode catalyst layer can be used. Regarding the carbon powder, proton conductive material, and binder related to the positive electrode catalyst layer, the above-described materials exemplified as the carbon powder, proton conductive material, and binder related to the negative electrode catalyst layer can be used.

  The solid electrolyte membrane 203 is not particularly limited as long as it is made of a material that can transport protons and does not exhibit electron conductivity. As a material that can constitute the solid electrolyte membrane 203, for example, polyperfluorosulfonic acid resin, specifically, "Nafion (registered trademark)" manufactured by DuPont, "Flemion (registered trademark)" manufactured by Asahi Glass, Examples include “Aciplex (trade name)” manufactured by Asahi Kasei Corporation. In addition, sulfonated polyether sulfonic acid resin, sulfonated polyimide resin, sulfuric acid-doped polybenzimidazole, and the like can also be used as the material of the solid electrolyte membrane 203.

  The MEA 200 is sandwiched between the positive electrode current collector plate 21 disposed above the positive electrode diffusion layer 201 and the negative electrode current collector plate 22 disposed below the negative electrode diffusion layer 204. The negative electrode current collector plate 22 is fixed by, for example, bolts 24 and nuts 25. Reference numeral 23 denotes a sealing material made of silicon rubber or the like.

  The positive electrode current collector plate 21 and the negative electrode current collector plate 22 are made of, for example, a noble metal such as platinum or gold, a corrosion-resistant metal such as stainless steel, or carbon. In addition, the surface may be plated or painted to improve the corrosion resistance.

  A plurality of air holes 21 a are formed in the positive electrode current collector plate 21, and oxygen in the atmosphere is supplied to the positive electrode of the MEA 200 through these air holes 21 a. On the other hand, the negative electrode current collector plate 22 is formed with a plurality of hydrogen introduction holes 22a, and hydrogen discharged from the hydrogen lead-out pipe 29 of the hydrogen generating material storage container 20a is supplied to the negative electrode of the MEA 200 through these hydrogen introduction holes 22a. The A conductive plate 27 is connected to the positive current collector 21 and the negative current collector 22.

  In the hydrogen supply cartridge 20 shown in FIG. 2, when the hydrogen generating substance storage container 20a and the hydrogen removing device 20b are connected by the screw portion 26 when removed from the fuel cell power generation system, the positive electrode-negative electrode of the MEA 200 is connected. The conductive plate 27 becomes conductive, and hydrogen supplied from the hydrogen generating substance storage container 20a to the hydrogen removing device 20b is consumed. Therefore, the hydrogen generated from the hydrogen supply cartridge 20 removed from the fuel cell power generation system can be completely eliminated or the amount of hydrogen can be greatly reduced.

  In the hydrogen removing device 20b shown in FIG. 2, the positive electrode and the negative electrode of the MEA 200 are connected via the conductive plate 27. As the conductive plate 27, for example, the stop of the fuel cell 1 according to the fuel cell power generation system is used. After that, it is sufficient to use a material having such a resistance value that the time required for the voltage between the positive electrode and the negative electrode of the MEA 200 to be 0.1 V or less is within one minute. If the voltage between the positive electrode and the negative electrode of the MEA 200 can be lowered as described above in a short time, the positive electrode and the negative electrode of the MEA 200 can be connected by a lead body or the like without using the conductive plate 27 and can be made conductive. Also good.

  Further, by providing the insulating film 28 or the like on the surface of the conductive plate 27, leakage can be prevented. The insulating film 28 is not particularly limited as long as it is a material having no electrical conductivity. For example, polypropylene or neoprene rubber can be used.

  In addition, since the reaction of generating hydrogen by reacting the hydrogen generating substance with water is accompanied by heat generation, the hydrogen generating reaction proceeds inside the hydrogen generating substance containing container 20a (described later in detail) that performs the reaction. For example, the surface temperature of the container increases. Therefore, as shown in FIG. 2, in the hydrogen supply cartridge 20, a temperature sensor 20c is installed in the vicinity of the hydrogen generating substance storage container 20a, and the surface temperature of the hydrogen generating substance storage container 20a is measured by the temperature sensor 20c. The degree of progress of the hydrogen generation reaction can be grasped. For example, when removing the hydrogen supply cartridge 20 from the fuel cell power generation system, the surface temperature of the hydrogen generating substance storage container 20a measured by the temperature sensor 20c is preferably 80 ° C. or less, and preferably 50 ° C. or less. It is more preferable. When the surface temperature of the hydrogen generating substance storage container 20a exceeds the above temperature, the hydrogen generation reaction inside the container has progressed so much that the hydrogen removal efficiency by the hydrogen removal device 20b may be reduced. Because.

  In addition, there is no restriction | limiting in particular about the minimum of the temperature at the time of removing the cartridge for hydrogen supply from a fuel cell power generation system, Even if it is the temperature [usually normal temperature (about 25 degreeC)] of the environment where a fuel cell power generation system is used. Good.

  The mounting position of the temperature sensor 20c for measuring the surface temperature of the hydrogen generating substance storage container 20a may be installed inside the container and a part of the surface as long as the temperature change of the container surface can be accurately detected. 1 is not particularly limited, such as being installed in a part of the fuel path 4 according to the fuel cell power generation system shown in FIG. 1, but a position that can be measured without depending on the external temperature is preferable, for example, near the bottom or near the bottom of the container 20a. The outside surface is desirable.

  The temperature sensor 20c is not particularly limited as long as it can accurately measure the container temperature. For example, a contact sensor such as a platinum resistance thermometer, thermistor, thermocouple, IC temperature sensor; radiation temperature for detecting heat A non-contact type sensor such as a meter is used, but a thermistor or a thermocouple is preferably used as a small and sensitive sensor.

  The surface temperature of the hydrogen generating substance storage container 20a is preferably calculated by monitoring the temperature change with the temperature sensor 20c and using a circuit such as a microcomputer. It is more preferable to install an indicator lamp indicating that the surface temperature of the container 20a is a temperature suitable for removing the hydrogen supply cartridge 20 from the fuel cell power generation system.

The hydrogen supply cartridge 20 shown in FIG. 2 has only one hydrogen removal device 20b, but the hydrogen supply cartridge has a plurality of hydrogen removal devices (two, three, four, etc.). May be. When the hydrogen supply cartridge has a plurality of hydrogen removal devices, even if the number of hydrogen removal devices is larger, even if the hydrogen removal performance of one hydrogen removal device decreases due to deterioration of the catalyst, for example, other hydrogen removal devices Since it can be supplemented by the apparatus, a cartridge for supplying hydrogen that can maintain the hydrogen removal performance for a longer period can be obtained. In addition, the standard of the area (area in a plan view) of the MEA used in the hydrogen removing device related to the hydrogen supply cartridge is, for example, when the amount of the Pt catalyst in the negative electrode catalyst layer is 0.3 mg / cm ^2. , With respect to 1 ml / min of hydrogen, it is preferably 2.0 mm ² or more, more preferably 3.0 mm ² or more, preferably 10 mm ² or less, more preferably 6.0 mm ^2. Good performance can be maintained.

  FIG. 3 schematically shows another example of the hydrogen supply cartridge of the present invention. In FIG. 3, components having the same functions as those in FIG. 3A shows a state immediately after the hydrogen supply cartridge is removed from the fuel cell power generation system and before the operation of the hydrogen removing device, and FIG. 3B shows a state where the hydrogen removing device is activated. ing.

  In the hydrogen supply cartridge 20 of FIG. 3, the lid portion is a hydrogen removing device 20b, which is fixed by an outer container 30 containing a hydrogen generating substance storage container 20a and a hinge 33. Yes. When the hydrogen supply cartridge 20 is attached to the fuel cell power generation system, when the lock device 34 is released, the hydrogen removing device 2b is opened in the vertical direction by the action of the leaf spring 31, and the hydrogen is led out by the action of the spring 32 in the outer container 30. The pipe 29 rises and becomes easy to attach to the fuel cell power generation system.

  Further, in the hydrogen supply cartridge 20 of FIG. 3, the temperature sensor 20 c is in contact with the side surface of the hydrogen generating substance storage container 20 a when attached to the fuel cell power generation system.

  When the hydrogen supply cartridge 20 shown in FIG. 3 is removed from the fuel cell power generation system and the lid is closed, the hydrogen generating substance storage container 20a moves downward. As described above, in the hydrogen supply cartridge shown in FIG. 3, the portion that functions as a lid after being removed from the fuel cell power generation system is a hydrogen removal device, and therefore, similar to the case of the hydrogen supply cartridge shown in FIG. In addition, it is possible to consume surplus hydrogen that continues to be discharged from the hydrogen generating substance storage container 20a even after being removed from the fuel cell power generation system.

  When the hydrogen generating substance storage container 20a and the hydrogen removing device 20b are integrated as shown in FIG. 3, it is possible to prevent the operation of the hydrogen removing device 20b from being forgotten or lost. Further, in the fuel cell power generation system, for example, a mechanism in which the lever for removing the hydrogen supply cartridge 20 and the lid are interlocked to each other so that the lid is closed simultaneously with the removal of the hydrogen supply cartridge 20, that is, the hydrogen supply cartridge 20 It is also possible to adopt a mechanism in which the hydrogen removing device 20b automatically operates simultaneously with the removal. Further, the hydrogen removing device 20 b can be configured to be completely detachable from the main body of the hydrogen supply cartridge 20, that is, the hydrogen generating substance storage container 20 a and the outer container 30.

  The material and shape of the hydrogen generating substance storage container 20a of the hydrogen supply cartridge is not particularly limited as long as it can store the hydrogen generating substance that generates hydrogen, but the hydrogen generating substance in the hydrogen generating substance storage container 20a is not limited. A material or shape that does not allow water or hydrogen to leak from other than the supply port for supplying water and the hydrogen outlet port is preferable. As a specific material of the container, a material that does not easily transmit water and hydrogen and that does not break even when heated to about 120 ° C. is preferable. For example, a metal such as aluminum or iron, or a resin such as polyethylene or polypropylene may be used. Can be used. Further, as the shape of the container, a prismatic shape, a cylindrical shape or the like can be adopted. Although not shown in FIGS. 2 and 3, the hydrogen generating substance storage container 20a is also provided with a water supply port for taking water therein.

  FIG. 2 and FIG. 3 show a hydrogen removal apparatus having an MEA as a hydrogen removal apparatus included in the hydrogen supply cartridge. As described above, the hydrogen removal apparatus includes a catalyst having hydrogen oxidation activity. Is preferably used. Further, as a hydrogen removal apparatus including a catalyst having hydrogen oxidation activity, in addition to the one having the above MEA, for example, a filter containing a catalyst having hydrogen oxidation activity, a hydrogen-oxidizing activity is applied to a cylindrical exterior body. What filled the catalyst which has can also be used. In addition, as a catalyst which has hydrogen oxidation activity, the various catalyst etc. which were illustrated previously as a catalyst in the negative electrode catalyst layer of MEA can be used, for example.

  In addition, as the hydrogen removal apparatus related to the hydrogen supply cartridge, one containing a substance having reactivity with hydrogen can be preferably used. As the substance having reactivity with hydrogen, for example, a chloride such as sodium chloride; a hydrogen storage alloy;

  As the hydrogen storage alloy, various alloys such as Mm (Misch metal) -Ni, Ti-V, Zr-Ni, and Mg-Ni are known. In particular, Mm-Ni alloys and Ti-V alloys are used as battery electrode materials and hydrogen storage materials. In addition, in hydrogen storage alloys, as a measure to further increase the amount of hydrogen storage, in addition to searching for new alloys, for example, ultra-fine / amorphization of alloy structure by mechanical alloying or liquid rapid solidification, Attempts have been made to develop processing for producing hydrogen storage alloys and to control the microstructure in the materials. For example, although the alloy system is a known Mg—Ni system, an amorphous Mg—Ni hydrogen storage alloy capable of absorbing and releasing hydrogen even at room temperature by making the alloy amorphous by mechanical alloying, etc. By using it, it is possible to absorb surplus hydrogen efficiently.

  In order to connect the hydrogen supply cartridge to the fuel cell power generation system, for example, by using the screw portion 26 of the hydrogen supply cartridge shown in FIG. A fuel flow path, a method of connecting to the fuel flow path of the hydrogen production apparatus shown in FIG. Parts provided in a cylindrical shape (tubes, etc.) in the water supply part), and parts formed in a cylindrical shape provided in the hydrogen outlet port and water supply port of the hydrogen generating substance storage container of the hydrogen supply cartridge It is possible to employ a method of inserting hydrogen (such as a tube) and sealing the connecting portion (insertion portion of the tube) with a packing such as an O-ring to prevent leakage of hydrogen or water.

  FIG. 4 schematically shows a configuration example of a hydrogen production apparatus applicable to the fuel cell power generation system of the present invention. The hydrogen production apparatus 2 shown in FIG. 4 includes a hydrogen supply cartridge 20 and means for supplying water continuously or intermittently to the hydrogen generation substance in the hydrogen generation substance storage container 20a of the hydrogen supply cartridge 20. It is a thing.

  That is, the hydrogen production apparatus 2 includes a hydrogen supply cartridge 20 and a water storage container 42 that stores water, and the hydrogen generating substance storage container 20a of the hydrogen supply cartridge 20 is moved from the water storage container 42. Water is supplied, and hydrogen is produced by reacting the hydrogen generating substance with water in the hydrogen generating substance storage container 20a. Hydrogen generated in the hydrogen generating substance storage container 20a is supplied to the fuel cell 1 through a fuel flow path constituted by hydrogen outlet pipes 29a and 29b.

  A water supply pump 43 is provided in the water supply pipe 40 for supplying water from the water storage container 42 to the hydrogen generating substance storage container 20a in the hydrogen supply cartridge 2. The water stored in the water storage container 42 may be any of neutral water, acidic aqueous solution, alkaline aqueous solution, etc. (that is, any liquid containing at least water), and the hydrogen generating material to be used. What is necessary is just to select a suitable thing according to the reactivity of this.

  As the hydrogen supply cartridge 20, for example, a hydrogen supply cartridge having the configuration shown in FIGS. 2 and 3 can be used. Further, the water storage container 42 may be removable. As a result, when the hydrogen generating material in the hydrogen generating material storage container 20a of the hydrogen supply cartridge 20 is consumed or when the water in the container 42 runs out, these are removed and the hydrogen generating material storage container 20a By newly attaching a hydrogen supply cartridge 20 filled with a hydrogen generating substance and a water storage container 42 filled with water, hydrogen production can be performed again.

  The hydrogen generating substance accommodated in the hydrogen generating substance containing container 20a is not particularly limited as long as it can generate hydrogen by reacting with water at a low temperature of 120 ° C. or lower. For example, metals such as aluminum, silicon, zinc, and magnesium; alloys based on one or more elements of aluminum, silicon, zinc, and magnesium; metal hydrides;

  In the case of an alloy mainly composed of one or more elements selected from aluminum, silicon, zinc and magnesium, elements other than the respective elements which are the main elements are not particularly limited. Here, the “main body” means that 80% by mass or more, more preferably 90% by mass or more is contained with respect to the entire alloy.

  Metals such as aluminum, silicon, zinc, and magnesium, and alloys mainly composed of one or more elements of aluminum, silicon, zinc, and magnesium are less likely to react with water at room temperature. It is a substance that facilitates exothermic reaction. In this specification, normal temperature is a temperature in the range of 20 to 30 ° C.

For example, in the case of aluminum and water, the reaction for producing hydrogen and oxidation products is as follows:
2Al + 6H ₂ O → Al ₂ O ₃ .3H ₂ O + 3H ₂ (1)
2Al + 4H ₂ O → Al ₂ O ₃ .H ₂ O + 3H ₂ (2)
2Al + 3H ₂ O → Al ₂ O ₃ + 3H ₂ (3)

  The hydrogen generating material made of the metal or alloy is stabilized by forming an oxide film on the surface. For this reason, it is preferable to make the particle size of the hydrogen generating material as small as possible and increase the reaction area. For example, the form of the hydrogen generating substance is preferably in the form of particles or flakes having a particle diameter of 0.1 to 100 μm, and the particle diameter is more preferably 0.1 to 50 μm. This is because hydrogen generation occurs smoothly when the particle size of the hydrogen generating substance is 100 μm or less. Further, when the particle size of the hydrogen generating material is reduced, the hydrogen generation rate is increased. However, when the particle size is smaller than 0.1 μm, the flammability is increased and handling becomes difficult. Moreover, since the bulk density is reduced, the filling density of the hydrogen generating material is lowered, and the energy density is likely to be lowered. For this reason, it is preferable that the particle size of the hydrogen generating substance is 0.1 μm or more.

  In addition, the particle size of the hydrogen generating substance referred to in the present specification is an average particle size, and means a value of a particle diameter at a volume-based integrated fraction of 50%. As a method for measuring the average particle diameter, for example, a laser diffraction / scattering method or the like can be used. Specifically, this is a particle diameter distribution measurement method using a scattering intensity distribution detected by irradiating a measurement target substance dispersed in a liquid phase such as water with laser light. As a particle size distribution measuring apparatus using a laser diffraction / scattering method, for example, “Microtrack HRA” manufactured by Nikkiso Co., Ltd. can be used.

  Examples of the metal hydride that can be used as the hydrogen generating substance include sodium borohydride and potassium borohydride. These metal hydrides are relatively stable in an aqueous alkali solution, but when a catalyst is present, they can rapidly react with water to generate hydrogen. As the catalyst, for example, metals such as Pt and Ni, acids, and the like can be used.

For example, in the case of sodium borohydride, it can react as the following formula to generate hydrogen.
NaBH ₄ + 2H ₂ O → NaBO ₂ + 4H ₂ (4)

  As the hydrogen generating substance, those exemplified above may be used alone or in combination of two or more.

  Further, by using the hydrogen generating material together with a heat generating material (a material other than the hydrogen generating material) that generates heat by reacting with water, even if low temperature (for example, about 5 ° C.) water is supplied, The temperature in the reaction system can be increased by exotherm, and rapid hydrogen generation can be enabled.

  Exothermic substances that generate heat by reacting with water, for example, calcium oxide, magnesium oxide, calcium chloride, magnesium chloride, calcium sulfate, etc., are converted into hydroxides by reaction with water or exothermic by hydration. Examples include alkali metal or alkaline earth metal oxides, chlorides, and sulfuric acid compounds. In addition, those that generate hydrogen by reaction with water, such as metal hydrides such as sodium borohydride, potassium borohydride, and lithium hydride, can be used as a hydrogen generating substance as described above. However, it can also be used as a heat generating material when the metal or alloy is used as a hydrogen generating material.

  For example, a heat-generating substance that reacts with oxygen and generates heat, such as iron powder, is also known. However, when iron powder is used as the exothermic substance, oxygen must be introduced during the reaction, and it occurs when the hydrogen generating substance and the exothermic substance are arranged in the same reaction vessel as described above. Problems such as reduction in the purity of hydrogen and reduction in the amount of hydrogen generated due to oxidation of the hydrogen generating substance by oxygen are likely to occur. Therefore, as the exothermic substance, a material that generates heat by reacting with water is preferably used.

  In particular, when a metal such as aluminum, silicon, zinc, or magnesium or an alloy mainly composed of one or more elements selected from aluminum, silicon, zinc, and magnesium is used as the hydrogen generating material, the exothermic material is used. It is preferable to use together. On the other hand, when the metal hydride is used as a hydrogen generating substance, hydrogen can be produced at a relatively good rate without using the exothermic substance. May be increased.

  When the hydrogen generating substance and the exothermic substance are used in combination, the amount of the hydrogen generating substance is preferably 85% by mass or more in a total of 100 mass% of the hydrogen generating substance and the exothermic substance introduced into the hydrogen generating substance storage container. . If the amount of hydrogen generating material in the total of the hydrogen generating material and the exothermic material is too small, the hydrogen generating amount may decrease, or if the amount of the exothermic material is too large, the heat generation may become intense and the hydrogen generating reaction may be difficult to control. .

  The exothermic substance may be put into the hydrogen generating substance storage container as a mixture obtained by uniformly or non-uniformly mixing with the hydrogen generating substance, or may be put into the hydrogen generating substance storage container separately from the hydrogen generating substance. In the latter case, for example, it is preferable to dispose the exothermic material in the vicinity of the mouth portion of the water supply pipe (40 in FIG. 6) related to the hydrogen generating material storage container. By arranging the exothermic material in this way, the inside of the reaction system can be heated more efficiently.

  There is no restriction | limiting in particular about the water storage container 42, For example, the tank etc. which store the water similar to the conventional hydrogen production apparatus 2 are employable.

  The water in the water storage container 42 is supplied to the hydrogen generating substance storage container 20a of the hydrogen supply cartridge 20 through the water supply pipe 40, thereby reacting with the hydrogen generating substance in the container 20a to generate hydrogen. In some cases, unreacted water present in the hydrogen generating substance storage container 20a is mixed into the generated hydrogen, and the mixture thereof is discharged out of the hydrogen production apparatus 2 through the hydrogen outlet pipe 29b.

  Therefore, as shown in FIG. 4, the hydrogen production apparatus 2 is preferably provided with a condensate separator 44 in the fuel flow path connecting the fuel cell 1 and the hydrogen production apparatus 2. The condensed water separator 44 is connected to the hydrogen generating substance storage container 20a through a hydrogen outlet pipe 29a, and a hydrogen outlet pipe 29b is attached. The water in the mixture with the hydrogen discharged from the hydrogen generating substance storage container 20a becomes condensed water by being cooled in the hydrogen outlet pipe 29a. When the hydrogen accompanying the condensed water is introduced into the condensed water separator 44, the condensed water falls to the lower part of the condensed water separator 44 by gravity and is separated.

  Then, as shown in FIG. 4, the condensed water separator 44 and the water storage container 42 are connected by the water recovery pipe 41 so that the water separated by the condensed water separator 44 is supplied to the water storage container 42. It can be recovered. Thus, by collecting the water separated by the condensate separator 44, it becomes possible to reduce the substantial supply amount of water used for hydrogen generation, and to make the water container 42 more compact. be able to.

  In FIG. 4, the water storage container is a separate hydrogen production apparatus from the hydrogen supply cartridge. However, the hydrogen supply cartridge has a water storage container together with a hydrogen generating substance storage container and a hydrogen removal apparatus. For example, as described above, the hydrogen production apparatus may be configured by only the hydrogen supply cartridge. That is, the condensate separator may also have a hydrogen supply cartridge. In this case, however, the structure of the hydrogen supply cartridge becomes complicated, and it is difficult to make the hydrogen supply cartridge compact. Therefore, the condensate separator is preferably provided outside the hydrogen supply cartridge.

  FIG. 5 schematically shows a configuration example of a fuel cell according to the fuel cell power generation system of the present invention. Although FIG. 5 is a cross-sectional view, in order to facilitate understanding of each component, some components are not hatched to indicate a cross section. Further, FIG. 5 does not show a configuration for enabling conduction between the positive electrode and the negative electrode of the MEA in the fuel cell 1 according to the fuel cell power generation system shown in FIGS. 6 and 7 described later.

  In the fuel cell 1 of FIG. 5, the MEA 100 in which the positive electrode composed of the positive electrode diffusion layer 101 and the positive electrode catalyst layer 102, the solid electrolyte membrane 103, and the negative electrode composed of the negative electrode diffusion layer 105 and the negative electrode catalyst layer 104 are sequentially laminated. Three MEAs 100 are arranged in a plane.

  On the positive electrode side of each MEA 100, positive electrode current collecting plates 57a and 57b, a positive electrode insulating plate 53, and a positive electrode panel plate 51 are sequentially arranged. Further, negative electrode current collecting plates 58a and 58b, a negative electrode insulating plate 54, and a negative electrode panel plate 52 are sequentially arranged on the negative electrode side of each MEA 100.

  All the MEAs 100 are sandwiched and integrated by the positive electrode panel plate 51 and the negative electrode panel plate 52. Although not shown in FIG. 5, adjacent MEAs 100 are connected in series by electrical connection between the positive electrode current collector plates 57a and 57b and the negative electrode current collector plates 58a and 58b.

  The positive electrode current collecting plates 57a and 57b, the positive electrode insulating plate 53, and the positive electrode panel plate 51 are provided with a plurality of oxygen introduction holes for introducing oxygen outside the fuel cell 1 into the positive electrode as air. Then, from the outer surface of the positive electrode panel plate 51 to the positive electrode diffusion layer 101 of the MEA 100 by the oxygen introduction holes of the positive electrode current collecting plates 57a and 57b, the oxygen introduction hole of the positive electrode insulating plate 53, and the oxygen introduction hole of the positive electrode panel plate 51. A plurality of reaching openings are formed, and oxygen (air) outside the fuel cell is supplied to the positive electrode diffusion layer 101 by diffusion from these openings.

  Further, in the fuel cell 1 of FIG. 5, fuel introduction holes for introducing the fuel (hydrogen) in the fuel tank portion 60 into the negative electrode are formed in the negative electrode current collecting plates 58a and 58b, the negative electrode insulating plate 54, and the negative electrode panel plate 52. A plurality are provided. Then, the negative electrode diffusion of the MEA 100 from the fuel tank 60 side surface of the negative electrode panel plate 52 by the fuel introduction holes of the negative electrode current collecting plates 58a and 58b, the fuel introduction hole of the negative electrode insulating plate 54, and the fuel introduction hole of the negative electrode panel plate 52. A plurality of openings reaching the layer 105 are formed, and the fuel in the fuel tank 60 is supplied to the negative electrode diffusion layer 105 from these openings.

  In the fuel cell 1 of FIG. 5, the positive electrode panel plate 51 and the negative electrode panel plate 52 (and the fuel tank portion 60) are fixed by bolts 63 and nuts 64. In FIG. 5, 59a and 59b are seals.

  The positive electrode diffusion layer 101, the positive electrode catalyst layer 102, the solid electrolyte membrane 103, the negative electrode catalyst layer 104, and the negative electrode diffusion layer 105 are the positive electrode diffusion layer 201, the positive electrode catalyst layer 202, and the solid electrolyte membrane 203 according to the MEA 200 described in FIG. The negative electrode catalyst layer 204 and the negative electrode diffusion layer 205 can be made of the same material.

  FIG. 6 shows a schematic diagram of another configuration example of the fuel cell power generation system of the present invention. In FIG. 6, components having the same functions as those in FIG. 1 are denoted by common reference numerals to avoid redundant description (the same applies to FIGS. 7 and 8 described later). In the fuel cell power generation system of FIG. 6, in each MEA 100 included in the fuel cell 1, the positive electrode and the negative electrode are connected by a lead body or the like via a resistor 7 so as to be conductive.

  In a fuel cell according to a fuel cell power generation system, even after the operation is stopped, hydrogen remains in the fuel cell, which may deteriorate the positive electrode and the negative electrode of the MEA and impair the life of the fuel cell. . However, in the fuel cell power generation system shown in FIG. 6, when the external load 6 is turned off and the operation of the fuel cell 1 is stopped, for example, a switch provided on the lead body that connects between the positive electrode and the negative electrode is provided in each MEA 100. The hydrogen remaining in the fuel cell 1 can be consumed by making the positive electrode and the negative electrode conductive by turning them on. As described above, in the fuel cell power generation system shown in FIG. 2, deterioration of the fuel cell 1 due to hydrogen remaining in the fuel cell 1 can be suppressed, and the life of the fuel cell can be extended.

  In the fuel cell power generation system of FIG. 6, the positive electrode and the negative electrode of each MEA 100 included in the fuel cell 1 are connected via a resistor 7. As the resistor 7, for example, a fuel cell according to the fuel cell power generation system is used. After stopping 1, it is sufficient to use one having a resistance value such that the time required for the voltage between the positive electrode and the negative electrode of the MEA 100 to be 0.1 V or less is within 1 minute. If the voltage between the positive electrode and the negative electrode of the MEA 100 can be lowered as described above in such a time, the connection may be made by connecting with a lead body or the like only through a switch without using a resistor.

  Furthermore, FIG. 7 shows a schematic diagram of another configuration example of the fuel cell power generation system according to the hydrogen supply cartridge of the present invention. In the fuel cell power generation system shown in FIG. 7, a monitoring device 8 is disposed between the fuel cell 1 and the hydrogen production device 2. The monitoring device 8 is not particularly limited as long as it is a device dedicated to hydrogen without leakage or the like. For example, a digital mass flow meter for monitoring the flow rate or a digital manometer for monitoring the supply pressure can be used. . By using such a monitoring device, the behavior of the gas can be directly grasped and reflected in the determination of whether or not the hydrogen supply cartridge can be removed.

  Although the present invention has been described above with reference to FIGS. 1 to 7, FIGS. 1 to 7 are only examples of the present invention, and the hydrogen supply cartridge of the present invention and the fuel cell power generation of the present invention. The system is not limited to that shown in FIGS.

  Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.

Example 1
<Fabrication of fuel cell>
A fuel cell power generation system having the configuration shown in FIG. 8 was produced. As the fuel cell 1, two fuel cells having the configuration shown in FIG. 5 (those configured by connecting three MEAs 100 in series) were connected in series. As the positive electrode and the negative electrode of MEA100, electrodes (“LT140E-W” manufactured by E-TEK, Pt amount: 0.5 mg / cm ² ) coated with Pt-supported carbon on carbon cloth were used. Further, “Nafion 112” manufactured by DuPont was used for the solid electrolyte membrane. Each electrode was 25 mm × 92 mm, and the solid electrolyte membrane was 29 mm × 96 mm.

  A positive electrode panel plate 51 made of stainless steel 304 and having a thickness of 2 mm was used. The positive electrode openings 21 were arranged in a total of 72 1 × 13 mm rectangular holes over the entire area corresponding to the upper part of the positive electrode diffusion layer 101 of each MEA 100 as shown in FIG. The negative electrode panel plate 52 has the same material and shape. That is, in the negative electrode panel plate, the oxygen introduction hole related to the positive electrode panel plate is a fuel introduction hole for forming the negative electrode opening (62 in FIG. 5).

  As the positive electrode current collecting plates 57a and 57b, those having a thickness of 0.3 mm in which nickel was plated with gold were used. The positive electrode insulating plate 53 is made of glass epoxy resin and has a thickness of 0.5 mm. The arrangement of the oxygen introduction holes of the positive electrode current collecting plates 57 a and 57 b and the positive electrode insulating plate 53 was arranged such that the positive electrode opening 61 could be formed together with the oxygen introduction holes of the positive electrode panel plate 51.

  The negative electrode current collecting plates 58 a and 58 b have the same material and shape as the positive electrode current collecting plates 57 a and 57 b, and the negative electrode insulating plate 54 has the same material and shape as the positive electrode insulating plate 53.

  The fuel tank 60 is made of glass epoxy resin and has a thickness of 3 mm. The depth inside the central tank is 2 mm. The seals 59a and 59b are made of silicon and have a thickness of 0.2 mm. The size of the hole formed in the portion where the electrode is accommodated was set to 26 m × 93 mm.

  The above members were stacked in the order shown in FIG. 5 and tightened with bolts 63 and nuts 64 to produce two fuel cells 1 having three MEAs 100.

<Production of cartridge for supplying hydrogen>
A hydrogen supply cartridge having the structure shown in FIG. 2 was used. The constituent members of the MEA 200 included in the hydrogen removing device 20b related to the hydrogen supply cartridge 20 were the same as the MEA of the fuel cell. The electrode was 30 mm square, and the solid electrolyte membrane was 35 mm square. As the positive electrode current collector plate 21, a stainless steel plate having a thickness of 2 mm obtained by performing gold plating was used. The air holes 21 a are arranged in a rectangular shape of 1 × 30 mm over the entire portion corresponding to the upper part of the positive electrode diffusion layer 201 of the MEA 200. The negative electrode current collector plate 22 also has the same shape and material as the positive electrode current collector plate 21. The seal 23 is made of silicon rubber and has a thickness of 0.2 mm. The size of the hole formed in the portion where the electrode is accommodated was 31 mm square.

  The above members were stacked in the order shown in FIG. 2 and tightened with bolts 24 and nuts 25 to produce MEA 200. Also, a conductive plate 27 for conducting the positive and negative electrodes of the MEA 200 and an insulating film 28 for preventing leakage are provided at the positions shown in FIG. Further, a hydrogen removing device 20b was fabricated so that it could be fixed to the hydrogen generation container 20a with screws.

Further, as the hydrogen generating substance storage container 20a, the one provided with the screw part 26 and the hydrogen outlet pipe 29 shown in FIG. 2 on the upper part of a polypropylene prismatic container having an internal volume of 50 cm ³ is used. 20.7 g of aluminum powder (hydrogen generating substance) having an average particle diameter of 6 μm and 3.5 g of calcium oxide (exothermic substance) were added. The hydrogen generating substance storage container 20a and the hydrogen removing device 20b constitute a hydrogen supply cartridge.

<Production of hydrogen production equipment>
A hydrogen production apparatus having the configuration shown in FIG. 4 was used. Polypropylene pipes having an inner diameter of 2 mm and an outer diameter of 3 mm were used for the water supply pipe 43, the hydrogen outlet pipes 29a and 29b, and the water recovery pipe 41. Further, as the water storage container 42, a polypropylene prismatic container having an internal volume of 50 cm ³ was used, and 30 g of water was put therein. Further, a polypropylene prismatic container having an internal volume of 30 cm ³ was used for the condensate separator 44. These members and the hydrogen supply cartridge were connected so as to have the configuration shown in FIG. 4 to assemble a hydrogen production apparatus.

<Assembly of fuel cell power generation system>
The fuel cell and the hydrogen production apparatus were arranged as shown in FIG. 8 to assemble a fuel cell power generation system.

<Power generation test>
The water supply pump 43 supplies the water in the water storage container 42 to the hydrogen generating substance storage container 20a of the hydrogen supply cartridge 20 to generate hydrogen, and the external load 6 performs a power generation test of the fuel cell 1 to 4.0V. For 2 hours. Note that when the operation of the fuel cell 1 to be described later was stopped, the resistor 7 was operated to remove residual hydrogen in the fuel cell power generation system.

  At the same time as the operation of the fuel cell 1 is stopped, the supply of water to the hydrogen generating substance storage container 2a of the hydrogen supply cartridge 20 is stopped, and after the power generation system is stopped, the temperature sensor 20c installed in the hydrogen generating substance storage container 20a. When the temperature measured by the above became 50 ° C. or less, the hydrogen supply cartridge 20 was removed, and the hydrogen removing device 20b was operated to remove excess hydrogen. At this time, in order to confirm whether surplus hydrogen has been removed, a monitoring device (“Mass Flow 3660” manufactured by KOFLOC) is attached to the hydrogen supply cartridge 20, and the hydrogen generation rate from the hydrogen generating substance storage container 20a and the hydrogen supply The total amount of hydrogen discharged to the outside after 1 hour from the removal of the cartridge was measured. The results are shown in Table 1.

Comparative Example 1
A hydrogen supply cartridge was produced in the same manner as in Example 1 except that no hydrogen removal device was installed, and a fuel cell power generation system was produced in the same manner as in Example 1 except that this hydrogen supply cartridge was used. Then, a power generation test similar to that in Example 1 was performed, and after the fuel cell power generation system was stopped, the hydrogen supply cartridge was removed, and the hydrogen generation rate from the hydrogen generating substance storage container and one hour after the removal of the hydrogen supply cartridge were removed. The total amount of hydrogen discharged to the outside was measured in the same manner as in Example 1. The results are also shown in Table 1.

  As shown in Table 1, in the fuel cell power generation system of Comparative Example 1 configured using a hydrogen supply cartridge that does not have a hydrogen removal device, 137 ml of hydrogen is 5.0 ml from the hydrogen supply cartridge that is removed after the system is stopped. The fuel cell power generation system of Example 1 configured using a hydrogen supply cartridge equipped with a hydrogen removal device was stopped while the hydrogen was discharged at a rate of / min and continued to be discharged for a relatively long time. Since the hydrogen discharged from the hydrogen supply cartridge removed later was quickly oxidized by the catalytic reaction of the negative electrode because the positive electrode and the negative electrode of the MEA incorporated in the hydrogen removal device were in a conductive state, the hydrogen supply cartridge The amount of hydrogen discharged from the plant is extremely small. Therefore, with the hydrogen supply cartridge (fuel cell power generation system) of Example 1, surplus hydrogen can be quickly processed after the removal of the hydrogen supply cartridge, and the amount discharged outside the system can be reduced.

  With the hydrogen supply cartridge of the present invention, it is possible to suppress discharge of hydrogen out of the system when the hydrogen supply cartridge is removed after the operation of the device such as the fuel cell is stopped. Therefore, a device to which the hydrogen supply cartridge of the present invention is applied (for example, the fuel cell power generation system of the present invention) is suitable for indoor use. In addition, since the suppression of the discharge of hydrogen to the outside of the system can be achieved with a relatively simple mechanism, it is easy to reduce the size of various hydrogen utilizing devices such as a fuel cell power generation system. Therefore, the hydrogen supply cartridge of the present invention can be preferably used as a fuel cartridge for various uses to which a conventional fuel cell is applied, for example, for use as a power source for high-performance portable electronic devices.

It is a schematic diagram which shows the structural example of the fuel cell power generation system of this invention. It is a schematic diagram which shows the structural example of the cartridge for hydrogen supply of this invention. It is a schematic diagram which shows the other structural example of the cartridge for hydrogen supply of this invention. It is a schematic diagram which shows the structural example of the hydrogen production apparatus using the cartridge for hydrogen supply of this invention. It is a cross-sectional schematic diagram which shows the structural example of the fuel cell which concerns on the fuel cell power generation system of this invention. It is a schematic diagram which shows the other structural example of the fuel cell power generation system of this invention. It is a schematic diagram which shows the other structural example of the fuel cell power generation system of this invention. 1 is a schematic diagram showing a configuration of a fuel cell power generation system of Example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Fuel cell 2 Hydrogen production apparatus 20 Hydrogen supply cartridge 20a Hydrogen generating substance storage container 20b Hydrogen removal apparatus 100, 200 Integrated electrode / electrolyte (MEA)

Claims (8)

A cartridge for supplying hydrogen that can be connected to an apparatus using hydrogen,
A hydrogen supply cartridge comprising: a storage container capable of storing a hydrogen generating substance that generates hydrogen by a reaction; and a hydrogen removing device for removing surplus generated hydrogen to prevent dissipating to the outside. .   The hydrogen supply cartridge according to claim 1, wherein the hydrogen removing device operates when disconnecting from a device using hydrogen.   The hydrogen supply cartridge according to claim 1 or 2, wherein the hydrogen removing device includes a substance having reactivity with hydrogen or a catalyst having hydrogen oxidation activity.   The hydrogen supply cartridge according to claim 3, wherein the hydrogen removing device has a hydrogen storage alloy. Contains a material that generates hydrogen by reacting with water as a hydrogen generator,
The hydrogen supply cartridge according to any one of claims 1 to 4, further comprising means for continuously or intermittently supplying water to the hydrogen generating substance.   The hydrogen supply cartridge according to claim 5, wherein the hydrogen generating substance is a metal hydride.   6. The hydrogen supply cartridge according to claim 5, wherein the hydrogen generating substance is at least one metal selected from the group consisting of aluminum, silicon, zinc and magnesium, and an alloy mainly composed of one or more of these elements. .   A fuel cell main body comprising an electrode / electrolyte integrated body having a positive electrode for reducing oxygen, a negative electrode for oxidizing hydrogen, and a solid electrolyte membrane disposed between the positive electrode and the negative electrode, and claims 1 to 7 A fuel cell power generation system comprising the hydrogen supply cartridge according to any one of the above.

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