JP2010097721A - Hydrogen generator, hydrogen generation method, and power feeding device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen generator and a hydrogen generation method, capable of controlling the generation amount of hydrogen by promoting generation of steam in generation of hydrogen by supplying steam to a hydrogen generating agent, and a power feeding device provided with the hydrogen generator. <P>SOLUTION: The hydrogen generator 30 for generating hydrogen to be supplied to a fuel cell includes a water storage part 31 storing water, a hydrogen generating agent 32 which reacts with steam resulting from vaporization of the water to generate hydrogen; and a fan 33 for fluidizing the steam. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hydrogen generator that generates hydrogen to be supplied to a fuel cell, a hydrogen generation method, and a power supply apparatus including the hydrogen generator.

  Conventionally, hydrogen generators that generate water by supplying water include those mainly composed of metals such as iron and aluminum, and those mainly composed of metal hydrides such as magnesium hydride and calcium hydride. It is known (see, for example, Patent Document 1). In particular, when a hydrogen generator mainly composed of calcium hydride is used, the reaction rate with water is steep, so there is a problem that hydrogen is generated explosively in the initial stage when water is supplied in liquid (water). there were.

  For example, when 1 g of calcium hydride is completely reacted with water, 1.16 L (theoretical amount) of hydrogen is generated, 0.89 g (theoretical amount) of water is required, and a water generation rate of 1 L / h. In this case, it is necessary to supply water at about 1 mL / h (0.28 μL / second). However, even if it is attempted to supply water at such a small flow rate using a syringe pump, the flow rate becomes uneven because the supply amount cannot be precisely controlled, and the influence of the size of the droplets is also affected. The amount of supply increases, especially when water is first supplied. This reacted rapidly with calcium hydride, and hydrogen was explosively generated at an early stage.

  Therefore, Patent Documents 1 and 2 disclose a hydrogen generation method for supplying generated water vapor to calcium hydride via a hydrophobic porous body for the purpose of appropriately controlling the reaction rate between calcium hydride and moisture. Has been.

  In the methods disclosed in Patent Documents 1 and 2, the amount of water vapor supplied to the hydrogen generator is controlled by the average pore diameter, porosity, surface area, and the like of the hydrophobic porous body. Furthermore, in the method disclosed in Patent Document 1, by adjusting the contact area between the hydrophobic porous body and water, the water pressure acting on the hydrophobic porous body, and the like, the water vapor that permeates the hydrophobic porous body is adjusted. The amount is controlled.

  However, in the methods of Patent Documents 1 and 2, since the generation of water vapor itself is performed by natural evaporation, the amount of water vapor generation is mainly determined by the amount of saturated water vapor depending on the temperature, and the amount of water vapor generation is reduced. It was difficult to control actively.

JP 2003-313001 A JP 2004-269323 A

  Accordingly, an object of the present invention is to provide a hydrogen generation apparatus, a hydrogen generation method, and a hydrogen generation apparatus capable of controlling the generation amount by promoting the generation of water vapor when supplying water vapor to the hydrogen generating agent to generate hydrogen. It is providing the electric power feeder provided with a generator.

  In order to solve the above problems, a hydrogen generator according to the present invention is a hydrogen generator that generates hydrogen to be supplied to a fuel cell, and includes a water storage section that stores water, and a reaction between the water vaporized and water vapor. And a hydrogen generating agent for generating hydrogen and a blowing means for causing the water vapor to flow.

  According to the hydrogen generator of the present invention, the water vapor vaporized from the water accommodated in the water accommodating part can be caused to flow by the blowing means. By causing the water vapor to flow, the evaporation of water in the water storage portion can be promoted, and the amount of water vapor generated can be controlled. That is, normally, the amount of water vapor generated is determined by the amount of saturated water vapor, but by flowing the vaporized water vapor, the amount of water vapor in the vicinity of the water containing part (especially near the surface of the water) is reduced, and further water evaporation occurs. Can be urged.

  In the hydrogen generator of the present invention, it is preferable that the blowing means has an evaporation amount control function for controlling the amount of water vapor generated by the amount of blowing.

  Compared to the case where water vapor is generated by natural evaporation, according to the hydrogen generator of the present invention, the evaporation amount control function provided in the air blowing means can control the amount of water vapor generated by changing the air flow. . It is possible to increase the amount of water vapor generated by increasing the amount of air flow, or to reduce the amount of water vapor generated by reducing the amount of air flow. By controlling the amount of water vapor generated, the amount of water vapor supplied to the hydrogen generating agent can also be controlled. As a result, the amount of hydrogen generated from the hydrogen generating agent can also be controlled.

  In the hydrogen generator according to the present invention, it is preferable that the water accommodating portion is provided with a water-absorbing sheet-like member that is partially in contact with the accommodated water, and the blowing unit blows air to the sheet-like member.

  A water-absorbing sheet-like member is provided so that a part contacts the water accommodated in the water accommodating portion, and the sheet-like member is blown by the blowing means. According to this structure, since the sheet-like member has water absorption, a part of the sheet-like member absorbs water by capillary action when it comes into contact with the water in the water storage portion, and water penetrates the entire surface. Evaporation of water from the sheet-like member is promoted by blowing air to the sheet-like member by the blowing means. In addition, the amount of water evaporation, that is, the amount of water vapor generated can be easily and reliably controlled by turning on / off the power supply of the blowing means and adjusting the on / off time.

  In the hydrogen generator of the present invention, it is preferable that the sheet-like member has a cylindrical portion, and the blowing unit blows air into the cylindrical portion.

  Since the surface area of the sheet-like member is increased by having the cylindrical portion, evaporation of water from the sheet-like member is further promoted by blowing air into the cylindrical portion with the blowing means.

  In the hydrogen generator of the present invention, it is preferable that a check valve is provided in a water vapor supply path for supplying the water vapor to the hydrogen generating agent.

  As described above, the amount of hydrogen generated from the hydrogen generating agent can be controlled by controlling the amount of water vapor supplied to the hydrogen generating agent. At this time, the water vapor is supplied to the hydrogen generating agent via the water vapor supply path. However, when the water vapor flows back through the water vapor supply path and returns to the water storage unit, the amount of hydrogen generated cannot be accurately controlled. By providing a check valve in the water vapor supply path, the back flow of water vapor can be prevented, the amount of water vapor supplied to the hydrogen generating agent can be controlled, and the amount of hydrogen generated can be accurately controlled.

  In order to solve the above-described problems, a power supply device according to the present invention includes a hydrogen generator according to the present invention, a fuel cell that supplies power generated by the hydrogen generator, and generates power, and at the initial stage of power generation by the fuel cell. And an auxiliary battery that supplies power to the blowing means.

  According to the power supply device of the present invention, the auxiliary battery supplies power to the blower means at the initial stage of power generation by the fuel cell, so that the blower means can be operated even at the initial stage of power generation such as at the start of power generation by the fuel cell. In addition, it is possible to stably supply water vapor to the hydrogen generating agent.

  In order to solve the above problems, a hydrogen generation method according to the present invention is a hydrogen generation method for generating hydrogen to be supplied to a fuel cell, and promotes the generation of water vapor from air by blowing air, Hydrogen is generated by reacting with the water vapor.

  The action and effect of the hydrogen generation method with such a configuration is as described above. According to the hydrogen generation method of the present invention, the generation amount of water vapor can be controlled by accelerating the generation of water vapor by blowing air. it can.

  A preferred embodiment of a power feeding device according to the present invention will be described with reference to the drawings. 1A and 1B are diagrams showing an example of a hydrogen generator of the present invention, in which FIG. 1A is a plan view and FIG. 1B is a cross-sectional view taken along line II of FIG.

<Hydrogen generator>
As shown in FIG. 1, the hydrogen generator 30 of the present invention includes a water storage unit 31 that stores water, a hydrogen generating agent 32 that generates hydrogen by reacting with water vapor, and a fan (for blowing means) that flows water vapor. Equivalent) 33.

  Water is stored in the water storage portion 31. The water may be configured to be simply stored in the container-shaped water storage case 31a. However, in the present invention, the water storage case 31a is provided so that the water remains in a certain place even if the posture to be used is changed. It is preferable that the water is retained by the water retaining material 31b disposed inside.

  Any water-retaining material can be used as long as it can be impregnated with water. Sponges, water-absorbing resins, absorbent cotton, water-absorbing nonwoven fabrics, water-absorbing paper, etc. are preferable.

  The water accommodating portion 31 is provided with a water absorbing sheet (corresponding to a sheet-like member) 34 having an end 34a in contact with the accommodated water and having a cylindrical portion 34b. The end portion 34 a contacts the water of the water retaining material 31 b through the slit 31 c provided in the water storage portion 31. The water-absorbing sheet 34 has water absorption, and the end 34a contacts the water of the water retaining material 31b to absorb water by a capillary phenomenon, so that water penetrates the entire surface of the tubular portion 34b. By penetrating the cylindrical portion 34b of the water absorbent sheet 34, the water is easily evaporated.

  The water absorbent sheet 34 may be any water-impregnated sheet, but is preferably a water absorbent resin, absorbent cotton, a water absorbent nonwoven fabric, a water absorbent paper, or the like.

  The periphery of the water absorbing sheet 34 is covered with a wind conditioned cover 37 having a U-shaped cross section. The wind regulation cover 37 is joined to the water accommodation case 31a. The air conditioning cover 37 has a structure in which a portion adjacent to the fan 33 is joined to the fan 33 and the surface opposite to the fan 33 is open, so that the wind sent from the fan 33 passes through the interior of the air conditioning cover 37. It has become.

  The fan 33 has substantially the same width as the air conditioning cover 37, and the wind taken from the blade portion of the fan 33 can be sent into the air conditioning cover 37 as indicated by the broken line in the figure. In other words, the fan 33 can send wind to the water absorbing sheet 34 (cylindrical portion 34 b) in the wind regulation cover 37. Thereby, the water vapor evaporated from the surface of the water absorbing sheet 34 can be flowed, and the evaporation of water can be promoted.

  Moreover, it is preferable that the fan 33 can adjust the ventilation volume. By adjusting the amount of air blown, it is possible to adjust the amount of air sent into the air conditioned cover 37. In other words, it is preferable that the fan 33 can adjust the amount of air blown to the water absorbing sheet 34 in the air conditioning cover 37. By increasing the amount of air blown to the water absorbent sheet 34, the amount of water vapor generated can be increased. Conversely, by reducing the amount of air blown, the amount of water vapor generated can also be reduced.

  The water vapor generated from the water absorbing sheet 34 is discharged from the end portion 37 a of the wind regulation cover 37 and supplied to the hydrogen generating agent 32 through the water vapor supply path 38. The hydrogen generating agent 32 is disposed in the internal space S formed by the internal space forming part 36.

<Hydrogen generator>
The hydrogen generating agent 32 in the present invention may be any one as long as it reacts with water vapor to generate hydrogen (hereinafter sometimes referred to as hydrogen gas), and examples thereof include metals, metal hydride compounds, and mixtures of both. It is done. These hydrogen generators 32 may be used as single particles, and if necessary, those further containing a catalyst component, an alkaline inorganic compound, and aggregation-suppressing particles can be used. In the present invention, a sheet-like material or a pulverized material in which a metal hydride compound is embedded with a resin is preferable. In the case of embedding with a resin, a porous body is preferable from the viewpoint of reactivity with water vapor.

  Examples of the metal include aluminum particles, iron particles, and magnesium particles. Examples of the metal catalyst include nickel, vanadium, manganese, titanium, copper, silver, zinc, zirconium, cobalt, chromium, calcium, and alloys thereof.

  Examples of the metal hydride compound include calcium hydride, lithium hydride, potassium hydride, sodium borohydride, potassium borohydride, lithium aluminum hydride, sodium aluminum hydride, and magnesium hydride. All of these compounds are known to react rapidly or explosively with water to generate hydrogen gas, and all show reactivity with water higher than magnesium hydride.

  Moreover, you may contain metals, such as aluminum, iron, magnesium, and calcium, metal hydrogen complex compounds other than the above, as hydrogen generating agents other than the said compound. A plurality of metal hydride compounds, metals, and metal hydride complex compounds can be used in combination, or they can be used in combination. When a compound is used in combination, it is preferable to include a compound that facilitates the formation of pores by bubbles. As such a compound, calcium hydride is particularly preferable.

  The average particle size of the granular hydrogen generator is preferably 1 to 100 μm, more preferably 6 to 30 μm, and still more preferably 8 to 10 μm from the viewpoint of controlling dispersibility and reactivity in the porous body.

  In the case of embedding with a resin, the content of the hydrogen generating agent is preferably 10 to 60% by weight, more preferably 30 to 50% by weight in the porous body, from the viewpoint of ensuring appropriate reactivity and a certain amount of hydrogen generation. .

  Examples of the resin used include a thermosetting resin, a thermoplastic resin, and a heat resistant resin, and a thermosetting resin is preferable. Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylic resin, fluororesin, polyester, and polyamide. Examples of the heat resistant resin include aromatic polyimide, polyamide, and polyester.

  Examples of the thermosetting resin include epoxy resins, unsaturated polyester resins, phenol resins, amino resins, polyurethane resins, silicone resins, and thermosetting polyimide resins. Especially, an epoxy resin is preferable from a viewpoint which can maintain a porous structure moderately during hydrogen generating reaction.

  When the resin is non-porous or porous with a low porosity, it is preferable to mainly use a water-soluble resin or a water-absorbing resin. Examples of the water-soluble resin include methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, and polyethylene oxide. Examples of water-absorbing resins include cross-linked acrylate polymers, cross-linked vinyl alcohol-acrylate copolymers, cross-linked maleic anhydride grafted polyvinyl alcohol, and acrylate-methacrylate copolymers. Cross-linked product, cross-linked product of saponified product of methyl acrylate-vinyl acetate polymer, cross-linked product of starch-acrylate graft copolymer, cross-linked product of hydrolyzate of starch-acrylonitrile copolymer, starch-ethyl acrylate Examples include a cross-linked product of a saponified graft copolymer, a cross-linked product of carboxymethyl cellulose, and the like.

  The content of the resin is preferably 30 to 90% by weight, more preferably 50 to 70% by weight in the porous body, from the viewpoint of securing an appropriate shape retention and a certain amount of hydrogen generation.

  The resin may contain other components such as a catalyst, a filler, and a foaming agent as optional components other than the above components. As the catalyst, an alkali compound such as sodium hydroxide, potassium hydroxide and calcium hydroxide is also effective in addition to the metal catalyst for the hydrogen generator.

  Examples of the foaming agent include a liquid that is phase-separated and dispersed in an uncured thermosetting resin and vaporizes at the reaction temperature of the thermosetting resin. It is also possible to add a small amount of a reaction solution that reacts with the hydrogen generator to generate hydrogen gas to the uncured thermosetting resin. Examples of such a reaction solution include water, an aqueous acid solution, and an alkaline aqueous solution.

  In this invention, the case where it has the structure made porous by the bubble is preferable. The bubbles for making the pores may be generated by a foaming agent, but are preferably hydrogen gas generated from a hydrogen generating agent.

  That is, the porous body is obtained by mixing a particulate hydrogen generator and an uncured thermosetting resin, and then applying the mixture to a water absorbent sheet to generate a hydrogen gas from the hydrogen generator. It is preferable to manufacture by the manufacturing method including the process of hardening | curing.

The porous body is preferably a density of 0.1~1.2g / cm ^3, more preferably ^{0.2~0.9g / cm 3, 0.3~0.5g / cm} 3 More preferably. By having a density in this range, the permeability of the reaction solution becomes appropriate, and the handleability becomes better. Such a density can be controlled by, for example, the amount of hydrogen gas generated.

  The bubble diameter of the hydrogen generating porous body is preferably 0.1 to 2 mm, more preferably 0.5 to 1 mm, from the viewpoint of appropriately controlling the permeability of the reaction solution. Such a bubble diameter can be controlled by, for example, the amount of hydrogen gas generated. In order to control the bubble diameter and density, the thermosetting resin may be cured under pressure.

  In order to generate hydrogen gas from the hydrogen generator, it is possible to add a small amount of reaction liquid to the uncured thermosetting resin in advance, or to use the reaction liquid contained in the uncured thermosetting resin. However, a method of desorbing hydrogen gas from the hydrogen generator (in the case of a metal hydride compound) by heating for the curing reaction is preferable.

  The temperature at which hydrogen gas is desorbed from the hydrogen generator varies depending on the type of metal hydride compound, but is preferably 50 to 250 ° C, more preferably 80 to 200 ° C. That is, it is preferable to select a temperature within this range as the curing temperature of the uncured thermosetting resin. It is also possible to change the generation temperature of hydrogen gas and the curing temperature.

  The thickness of the sheet-like porous body obtained by curing is preferably from 0.1 to 10 mm, more preferably from 0.5 to 2 mm, from the viewpoint of allowing water and the like to permeate sufficiently and uniformly to perform a uniform reaction.

  The hydrogen generating agent 32 in the present invention is surrounded by a packaging material 35 at least partially formed of a hydrophobic porous film 35a. Hydrogen gas is generated by the flow of water vapor through the hydrophobic porous membrane 35a.

  The packaging material 35 (or the hydrogen generating agent 32) may not be fixed to the internal space forming portion 36, but is preferably fixed to the internal space forming portion 36 by adhesion or the like.

  The hydrophobic porous membrane 35a can permeate water vapor and hydrogen gas without permeating water. Accordingly, the pore diameter of the hydrophobic porous membrane 35a is preferably 0.1 to 10 μm. 0.5-5 micrometers is more preferable. The thickness of the hydrophobic porous membrane 35a is preferably 10 to 500 μm, more preferably 50 to 200 μm, from the viewpoint of providing sufficient air permeability and a certain level of strength.

  Examples of the material of the hydrophobic porous membrane 35a include fluorine resin, polyolefin resin, polyether sulfone, polysulfone, and the like. Of these, fluorine resins such as polytetrafluoroethylene and polyolefin resins such as polypropylene are preferable.

  In the packaging material 35 other than the hydrophobic porous membrane 35a, a film, sheet, case, or the like made of the same material as described above can be used. However, in this invention, it is preferable that the whole packaging material 35 is formed with the hydrophobic porous membrane 35a.

  The packaging material 35 (or the hydrophobic porous membrane 35a) is preferably formed in a bag shape, and the opening is sealed after the hydrogen generating agent 32 is introduced inside. Examples of the sealing method include heat fusion and adhesion with an adhesive. In the illustrated example, four sides of the two hydrophobic porous membranes 35a are sealed by thermal fusion.

<Configuration of power generation cell>
A fuel cell that generates electricity by being supplied with hydrogen generated by the hydrogen generator of the present invention will be described with reference to the drawings. 2A and 2B are diagrams showing an example of a fuel cell, in which FIG. 2A is a perspective view, FIG. 2B is a plan view, FIG. 2C is a perspective view showing a configuration of a metal plate, and FIG. FIG. 3B is a sectional view taken along the line II-II, and FIG. 3B is a sectional view taken along the line II-II.

  As shown in FIG. 2, the fuel cell includes a plurality of unit cells C1 to C4 (hereinafter, each unit cell is referred to as a unit cell C when it is not necessary to distinguish each unit cell). And the conductive layers of the other unit cells C are electrically connected to each other by a connecting portion. In the present embodiment, for example, the first conductive layer (first metal layer 4) of the unit cell C1 and the second conductive layer (second metal layer 5) of the unit cell C2 adjacent thereto are electrically connected (in series). In this example, any one unit cell C and another unit cell C can be connected in parallel. In that case, the first conductive layers and the second conductive layers of any unit cell C and the other unit cell C are electrically connected. Of course, it is also possible to combine parallel connection and series connection.

  The number of unit cells C to be connected can be set according to the required voltage or current. In the present embodiment, an example in which four unit cells C1 to C4 are connected is shown, but the number of unit cells C may be one, or five or more. For example, using eight unit cells, two pairs can be connected in parallel to form four pairs, and each pair can be connected in series. In this case, with respect to the configuration in which four unit cells are connected in series, the voltage is the same, but the amount of current can be doubled.

  Each unit cell C in the present embodiment includes a solid polymer electrolyte layer 1, a first electrode layer 2 and a second electrode layer 3 provided on both sides of the solid polymer electrolyte layer 1, the electrode layers 2, 3 and a first conductive layer and a second conductive layer respectively disposed on the outer side. In the present embodiment, the first conductive layer and the second conductive layer are formed from the first metal layer 4 and the second metal layer 5 having exposed portions that partially expose the first electrode layer 2 and the second electrode layer 3. An example will be shown.

  Examples of the material for the conductive layer include metals, conductive polymers, conductive rubbers, conductive fibers, conductive pastes, and conductive paints.

  The solid polymer electrolyte layer 1 may be any solid polymer membrane type fuel cell as long as it is used, but from the viewpoint of chemical stability and conductivity, a sulfonic acid group that is a super strong acid is used. A cation exchange membrane made of a perfluorocarbon polymer is preferably used. Nafion (registered trademark) is preferably used as such a cation exchange membrane. In addition, for example, a porous film made of a fluororesin such as polytetrafluoroethylene impregnated with the above Nafion or other ion conductive material, a porous film made of a polyolefin resin such as polyethylene or polypropylene, or a non-woven fabric. A material carrying Nafion or another ion conductive material may be used.

  The thinner the solid polymer electrolyte layer 1 is, the more effective it is to make the whole thinner. However, considering the ion conduction function, strength, handling property, etc., 10 to 300 μm can be used, but 25 to 50 μm. preferable.

  The electrode layers 2 and 3 may be any as long as they cause an electrode reaction on the anode side and the cathode side near the surface of the solid polymer electrolyte layer 1. Among them, the one that exhibits the function as a gas diffusion layer to supply and discharge the fuel gas, the fuel liquid, the oxidizing gas, and the water vapor and at the same time exhibits the current collecting function can be preferably used. As the electrode layers 2 and 3, the same or different ones can be used, and it is preferable to support a catalyst having an electrode catalytic action on the base material. The catalyst is preferably supported at least on the inner surface side in contact with the solid polymer electrolyte layer 1.

  As the electrode substrate of the electrode layers 2 and 3, for example, conductive carbon such as carbon paper, fibrous carbon such as carbon fiber nonwoven fabric, and an aggregate of conductive polymer fibers can be used. It is also possible to use the electrode layers 2 and 3 that are attached to the solid polymer electrolyte layer 1 by directly attaching the catalyst to the solid polymer electrolyte layer 1 or supporting the catalyst on conductive particles such as carbon black.

  In general, the electrode layers 2 and 3 are prepared by adding a water-repellent substance such as a fluororesin to such a conductive porous material. When the catalyst is supported, a catalyst such as platinum fine particles and fluorine It is formed by mixing a water-repellent substance such as a resin, mixing it with a solvent to form a paste or ink, and then applying this to one side of an electrode substrate that should face the solid polymer electrolyte membrane. The

  In general, the electrode layers 2 and 3 and the solid polymer electrolyte layer 1 are designed according to the reducing gas and the oxidizing gas supplied to the fuel cell. In the present invention, it is preferable to use air as the oxidizing gas and hydrogen gas as the reducing gas. It is also possible to use a fuel liquid such as methanol instead of the reducing gas.

  For example, when hydrogen gas and air are used, the second electrode layer 3 on the cathode side on which air is naturally supplied (in this specification, the anode side is assumed to be the first electrode layer and the cathode side is assumed to be the second electrode layer). In this case, since a reaction between oxygen and hydrogen ions occurs and water is generated, it is preferable to design according to the electrode reaction. In particular, under the operating conditions of low operating temperature, high current density, and high gas utilization rate, the electrode porous body is likely to be clogged (flooded) due to the condensation of water vapor, particularly at the air electrode where water is generated. Therefore, in order to obtain stable characteristics of the fuel cell over a long period of time, it is effective to ensure the water repellency of the electrode so that the flooding phenomenon does not occur.

  As the catalyst, at least one metal selected from platinum, palladium, ruthenium, rhodium, silver, nickel, iron, copper, cobalt and molybdenum, or an oxide thereof can be used. A supported one can also be used.

  The thickness of the electrode layers 2 and 3 is more effective for reducing the overall thickness as the thickness is reduced. However, in consideration of electrode reaction, strength, handling property, etc., 1 to 500 μm is preferable, and 100 to 300 μm is more preferable. The electrode layers 2 and 3 and the solid polymer electrolyte layer 1 may be laminated and integrated in advance by adhesion, fusion, coating formation, or the like, or may simply be arranged in a stacked manner. Such a laminated body can also be obtained as a membrane / electrode assembly (MEA), and may be used.

  In the present invention, the outer shape of the first electrode layer 2 and the second electrode layer 3 may be smaller than the outer shape of the solid polymer electrolyte layer 1, but the outer shape of the first electrode layer 2 and the second electrode layer 3 and the solid polymer. It is preferable that the outer shape of the electrolyte layer 1 is the same. If the outer shape of the electrode layer is the same as the outer shape of the solid polymer electrolyte layer, the laminate of the electrode plate and the solid polymer electrolyte can be punched out to produce a solid polymer electrolyte / electrode / joint. The cost of the joined body can be reduced by the effect. Moreover, the outer periphery of a metal layer is formed inside from the outer periphery of an electrode layer, Therefore The outer periphery of an electrode layer and the outer periphery of a solid polymer electrolyte layer can be sealed more reliably.

  A first metal layer 4 on the anode side is disposed on the surface of the anode side electrode layer 2, and a second metal layer 5 on the cathode side is disposed on the surface of the cathode side electrode layer 3 (in this specification, the anode side Is the first metal layer and the cathode side is the second metal layer). The first metal layer 4 has an exposed portion that partially exposes the first electrode layer 2. In the present embodiment, the anode side metal layer 4 is provided with an opening 4 a for supplying fuel gas or the like. An example is shown.

  The exposed portion of the first metal layer 4 may be any number, shape, size, formation position, etc. as long as the anode-side electrode layer 2 can be exposed. The opening 4a of the anode-side metal layer 4 is, for example, provided with a plurality of circular holes, slits, or the like regularly or randomly, or provided with the openings 4a by a metal mesh, or the first metal layer 4 as a comb electrode. The anode side electrode layer 2 may be exposed in any shape. The ratio (opening ratio) at which the area of the opening 4a is tightened is preferably 10 to 50%, more preferably 15 to 30%, from the viewpoint of the balance between the contact area with the electrode and the gas supply area.

  Further, the second metal layer 5 on the cathode side has an exposed portion that partially exposes the second electrode layer 3. In this embodiment, oxygen in the air is supplied to the cathode side metal layer 5 (naturally An example in which a large number of openings 5a for intake) is provided is shown. As long as the cathode-side electrode layer 3 can be exposed, the number, shape, size, formation position, and the like of the openings 5a may be any. The opening 5a of the cathode-side metal layer 5 is provided with, for example, a plurality of circular holes or slits regularly or randomly, or the openings 5a are formed by a metal mesh, and the second metal layer 5 is like a comb-shaped electrode. The cathode side electrode layer 3 may be exposed in any shape. From the viewpoint of the balance between the contact area with the electrode and the supply area of the gas, the ratio of the area of the opening 5a portion (opening ratio) is preferably 10 to 50%, and more preferably 15 to 30%.

  As the metal layers 4 and 5, any metal can be used as long as it does not adversely affect the electrode reaction, and examples thereof include stainless steel plates, nickel, copper, and copper alloys. However, copper, a copper alloy, a stainless steel plate, and the like are preferable from the viewpoints of conductivity, cost, shape imparting property, strength for pressurization, and the like. Moreover, what gave metal plating, such as gold plating, to said metal may be used.

  In addition, although the thickness of the metal layers 4 and 5 is effective in reducing the overall thickness as the thickness is reduced, considering conductivity, cost, weight, shape imparting property, strength for pressurization, etc., the thickness is 10 to 1000 μm. Preferably, 50-200 micrometers is more preferable.

  In the present invention, from the viewpoint of satisfactorily integrating the electrode layers 2 and 3 and the metal layers 4 and 5 with a resin, the outer periphery of the first metal layer 4 is formed on the inner side of the outer periphery of the first electrode layer 2. It is preferable that the outer periphery of the second metal layer 5 is formed on the inner side of the outer periphery of the second electrode layer 3. The outer periphery of the first metal layer 4 may be formed outside the outer periphery of the first electrode layer 2, and the outer periphery of the second metal layer 5 may be formed outward from the outer periphery of the second electrode layer 3. May be.

  When at least a part of the metal layer 4 and the metal layer 5 is exposed from the resin, electricity can be taken out using the part as an electrode. For this reason, although the terminal part which exposed the metal layer 4 and the metal layer 5 partially may be provided with respect to the resin molding 6, in this invention, in the case of series connection, the unit cell C of the both ends is provided. It is preferable that the metal layer 4 or the metal layer 5 is provided with projecting portions 4b and 5b serving as the electrodes of the unit cell C, and these protrude from the resin molded body 6 to the outside. The protrusions 4b and 5b can also be used for holding the metal layers 4 and 5 (laminate L) in the mold when performing insert molding.

  The formation of the metal layer 4 and the metal layer 5 and the formation of the openings 5a and 4a can be performed using press work (press punching process). In addition, the protrusions 4b and 5b of the metal layer 4 and the metal layer 5 may be provided with through holes in the insert-molded portions for the purpose of improving the flow and adhesion of the resin. Furthermore, in order to perform connection and fixation satisfactorily, through holes may be provided in the exposed portions of the protrusions 4b and 5b.

  As shown in FIG. 2, the fuel cell according to the present invention includes a connection portion J that electrically connects conductive layers of any unit cell C and other unit cells C. The first conductive layer of any unit cell C and the second conductive layer of another unit cell C are electrically connected. In the present embodiment, one first conductive layer (metal layer 4) of the adjacent unit cell C, the other second conductive layer (metal layer 5), and the connection portion J are formed from a continuous metal plate (integrated). An example in which the metal layer is formed of a single metal part).

  In this embodiment, since the unit cells C1 to C4 are connected in series, the protruding portions 4b and 5b of the metal layer are provided only in the unit cell C1 and the unit cell C4, respectively.

  The metal plate in which the first metal layer 4 and the second metal layer 5 are integrated via the connection portion J is a member for connecting adjacent unit cells C in series. Instead of arranging the first metal layer 4 and the second metal layer 5 independently, by using this integrated metal plate, the unit cells C1 to C4 are connected in series only by arranging them in the mold 10. Can be manufactured (see FIG. 5).

  As shown in FIG. 2C, the metal plate includes a first metal layer 4 and a second metal layer 5 which are arranged adjacent to each other in a plane parallel to each other and extend outward in the same plane. The extending portions 4j and 5j are connected and integrated by a step portion 4s. Such a stepped portion can be produced by subjecting a metal plate to sheet metal processing. In addition, when performing parallel connection, for example, the metal in which the first metal layers 4 (or the second metal layers 5) arranged adjacent to each other in the same plane are connected and integrated by the extended extending portion. A board can be used. Further, the connection portion J has a shape partially protruding outside the resin molded body 6.

  The protruding portions 4b and 5b are connected to a circuit portion (not shown) and can be taken out as an output voltage. Further, the connection portion J can be monitored for an intermediate potential by connecting to the circuit portion.

  In this embodiment, the connecting portion J has a shape that partially protrudes to the outside of the resin molded body 6, but the connecting portion J may have a rectangular shape having a step portion at the center. As will be described later, when the insert is formed, it is necessary to fix the position of the laminate in the mold, and when the position is fixed, the connecting portion J partially protrudes outside the resin molded body 6. Preferably there is.

  The connecting portion J connects adjacent unit cells C in series, and is a metal plate integrated with the first metal layer 4 and the second metal layer 5. Instead of disposing the first metal layer 4 and the second metal layer 5 independently, by using this metal plate, the fuel cell in which the unit cells C are connected in series simply by disposing the metal plate in the mold. Can be manufactured.

<Resin molding>
As shown in FIG. 2, the fuel cell of the present invention includes a resin molded body 6 in which the unit cell C and the connecting portion J as described above are integrated by insert molding. The resin molded body 6 preferably has a supply part for supplying gas or liquid to the first electrode layer 2 and the second electrode layer 3, and this supply part is the first metal layer 4 or the second metal layer 5. The opening 6a is preferably provided at a position corresponding to the exposed portion.

  In the present embodiment, resin molding is performed in a state where the first metal layer 4 and the second metal layer 5 are pressed from both sides so that the first electrode layer 2 and the second electrode layer 3 are exposed from the opening 6a. An example in which the body 6 is insert-molded and integrated is shown.

  In the present invention, the size of the openings 4a and 5a corresponding to the exposed portions of the metal layers 4 and 5 may be larger, the same size, or smaller than the size of the opening 6a of the resin molded body 6. Also good. However, the resin molded body 6 is preferably molded so that the size of the exposed portion of the first metal layer 4 and / or the second metal layer 5 is substantially equal to the size of the opening 6a. Specifically, the area of each opening 6a is preferably 60 to 150%, more preferably 80 to 130% of the area of each exposed portion.

  In the present embodiment, an example in which the size of the openings 4a and 5a corresponding to the exposed portions of the metal layers 4 and 5 is smaller than the size of the opening 6a of the resin molded body 6 is shown. Thereby, it is possible to pressurize the periphery of the openings 4a and 5a of the metal layers 4 and 5 at the time of molding using a portion corresponding to the opening 6a of the resin molded body 6 (see FIG. 5C). ).

  Examples of the material of the resin molded body 6 include a thermosetting resin, a thermoplastic resin, and a heat resistant resin, and a thermoplastic resin and a thermosetting resin are preferable. Examples of the thermoplastic resin include polycarbonate resin, ABS resin, liquid crystal polymer, polypropylene, polystyrene, acrylic resin, fluororesin, polyester, and polyamide. Examples of the thermosetting resin include epoxy resins, unsaturated polyester resins, phenol resins, amino resins, polyurethane resins, silicone resins, and thermosetting polyimide resins. Among these, polyester, polypropylene, and acrylic resin are preferable from the viewpoint of fluidity, strength, melting temperature, and the like of the resin in the mold, and these can be selected depending on the application.

  As the resin molded body 6, it is also possible to use a resin elastomer such as a thermoplastic elastomer or rubber. In that case, it is possible to make the whole fuel cell flexible by using another material having flexibility.

  The overall thickness of the resin molded body 6 is preferably 0.3 to 4 mm, and more preferably 0.5 to 2 mm, from the viewpoints of the strength of integration with the resin, the pressure for pressing the metal layer, and the thinning. In particular, the thickness of the resin molded body 6 at the portion covering the metal layer is preferably 0.2 to 1.5 mm, and more preferably 0.3 to 1.0 mm, from the viewpoint of pressure to pressurize the metal layer.

  The area of the outer shape of the resin molded body 6 is preferably 101 to 200% of the outer area of the solid polymer electrolyte layer 1 from the viewpoint of the strength of integration by the resin and the pressure to pressurize the metal layer, and is preferably 150 to 180. % Is more preferable.

  An example of the shape of the resin molded body 6 is shown in FIG. As shown in FIG. 4, the resin molded body 6 includes a front wall 6b in which an opening 6a is formed, a side wall 6c and a bottom wall 6d that are integrally formed on the left and right sides of the front wall 6b. By connecting the resin flat plate 60 to the rear side where the side wall 6c and the bottom wall 6d are formed, a flat box can be obtained. The material of the resin flat plate 60 can be the same as that of the resin molded body 6, and the two can be connected by mechanical connection such as adhesion or screws.

  In addition, about the shape of the resin molding 6 and the resin flat plate 60 for forming a flat box, it can change suitably according to the number, size, etc. of a unit cell. For example, the resin molded body 6 in which the unit cell C is insert-molded may have a flat plate shape, and the resin flat plate 60 side may have a shape with a side wall and a bottom wall.

  The fuel cell of the present invention can generate power by supplying fuel or the like as follows. For example, power generation can be performed by leaving the cathode side open to the atmosphere as it is and generating fuel such as hydrogen gas in a space provided on the anode side. It is also possible to attach a flow path forming member for forming a flow path to the anode side and / or the cathode side and supply an oxygen-containing gas or fuel to the flow path. As the flow path forming member, for example, a plate-like body provided with a flow path groove, a supply port, and a discharge port, or a structure similar to a separator of a stack type fuel cell can be used. When the latter is used, a stack type fuel cell can be constructed.

<Fuel cell manufacturing method (insert molding)>
The fuel cell as described above can be manufactured, for example, by the following manufacturing method. That is, as shown in FIGS. 5A to 5D, the fuel cell manufacturing method of the present embodiment includes a solid polymer electrolyte layer 1, a first electrode layer 2 and a second electrode layer disposed on both sides thereof. 3, and a plurality of laminates L including the first conductive layer and the second conductive layer disposed on the outside thereof are electrically connected to each other by the connecting portion J. A step of disposing in the mold 10 in a state of being connected to each other. In the case of series connection, one first conductive layer of the adjacent laminate L is connected to the other second conductive layer, and in the case of parallel connection, one first conductive layer of the adjacent laminate L and the other second conductive layer are connected. One conductive layer is connected, and one second conductive layer and the other second conductive layer are connected.

  In this embodiment, the first metal layer 4 having exposed portions (for example, openings 4a and 5a) in which the first conductive layer and the second conductive layer partially expose the first electrode layer 2 and the second electrode layer 3, and An example is shown in which the second metal layer 5 is disposed in the mold 10 in a state where the exposed portion is closed by the convex portions 11 a and 12 a of the mold 10.

  A plurality of the laminates L constituting the unit cell C may be arranged side by side in the same plane, L-shaped two sides, square or rectangular two to four sides, triangular two to three sides It may be arranged on each side. In the present embodiment, an example in which two laminates L are arranged in the same plane is shown.

  In addition, the method of manufacturing the fuel cell according to the present embodiment includes a step of molding the resin molded body 6 that integrates the laminate L and the connection portion J by injecting resin into the molding die 10 described above. In this embodiment, the first metal layer 4 and the second metal layer 5 are pressurized from both sides, and a resin is injected into the mold 10 so that the first electrode layer 2 and the second electrode layer 3 are injected. An example including a step of forming a resin molded body 6 having a supply portion for supplying gas or liquid and integrating the laminate L will be described. That is, an example in which almost all of the laminate L is covered with the resin molded body 6 except for the opening 6a corresponding to the supply unit.

  First, as shown in FIG. 5A, for example, a lower mold 11 having a convex portion 11a is prepared on the bottom surface of each unit cell C formation region. In the present embodiment, the projections 11 a and 12 a are provided on the inner surface of the mold member divided into the molding die 10 and the projections 11 a and 12 a are pressed against the first metal layer 4 and the second metal layer 5. An example is shown. The convex portion 11a has an upper surface large enough to close the opening 4a of the first metal layer 4 on the lower side of the laminate L, and is provided at a position facing each opening 4a. The lower mold 11 has a side wall around the bottom surface, and the upper mold 12 can be inserted along the inner surface of the side wall.

  The lower mold 11 (or the upper mold 12) is provided with a resin injection port 11b, but a plurality of injection ports 11b may be provided. Moreover, in order to improve the flow of the resin at the time of molding, one or more small resin outlets may be provided.

  Further, in order to expose the protruding portions 4b and 5b of the first metal layer 4 and the second metal layer 5 from the resin molded body 6 after molding, the side wall of the lower mold 11 has a divided structure (not shown). . When the laminate L is placed in the mold 10, the protrusions 4 b and 5 b of the first metal layer 4 and the second metal layer 5 are positioned in the rectangular notch provided on the side wall of the lower mold 11. The projecting portions 4b and 5b are structured to be pressed by the mold member. Thereby, protrusion part 4b, 5b can be exposed from the resin molding 6. FIG.

  Next, for example, as shown in FIG. 5B, a plurality of laminates L are arranged on the bottom surface of the lower mold 11. In that case, the upper surface of the convex part 11a formed in the bottom face of the formation area of each unit cell C arrange | positions in the position which can block | close the opening 4a of the 1st metal layer 4 of each laminated body L. FIG.

  In the present embodiment, one first conductive layer and the other second conductive layer of the adjacent laminate L are arranged in the mold 10 in a state where they are electrically connected by the connecting portion J. In the present embodiment, one of the first conductive layers (metal layer 4), the other second conductive layer (metal layer 5) of the adjacent laminate L, and the connection portion J are formed of a continuous metal plate. An example in which layers are formed is shown.

  When arranging the laminate L, some or all of each layer may be integrated or may not be integrated. Moreover, when a part is not integrated, each layer may be arrange | positioned separately or may be arrange | positioned simultaneously. The configuration of the laminate L to be arranged is as described above. When the arrangement is performed, this preformed body is used by using a preformed body in which a part of the shape of the final resin molded body 6 is molded in advance. It is also possible to arrange it in the mold 10 together with the laminate L.

  Next, for example, as shown in FIG. 5 (c), the upper mold 12 is inserted along the inner surface of the side wall of the lower mold 11, and the region of each unit cell C of the upper mold 12 is formed. A convex portion 12a is provided on the lower surface. The convex portion 12a has an upper surface large enough to close the opening 5a of the second metal layer 5 on the upper side of the laminate L and is provided at a position facing each opening 5a. Then, the laminate L is placed in the molding die 10 with the metal layers 4 and 5 being pressed by the convex portion 11 a of the lower mold 11 and the convex portion 12 a of the upper mold 12. At that time, the protrusions 4 b and 5 b of the first metal layer 4 and the second metal layer 5 may be disposed outside the inner space of the mold 10.

  In this state, a resin (“resin” contains a resin raw material liquid and an uncured product) is injected into the mold 10, but the exposed portions (for example, the openings 4 a and 5 a) have the convex portions 11 a and the convex portions 12 a. Therefore, as shown in FIG. 5D, in the obtained molded body, the first electrode layer 2 and the second electrode layer 3 are exposed from the opening 6a. Moreover, the injection | pouring of resin can integrate the several of the laminated bodies L containing the solid polymer electrolyte layer 1, the electrode layers 2 and 3, the 1st metal layer 4, and the 2nd metal layer 5 by insert molding.

<Example of overall configuration of fuel cell>
FIG. 6 is a perspective view showing the overall configuration of the fuel cell. The number of unit cells C1 to C4 is four, and the configuration is the same as that described in FIG. The resin molded body 6 and the resin flat plate 60 constitute a cell holder A that is a flat box. The unit cells C1 to C4 are held on the resin molded body 6 by insert molding. A water storage case 31a of the hydrogen generator 30 is detachably attached to the lower part of the cell holder A.

  FIG. 7 is an exploded perspective view showing main components of the fuel cell. A groove 6e is formed in the resin molded body 6 and the resin flat plate 60 constituting the cell holding body A. That is, the groove 6e is formed in the mounting portion between the cell holder A and the water storage case 31a. The groove 6e is formed over the entire circumference of the mounting portion. A waterproof seal is provided in the groove 6e. Examples of the waterproof seal include a configuration in which liquid rubber is applied and dried.

  In addition, in embodiment shown in FIG. 7, although the structure which fits the water storage case 31a in the outer peripheral surface of the cell holding body A is employ | adopted, it is not limited to this. That is, you may employ | adopt the structure which inserts the water storage case 31a in the inner peripheral surface side of the cell holding body A. FIG. In this case as well, it is preferable to similarly adopt a seal structure using a waterproof seal.

  In a state where the hydrogen generator 30 is mounted on the cell holder A, the internal space of the cell holder A has a portion other than the water storage case 31a in the hydrogen generator 30, that is, the packaging material 35 (or the hydrogen generator 32). ), A fan 33, an air conditioning cover 37, and the like are disposed.

<Operation of fuel cell>
When hydrogen is generated by the hydrogen generator 30 and supplied to the unit cell C, the hydrogen generator 30 is mounted from the lower side of the cell holder A. A cross-sectional view when the mounting is completed is shown in FIG.

  As shown in FIG. 8, in a state where the hydrogen generator 30 is mounted on the cell holder A, the unit cell C held by the cell holder A and the hydrogen generator 32 of the hydrogen generator 30 face each other. The hydrogen generating agent 32 is disposed in the internal space S formed by the internal space forming part 36 and the cell holder A (resin molded body 6). The internal space S may be sealed, but may have an opening, a gap or the like for leaking excessive hydrogen generated.

  The water held by the water retaining material 31 b is absorbed by the water absorbing sheet 34 and permeates the entire surface of the water absorbing sheet 34. The water vapor generated by the evaporation of water from the water absorbing sheet 34 diffuses throughout the internal space S through the water vapor supply path 38, and the water vapor is supplied to the hydrogen generating agent 32 through the hydrophobic porous membrane 35a. The

  The hydrogen generator 30 according to the present invention includes a fan 33 and can cause water vapor generated from the water absorbent sheet 34 to flow. By causing the water vapor to flow, the evaporation of water from the water absorbent sheet 34 can be promoted. Further, the fan 33 can increase or decrease the amount of water vapor generated by adjusting the air flow rate. By controlling the amount of water vapor generated, the amount of water vapor supplied to the hydrogen generating agent 32 can also be controlled. Note that the amount of water vapor generated also varies depending on the material, size, thickness, and the like of the water absorbent sheet 34, so these need to be set as appropriate.

  The hydrogen generating agent 32 generates hydrogen by a reaction with the supplied water vapor, and the hydrogen is released into the internal space S through the hydrophobic porous membrane 35a. Since this hydrogen is supplied from one surface of the unit cell C and oxygen in the air is supplied from the other surface, an electrode reaction occurs at each electrode, and power generation can be performed. The power generation continues until the generation of water vapor ends or the hydrogen generating agent is consumed.

  The fan 33 is operated by the electric power generated by the fuel cell. However, when the electric power generation by the fuel cell is started, the electric power is not supplied and the fan 33 cannot be operated. When the fan 33 is not operated, the water vapor generated from the water absorbing sheet 34 gradually diffuses throughout the internal space S and is supplied to the hydrogen generating agent 32. If it is this structure, the electric power generation by a fuel cell will be started slowly, and a start-up is not good.

  Therefore, the power supply device according to the present invention preferably includes an auxiliary battery (not shown) that supplies power to the fan 33 at the initial stage of power generation by the fuel cell. By operating the fan 33 with the power of the auxiliary battery, steam can be forcibly supplied to the hydrogen generating agent 32 at the start of power generation by the fuel cell, and power generation can be started quickly. However, the auxiliary battery is not always necessary.

  In the hydrogen generator 30 of the present invention, a check valve (not shown) is preferably provided in the water vapor supply path 38. By providing a check valve in the water vapor supply path 38, it is possible to prevent water vapor from flowing back through the water vapor supply path 38 and returning to the water containing portion 31. By preventing the backflow of water vapor, the amount of water vapor supplied to the hydrogen generating agent 32 can be controlled, and the amount of hydrogen generated can be accurately controlled.

<Another embodiment of the hydrogen generator>
In the above-described embodiment, the example in which the fan 33 directly blows air to the water absorbent sheet 34 and causes the water vapor to flow is shown, but the fan 33 may not directly blow air to the water absorbent sheet 34. Specifically, the fan 33 may be arranged as shown in FIG. In this example, the fan 33 only causes the water vapor naturally generated from the water absorbent sheet 34 to flow in the space, and does not directly apply wind to the water absorbent sheet 34. Even in such a configuration, by causing the water vapor to flow, the evaporation of water from the water absorbent sheet 34 can be promoted, and the amount of water vapor generated can be controlled.

  Moreover, although the water absorption sheet 34 showed the example which has the cylindrical part 34b in the above-mentioned embodiment, the water supply sheet 34 is not limited to this shape. That is, the shape of the water supply sheet 34 and the arrangement of the fans 33 may be as shown in FIG. FIG. 10 shows another embodiment of the hydrogen generator, where (a) is a perspective view and (b) is a cross-sectional view taken along the line II of (a). In FIG. 10, the hydrogen generating agent 32 is omitted and not shown. In this example, the fan 33 is disposed at the center in the water accommodating portion 31, and the water retaining material 31b is disposed so as to surround the periphery thereof. As shown in FIG. 10, the mesh-shaped water absorption sheet 34 covers the upper part of the fan 33, and is comprised so that the edge part 34a of the 4 sides may contact the water retention material 31b. The water absorbent sheet 34 has water absorbency, and the end 34a absorbs water by coming into contact with the water of the water retaining material 31b, and water penetrates the entire surface of the mesh water absorbent sheet 34. According to this configuration, since the fan 33 blows air from below the mesh-like water absorbent sheet 34, the evaporation of water from the water absorbent sheet 34 can be promoted.

  In the above-described embodiment, an example is shown in which the amount of water vapor generated is controlled by causing the water vapor generated from the water absorbent sheet 34 to flow with the fan 33. However, in the present invention, for example, an ultrasonic oscillator or the like is used. The structure which controls the quantity of the water vapor | steam which the mist which generate | occur | produced from the water accommodating part 31 using it may be made to flow with a fan, and the mist vaporized may be sufficient.

<Another embodiment of the power generation cell>
(1) In the above-described embodiment, an example in which a power generation cell is configured by a plurality of unit cells connected in series has been described. However, in the present invention, a power generation cell may be configured by a single unit cell. A plurality of unit cells may be connected in parallel.

  (2) In the above-described embodiment, an example in which the unit cell C is formed by integrating the solid polymer electrolyte layer 1, the electrode layers 2 and 3, the first metal layer 4 and the second metal layer 5 by insert formation has been shown. However, the unit cell C having a structure in which the first metal layer 4 and the second metal layer 5 have a larger area, and the peripheral portions of both are sealed by caulking while interposing an insulating material may be used. Such a unit cell C having a crimped structure is disclosed in, for example, International Publication No. WO2005 / 050766, and a manufacturing method and a manufacturing facility for performing crimping sealing are disclosed in, for example, Japanese Patent Application Laid-Open No. 2006-86041. The technique disclosed in the Japanese Patent Publication can be used.

  The unit cells C having such a caulking structure can be integrated with a cell holder by insert formation or the like after electrically connecting a plurality of the unit cells C as necessary to form a plate-shaped power generation cell. The plate-shaped power generation cell can be used in the present invention in the same manner as shown in FIG.

<About ammonia remover>
In the present invention, an ammonia removing agent may be provided in the internal space S in order to remove ammonia as an impurity from hydrogen generated from the hydrogen generating agent 32. Specifically, a sheet-like ammonia removing agent can be disposed so as to overlap with the packaged hydrogen generating agent 32. Such an ammonia removing agent is commercially available in the form of a sheet, but it is also possible to use one in which a granular adsorbent or the like is contained in a breathable bag.

  As the ammonia removing agent, for example, an adsorbent that adsorbs and removes ammonia in hydrogen (including chemical adsorption such as adsorption / decomposition and reaction adsorption), an absorbent that dissolves and removes ammonia, a reactant that removes ammonia by reaction, Examples include decomposition means for removing ammonia by decomposition (thermal decomposition, catalytic reaction decomposition, etc.), and it is preferable to provide an adsorbent that removes ammonia by physical adsorption or chemical adsorption.

<Circuit configuration>
The fuel cell of the present invention may further include an electronic circuit for boosting and current control. For example, the output voltage of each unit cell C is preferably boosted to a predetermined voltage by a DC-DC converter (corresponding to a booster circuit). The circuit unit is provided with a stabilization circuit and the like, and is controlled so that an appropriate output voltage and output current can be supplied. Further, power is supplied from the power supply terminal to an external device, a mobile phone, or the like via a circuit unit added on the downstream side of the converter.

  Hereinafter, examples and the like specifically showing the configuration and effects of the hydrogen generator of the present invention will be described.

Example 1
Using the hydrogen generator 30 provided with the fan 33 that can be blown to the tubular portion 34b of the water absorbent sheet 34 described in the above embodiment, the amount of water vapor generated (evaporation amount) was examined. Further, the generated water vapor was supplied to the hydrogen generating agent 32, and the amount of hydrogen generated was examined.

  As the hydrogen generating agent 32, 1.2 g of a pulverized product in which calcium hydride was embedded in a resin was used. In the following comparative examples, the same hydrogen generator 32 was used.

(Comparative Example 1)
In Comparative Example 1, the amount of water vapor generated was examined using the same hydrogen generator 30 as in Example 1 above. However, in Comparative Example 1, water vapor was naturally generated from the water absorbent sheet 34 without operating the fan 33.

(Example 2)
The hydrogen generator of Example 2 includes the same fan 33 as that of Example 1, but the arrangement of the fans 33 was changed. Specifically, using the hydrogen generator shown in FIG. 9, the fan 33 only plays a role of allowing water vapor naturally generated from the water absorbent sheet 34 to flow in the space without directly blowing air to the water absorbent sheet 34. I did it. The amount of hydrogen generated at this time was examined.

  The results of the amount of water vapor generated with the passage of time in Example 1 and Comparative Example 1 are shown in FIG. In FIG. 11A, the vertical axis is the evaporation amount (cc), the horizontal axis is the time (minute), and in FIG. 11B, the vertical axis is the total evaporation amount (cc), and the horizontal axis is the time (minute). It is. In Example 1, the fan was operated continuously, and in Comparative Example 1, the fan was kept stopped. From this result, it can be seen that the amount of water vapor generated is greatly increased by operating the fan, and the fan has the effect of promoting the evaporation of water.

  The result of the hydrogen generation amount in Example 1 is shown in FIG. The result of the hydrogen generation amount in Example 2 is shown in FIG. 12 and 13, the amount of hydrogen generation is expressed as a flow rate (cc / min), the vertical axis is the flow rate, and the horizontal axis is the time (minutes). In Example 1 and Example 2, as shown in FIGS. 12 and 13, the fan was repeatedly turned on and off. From these results, it can be seen that in both Example 1 and Example 2, the amount of hydrogen generated increases by turning on the fan. That is, it is understood that by causing the steam to flow with the fan, the evaporation of water is promoted and the amount of water vapor generated is controlled, and as a result, the amount of hydrogen generated can be controlled. It can also be seen that the hydrogen generator of Example 1 has a larger amount of hydrogen generation than the hydrogen generator of Example 2.

It is a figure which shows an example of the hydrogen generator of this invention, (a) Top view, (b) is II sectional drawing of (a). It is a figure which shows an example of a fuel cell, (a) is a perspective view, (b) is a top view, (c) is a perspective view which shows the structure of a metal plate. It is a figure which shows an example of a fuel cell, (a) is II sectional drawing of FIG.2 (b), FIG.3 (b) is II-II sectional drawing similarly. It is a figure which shows the structure of a resin molding and a resin flat plate. It is front view sectional drawing which shows an example of the manufacturing method of the fuel cell of this invention. It is a perspective view which shows the whole structure of a fuel cell. It is a disassembled perspective view which shows the component of the fuel cell shown in FIG. It is a longitudinal cross-sectional view which shows the internal structure of the fuel cell of this invention. It is a figure which shows an example of the hydrogen generator of another embodiment, a is a top view, (b) is II sectional drawing of (a). It is a figure which shows an example of the hydrogen generator of another embodiment, a) is a perspective view, (b) is II sectional drawing of (a). It is a figure which shows the result of the water vapor generation amount in Example 1 and Comparative Example 1. It is a figure which shows the result of the hydrogen generation amount in Example 1. FIG. It is a figure which shows the result of the amount of hydrogen generation in Example 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Solid polymer electrolyte layer 2 Anode side electrode layer 3 Cathode side electrode layer 4 Anode side metal layer 5 Cathode side metal layer 6 Resin molding 30 Hydrogen generator 31 Water accommodating part 31a Water accommodating case 31b Water retention material 32 Hydrogen generating agent 33 Fan 34 Water absorbing sheet 34a End 34b Cylindrical part 37 Air conditioning cover 38 Water vapor supply path 60 Resin flat plate C Unit cell

Claims (7)

A hydrogen generator for generating hydrogen to be supplied to a fuel cell,
A water storage section for storing water;
A hydrogen generating agent that reacts with vaporized water vapor to generate hydrogen;
A hydrogen generator comprising: a blowing means for causing the water vapor to flow.   The hydrogen generating apparatus according to claim 1, wherein the blower unit has an evaporation amount control function of controlling the amount of water vapor generated by the amount of blown air. The water storage portion is provided with a water-absorbing sheet-like member that is partially in contact with the stored water,
The hydrogen generator according to claim 1, wherein the blowing unit blows air to the sheet-like member. The sheet-like member has a cylindrical portion,
The hydrogen generating apparatus according to claim 3, wherein the blowing unit blows air into the cylindrical portion.   The hydrogen generator according to any one of claims 1 to 4, wherein a check valve is provided in a steam supply path for supplying the steam to the hydrogen generating agent. A hydrogen generator according to any one of claims 1 to 5;
A fuel cell that is supplied with hydrogen generated by the hydrogen generator and generates power;
An auxiliary battery that supplies power to the blowing means at the initial stage of power generation by the fuel cell. A hydrogen generation method for generating hydrogen to be supplied to a fuel cell,
A hydrogen generation method for generating hydrogen by reacting a hydrogen generating agent with the water vapor while promoting generation of water vapor from water by blowing air.

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