JP2010027594A - Fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel cell with a reaction liquid containing section and a fuel generation section separated from each other, generating no useless fuel gas in replacing consumable supplies. <P>SOLUTION: The fuel cell includes a power generation cell C for generating power when hydrogen gas is supplied from one surface and oxygen is supplied from another surface, a cell holding body A forming an inner space together with the power generation cell C by holding the power generation cell C with the one surface turned inside, a fuel generation section D arranged in the inner space and containing a gas generating agent for generating hydrogen gas by reacting with water, a water containing cartridge B detachable from the cell holding body A, and a reaction liquid introducing mechanism for guiding the water to the gas generating agent 20 in the fuel generation section D. The reaction liquid introducing mechanism includes an outlet port 31a formed on the water containing cartridge B and a water absorbing sheet 20c arranged on the fuel generation section D. When the cartridge B is mounted on the cell holding body A, the water absorbing sheet 20c is inserted in the outlet port 31a, and the water is supplied to the gas generating agent 20 through the water absorbing sheet 20c. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a fuel cell including a power generation cell, a cell holder that holds the power generation cell, a fuel generation unit, and the like, and is particularly useful as a fuel cell used for mobile devices (portable devices) and the like.

  With the development of IT in recent years, lithium-ion secondary batteries are used for most power sources of mobile devices such as mobile phones, notebook computers, and digital cameras. However, as these mobile devices become highly functional, power consumption tends to increase more and more, and attention is focused on clean and highly efficient fuel cells for power supply or charging.

  In particular, when used in a portable device such as a notebook computer or a mobile phone, a structure that can maintain portability or downsizing is desired. For this reason, in order to comprise a fuel cell, it is necessary to arrange | position efficiently each part, such as a power generation cell and a fuel gas generation part.

  A portable or miniaturized fuel cell is known from the following Patent Document 1 by the present applicant. This fuel cell is mounted on the support substrate, a main body case formed of a wall surface portion that forms the appearance of the main body portion and faces at least in a different direction, a support substrate disposed along the wall surface portion, and the support substrate. A power generation unit cell (power generation cell) and a fuel gas generation unit that generates fuel gas such as hydrogen gas supplied to the power generation cell. The fuel gas generation unit is configured to be detachable from the main body case.

  This fuel gas generation unit is composed of a metal storage part (corresponding to a fuel generation part) containing metal (pure iron) as a hydrogen generating agent and a water storage part containing water as a reaction liquid. A mechanism is adopted in which the reaction liquid in the water storage part is supplied to the metal in the metal storage part by water-absorbing paper, whereby both react to generate hydrogen gas.

Utility Model Registration No. 3114148

  However, in the fuel gas generation unit, since the water storage portion and the metal storage portion are provided in the same container, both cannot be separated separately. Since water and metals are consumables, they must be replaced after they are consumed. At the time of this replacement (when the fuel gas generation unit is removed from the main body case), if the water storage portion and the metal storage portion are always connected by the absorbent paper, the fuel gas generation unit is connected to the main body case (power generation cell). ) Hydrogen gas is generated before being mounted, and waste occurs.

  Although the structure which controls supply of the water from a water accommodating part to a metal accommodating part with a pump is also considered, since a structure becomes complicated and it becomes a cost increase, it is a problem.

  The present invention has been made in view of the above circumstances, and its problem is to provide a fuel cell in which the reaction liquid storage unit and the fuel generation unit can be separated separately, and wasteful fuel gas is not generated when exchanging consumables. Is to provide.

  The above object can be achieved by the present invention as follows.

That is, the fuel cell of the present invention includes a power generation cell that generates power by supplying fuel gas from one surface and oxygen from the other surface;
A cell holder that forms an internal space with the power generation cell by holding the power generation cell with the one surface facing inward,
A fuel generating unit that is disposed in the internal space of the cell holder and contains a gas generating agent that reacts with a reaction solution to generate a fuel gas;
And a reaction liquid introduction mechanism that guides the reaction liquid to a gas generating agent in the fuel generation part via a reaction liquid introduction member having one end provided on the outside of the fuel generation part.

  According to the fuel cell of the present invention, the fuel gas generated in the fuel generator is discharged into the internal space of the cell holder and supplied from one surface of the power generation cell, and oxygen in the air is supplied from the other surface. Therefore, power generation can be performed without using piping between the power generation cells or piping from the fuel generation unit. Further, since the fuel generating part can be arranged in the internal space, space saving can be achieved. Furthermore, since the reaction liquid introduction member having one end is provided outside the fuel generation part, the reaction liquid can be guided to the gas generating agent in the fuel generation part through this. Since such a reaction liquid introduction mechanism is provided, for example, a reaction liquid storage cartridge for storing the reaction liquid is made detachable, and the reaction liquid is supplied from there, or the reaction liquid is put in a container having an open top. The reaction liquid can be supplied by bringing the reaction liquid introduction member into contact therewith. In the present invention, there may be one power generation cell or a plurality of power generation cells.

  In the above, it further includes a reaction liquid storage cartridge that is detachable from the cell holder and stores the reaction liquid, and the reaction liquid introduction mechanism includes a lead-out portion formed in the reaction liquid storage cartridge, When the reaction liquid storage cartridge is attached to the cell holder, the reaction liquid introduction member is brought into contact with or inserted into the lead-out portion, so that the reaction liquid is passed through the reaction liquid introduction member to generate a gas generating agent. It is preferable to be supplied to.

  According to this configuration, the reaction liquid introduction member is provided in the fuel generation section, and can be completely separated from the fuel generation section when the reaction liquid storage cartridge is removed. Therefore, fuel gas is not generated unnecessarily. Further, when the reaction liquid storage cartridge is mounted, the reaction liquid introduction member is brought into contact with or inserted into the lead-out portion formed in the reaction liquid storage cartridge. Accordingly, since the reaction liquid is supplied to the gas generating agent via the reaction liquid introducing member, fuel gas is generated by the reaction between the gas generating agent and the reaction liquid. As a result, it is possible to provide a fuel cell in which the reaction liquid storage unit (cartridge) and the fuel generation unit can be separated separately, and wasteful fuel gas is not generated when consumables are replaced.

  In this invention, it is preferable that the said fuel generation part accommodates the hydrogen generating agent which reacts with the reaction liquid containing water and generate | occur | produces hydrogen gas.

  The reaction liquid introducing member according to the present invention is preferably a sheet-like member having water absorption. By using a sheet-like member, the space can be reduced, which can contribute to downsizing. Moreover, a reaction liquid can be supplied using a capillary phenomenon because a sheet-like member has water supply. Therefore, the reaction liquid can be supplied without using an actuator such as a pump, which can contribute to simplification of the configuration and cost reduction.

  The reaction liquid introduction mechanism includes a surface of one end of a reaction liquid introduction member that is a sheet-like member having water absorption, and a surface of a lead-out portion that is formed of the water-absorbing sheet-like member formed in the reaction liquid storage cartridge. Are preferably brought into contact with each other. If comprised in this way, since a sheet-like member will be in a non-contact state or a contact state by attachment or detachment of a reaction liquid accommodation cartridge, supply of the reaction liquid more stably by the reaction liquid introduction mechanism is attained.

  Moreover, it is preferable that the mounting part of the cell holding body and the reaction liquid storage cartridge has a nested structure, and that the mounting part is provided with a waterproof seal. By providing the mounting portion as a nested structure and providing a waterproof seal, it is possible to prevent the reaction solution from inadvertently leaking outside the reaction solution storage cartridge.

  Or it is preferable that the said cell holding body comprises a flat box with the said power generation cell, and the said power generation cell is arrange | positioned on the single side | surface or both surfaces of the opposing surface of the box. Thereby, a flat fuel cell in which the power generation cells are arranged on the same plane can be formed. Such a fuel cell is particularly advantageous when incorporated in a device for supplying electric power.

  Furthermore, it is preferable that the power generation cells are integrally formed with the cell holder by insert molding in a state where a plurality of the power generation cells are electrically connected to each other. In the present invention, since piping between power generation cells (when a plurality of power generation cells are provided) is not necessary, insert molding can be performed while being electrically connected to each other, whereby the power generation cells are integrated with the cell holder. By forming into a shape, the internal space of the cell holder can be formed by a simple manufacturing method.

  It is preferable that the reaction liquid in the reaction liquid storage cartridge in the present invention is held by an elastic water absorbing body, and the tip of the reaction liquid introduction member presses the water absorption body when the reaction liquid storage cartridge is mounted. Examples of the water-absorbing body having elasticity include absorbent cotton, sponge, urethane foam, and the like, which hold the reaction liquid. The tip of the reaction liquid introduction member presses the water absorption body when the reaction liquid storage cartridge is mounted, so that the reaction liquid can be easily transmitted from the water absorption body to the reaction liquid introduction member.

  Further, the reaction liquid in the reaction liquid storage cartridge in the present invention is held by a water absorbent, the surface of the water absorbent is covered with a water absorbent sheet, and the tip of the reaction liquid introduction member is the water absorbent when the reaction liquid storage cartridge is mounted. It is preferable to press the body. According to this configuration, the tip of the reaction liquid introduction member presses the water absorption sheet when the reaction liquid storage cartridge is mounted, thereby transmitting the reaction liquid held by the water absorbent through the water absorption sheet and the reaction liquid introduction member. Can do.

  In the above, examples of the water absorbent include absorbent cotton, sponge, and urethane, and examples of the water absorbent sheet include filter paper and nonwoven fabric. For example, when absorbent cotton is used as the water absorbent body, the direction in which the reaction liquid is transmitted may be limited to a specific direction, and the reaction liquid held in an area where the absorbent cotton is present may not be taken out. In such a case, by covering the surface of the water absorbing body with the water absorbing sheet, the reaction liquid held in the region can be transmitted to the reaction liquid introducing member via the water absorbing sheet. Thereby, the reaction liquid currently hold | maintained at the water absorption body can be consumed without waste.

The figure which shows an example of the fuel cell of this invention Sectional view of the fuel cell shown in FIG. The figure which shows the composition of a resin molding and a resin flat plate Front view sectional drawing which shows an example of the manufacturing method of the fuel cell of this invention The perspective view which shows the whole structure of a fuel cell The disassembled perspective view which shows the main components of the fuel cell shown in FIG. Development view showing the configuration of the fuel generator 1 is a longitudinal sectional view showing the internal structure of a fuel cell according to the present invention. Partial perspective view which shows the state which removed the water cartridge Front view sectional drawing which shows the other example of the fuel cell of this invention The figure which shows the structure of another embodiment of a water cartridge. Front view sectional drawing which shows the other example of the fuel cell of this invention Front view sectional drawing which shows the other example of the fuel cell of this invention

  A preferred embodiment of a fuel cell according to the present invention will be described with reference to the drawings. 1A and 1B are diagrams showing an example of a fuel cell according to the present invention, in which FIG. 1A is a perspective view, FIG. 1B is a plan view, FIG. 1C is a perspective view showing a configuration of a metal plate, and FIG. FIG. 1B is a cross-sectional view taken along the line II, and FIG. 2B is a cross-sectional view taken along the line II-II.

<Configuration of power generation cell>
As shown in FIG. 1, the fuel cell of the present invention includes a plurality of unit cells C1 to C4 (hereinafter referred to as unit cell C when it is not necessary to distinguish each unit cell). The conductive layers of the unit cell C and the other unit cells C are electrically connected by a connection 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 the present invention, any 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 invention 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, and these electrode layers 2, 3 The first conductive layer and the second conductive layer are disposed on the outer side of the first and second conductive layers, respectively. 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. 1, the fuel cell of the present invention includes a connection portion J that electrically connects the 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. 4).

  As shown in FIG. 1C, 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. 1, 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. 2C). ).

  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. 3, 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 (corresponding to a cell holder) 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 power generation cell. For example, the resin molded body 6 in which the power generation 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, the cathode side is left open to the atmosphere as it is, and power is generated by supplying fuel such as hydrogen gas to the space provided on the anode side or generating fuel such as hydrogen gas in the space provided on the anode side. be able to. 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 manufacturing method of the present invention. That is, the method for producing a fuel cell of the present invention comprises a solid polymer electrolyte layer 1, a first electrode layer 2 and a second electrode layer 3 disposed on both sides thereof, as shown in FIGS. In addition, a plurality of the laminates L including the first conductive layer and the second conductive layer disposed outside them are electrically connected to each other by the connection portion J. Including a step of placing the molding die 10 in a state of being connected to the molding die 10. 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 for manufacturing a fuel cell according to the present invention includes a step of molding a resin molded body 6 that integrates the laminate L and the connection portion J by injecting a resin into the mold 10. 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, for example, as shown in FIG. 4A, a lower mold 11 having a convex portion 11a on the bottom surface of each unit cell C formation region is prepared. 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. 4B, 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 this invention, it arrange | positions in the shaping | molding die 10 in the state which electrically connected one 1st conductive layer and the other 2nd conductive layer of the adjacent laminated body L by the connection part J. FIG. 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. 4C, 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. 4D, 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 formation.

<Example of overall configuration of fuel cell>
FIG. 5 is a perspective view showing the overall configuration of the fuel cell. The number of power generation cells C1 to C4 is four, and the configuration thereof 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 power generation cells C1 to C4 are held by the resin molded body 6 by insert molding. A water cartridge B (corresponding to a reaction liquid storage cartridge) is detachably attached to the lower part of the cell holder A. The water cartridge B contains water as a reaction solution.

  FIG. 6 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 of the cell holder A and the water cartridge B. The groove 6e is formed over the entire circumference of the mounting portion. A waterproof seal is provided in the groove 6e. An example of the waterproof seal is a configuration in which liquid rubber is applied and dried, for example.

  A fuel generator D is detachably mounted in the internal space of the cell holder A. The fuel generator D is folded when it is mounted, but before it is folded, it can be developed into the shape shown in FIG. When folded on the inside of the broken line L, the form shown in FIG. 6 is obtained. As shown in FIG. 7, the fuel generating part D is composed of a sheet-like hydrogen generating agent 20.

  The sheet-like hydrogen generator 20 has a porous layer 20a containing a granular hydrogen generator and a resin formed on the upper surface of the base member 20b, and details thereof will be described later. Further, a water absorbing sheet 20c (corresponding to a reaction liquid introduction member and a sheet-like member) is attached to the surface of the porous layer 20a. The connection between the porous layer 20a and the water absorbent sheet 20c can be performed by an appropriate method such as an adhesive tape.

  The water absorbent sheet 20c may be any sheet that can be impregnated with water, but is preferably a water absorbent resin, absorbent cotton, a water absorbent nonwoven fabric, a water absorbent paper, or the like.

  When the water-absorbing sheet 20c is formed of a flexible material, it is preferable to back it with a hard sheet. The hard sheet may be anything as long as it can reinforce the water absorbent sheet 20c, and a metal sheet, a resinous sheet, or the like can be used. The backing of the water absorbent sheet 20c and the hard sheet can be performed by bonding or other appropriate methods.

  The water cartridge B contains water as a reaction solution. The water cartridge B includes an outer case member 30 and an inner case member 31, and water is accommodated inside the inner case member 31. Since water is held in the water supply body 32 such as absorbent cotton, sponge, urethane foam, the water does not leak outside the water cartridge B. The outer case member 30 and the inner case member 31 can be connected by mechanical connection such as adhesion or screws.

  On the upper surface of the inner case member 31, an elongated slit-shaped outlet 31a is formed as a lead-out portion. The tip of the water absorbent sheet 20c is configured to be insertable from the outlet 31a. A water absorbent sheet support member 21 is provided inside the mounting portion of the cell holder A. The water absorbent sheet support member 21 is formed in a rectangular ring shape, and an elongated slit hole 21a is formed. The water absorbing sheet 20c is held in a state of passing through the slit hole 21a. The water absorbent sheet support member 21 can be formed of the same material as the resin molded body 6.

  Since both the fuel generator D and the water in the water cartridge B are consumables, it is necessary to replace them with new ones when they are consumed. If both are consumed at the same timing, they can be replaced at the same time. Of course, you may be comprised so that it may be consumed at a different timing. For example, when the water is consumed earlier than the fuel generation part D, only the water in the water cartridge B may be newly accommodated.

<Installation of water cartridge>
When hydrogen is generated by the fuel generator D and supplied to the power generation cell C, first, the fuel generator D is set in the internal space of the cell holder 6. Alternatively, when the fuel generating part D is not yet consumed, the fuel generating part D is set in the internal space of the cell holder 6. A state in which only the fuel generation part D is set is shown in a perspective view seen from the lower part of FIG. Next, the water cartridge B containing water is mounted on the mounting portion of the cell holder 6.

  As shown in FIG. 9, the water cartridge B is mounted from the lower side of the cell holder A. When attached, the tip of the water absorbent sheet 20 c is inserted from the outlet 31 a and comes into contact with the water supply body 32. Thereby, the water accommodated by the water absorbing body 32 penetrates through the water absorbing sheet 20c by the capillary phenomenon and is transmitted. And it reaches the porous layer 20a containing a hydrogen generating agent. As a result, the hydrogen generating agent and water react to generate hydrogen gas. In the above, the water absorbing sheet 20c and the outlet 31a correspond to a reaction liquid introduction mechanism. The water absorbent sheet 20c corresponds to a reaction liquid introduction member having one end provided outside the fuel generation part, and constitutes a reaction liquid introduction mechanism that guides the reaction liquid to the gas generating agent in the fuel generation part via this. ing. A cross-sectional view when the mounting is completed is shown in FIG.

  As described above, water is held in the water supply body 32 such as absorbent cotton, sponge, urethane foam, etc., and these water absorption bodies 32 have elasticity. Therefore, the surface of the water absorbing body 32 can be pressed by the tip of the water absorbing sheet 20c. In particular, the surface of the water-absorbing body 32 can be reliably pressed by lining the water-absorbing sheet 20c as described above. Thereby, the water currently hold | maintained at the water absorption body 32 can be transmitted to the water absorption sheet 20c.

  In the above, if the rigid sheet is lined on the flexible water absorbent sheet 20c, the water absorbent sheet 20c can be reliably inserted from the outlet 31a without being inadvertently deformed.

  The generation rate of hydrogen gas can be controlled by controlling the rate at which water reaches the hydrogen generating agent. For example, the speed at which water reaches the hydrogen generating agent can be controlled by a method using the water absorbing body 32 itself having a low water diffusion rate. The speed can also be controlled by the material, size, thickness, etc. of the water absorbent sheet 20c.

  As shown in FIG. 8, with the water cartridge B mounted on the cell holder A, the mounting portion has a nested structure. That is, the resin molded body 6 and the resin flat plate 60 are mounted in a state where the tip portions of the resin molded body 6 and the resin flat plate 60 are inserted into a gap formed between the outer case member 30 and the inner case member 31. Further, a waterproof seal 22 is provided in the groove 6 e between the inner wall surface of the outer case member 30 and the outer wall surface of the resin molded body 6 and the resin flat plate 60. Thereby, hydrogen gas inside cell holder A can be prevented from leaking outside.

  In the embodiment shown in FIG. 8, a configuration is adopted in which the water cartridge B is fitted into the outer peripheral surface of the cell holder 6, but is not limited thereto. That is, a configuration in which the water cartridge B is fitted on the inner peripheral surface side of the cell holder 6 may be employed. In this case as well, it is preferable to similarly adopt a seal structure using a waterproof seal.

<Hydrogen generator in sheet form>
As the sheet-like hydrogen generating agent 20, a porous hydrogen layer 20a containing a granular hydrogen generating agent and a resin formed on the upper surface of the base member 20b can be used. The hydrogen generating agent generates hydrogen gas by reacting with a reaction liquid such as water.

  Examples of such highly reactive hydrogen generators include calcium hydride, lithium hydride, potassium hydride, sodium borohydride, potassium borohydride, lithium aluminum hydride, sodium aluminum hydride, or magnesium hydride. And those containing a metal hydride compound. 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.

  The content of the hydrogen generating agent is preferably 10 to 60% by weight, and 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.

  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 porous layer 20a 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.

  The porous layer 20a has a structure made porous by air bubbles (foaming), sintering, phase separation, or the like, but preferably has a structure made porous by air bubbles. 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 layer 20a is prepared by mixing a granular hydrogen generator and an uncured thermosetting resin, and then applying the mixture onto the base member 20b to generate heat while generating hydrogen gas from the hydrogen generator. It is preferable to manufacture by the manufacturing method including the process of hardening curable resin.

The porous layer 20a is preferably density of 0.1~1.2g / cm ^3, more preferably 0.2~0.9g / cm ^3, 0.3~0.5g / cm ³ is more preferable. 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 porous layer obtained by curing is preferably from 0.1 to 10 mm, and more preferably from 0.5 to 2 mm, from the viewpoint of allowing water and the like to penetrate sufficiently and uniformly to perform a uniform reaction.

  As the base member 20b, a material such as a metal foil, particularly an aluminum foil or a copper foil can be used. In this case, the thickness is preferably 0.01 to 1 mm, more preferably 0.025 to 0.1 mm, taking into account the ease of bending and strength.

  Moreover, a water-absorbent sheet can be used as the base member 20b, and in that case, the following configuration is preferable. That is, examples of the water absorbent sheet include those made into a porous sheet using a hydrophilic material, but a water absorbent nonwoven fabric, a water absorbent woven fabric, a water absorbent paper, a filter paper, and the like are preferable. Furthermore, these can be used in combination or in combination with a water absorbent resin.

  Moreover, when using a water absorbing sheet as the base member 20b, it is preferable to integrate with the water absorbing sheet 20c. Thereby, a structure can be simplified.

The thickness of the water-absorbent sheet is preferably from 0.1 to 10 mm, more preferably from 0.2 to 2 mm, from the viewpoint of maintaining strength and enhancing in-plane permeability. The density of the water-absorbent sheet is preferably 0.1 to 1 g / cm ^{3 and} more preferably 0.4 to 0.6 g / cm ³ from the viewpoint of water retention and uniform in-plane permeability.

  The water-absorbent sheet may be provided only on one side of the porous layer, but can also be provided on both sides. When the water-absorbing sheet is provided on both sides, the water-absorbing sheet can be produced by further laminating the water-absorbing sheet on the upper surface after applying the raw material of the porous layer to any one of the water-absorbing sheets. Moreover, after applying the raw material of the porous layer, the hydrophobic porous film is laminated on the upper surface thereof, so that it is not necessary to separately arrange the hydrophobic porous film in the container.

  When the sheet-like hydrogen generating agent 20 is folded, it is preferable to apply the raw material for the porous layer to the planar water-absorbing sheet and then bend it before curing to maintain the shape. In that case, it is particularly preferable to laminate a water-absorbent sheet or a hydrophobic porous membrane on the upper surface of the porous layer.

<About ammonia remover>
In the present invention, an ammonia removing agent may be provided on the inner wall of the cell holder A, for example, in order to remove ammonia, which is an impurity, from hydrogen gas or the like generated in the fuel generator B. Specifically, a sheet-like ammonia removing agent can be disposed around the inner wall of the cell holder A. 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.

  The hydrogen generator as described above can generate hydrogen gas having a hydrogen composition of approximately 100% (excluding moisture), and this hydrogen gas may contain a trace amount of ammonia as an impurity. It is considered that this ammonia reacts with nitrogen in the air to produce a nitrogen compound (magnesium nitride or the like) when producing a hydrogen generating agent using magnesium, and this is produced by reaction with water. It is considered that the following reaction occurs at that time.

Mg ₃ N ₂ + 3H ₂ O → 3Mg (OH) ₂ + 2NH ₃
For other metal hydrides, the generated hydrogen gas may contain a small amount of ammonia by the same mechanism.

  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.

  Among them, it is more preferable that the adsorbent is one that removes ammonia by physical adsorption or chemical adsorption, solid acid, activated carbon (excluding those corresponding to solid acids), zeolite (excluding those corresponding to solid acids), And at least one selected from the group consisting of molecular sieves. Among these, it is preferable to use a solid acid from the viewpoint of adsorption / removal ability of ammonia and a viewpoint capable of adsorption at a higher temperature.

  Examples of the solid acid include those in which the solid acid itself is granular, and those in which a solid acid or liquid acid is supported on a granular material, but those in which a metal salt is supported on activated carbon are from the viewpoint of cost and manufacturability. More preferred. Examples of the metal salt include sulfates, phosphates, chloride salts, and nitrates. As the metal forming the salt, a metal exhibiting acidity can be suitably used.

  As the activated carbon (including those corresponding to solid acids), GW48 / 100, GW-H48 / 100, GG10 / 20, 2GG, GLC10 / 32, 2GS, GW10 / 32, GW20 / 40, KLY10 / 32, KW10 / 32, KW20 / 42 (above, manufactured by Kuraray Chemical Co., Ltd.), SWWB agent (for alkali), WB agent, S agent (for acid) (above, manufactured by Anico Japan Co., Ltd.), 4T-B, 4T-C 4G-H, 4SA, 2GS, GW20 / 4042 (manufactured by Kuraray Chemical Co., Ltd.) and the like, and 4T-B, SWWB agent (for alkali), and WB agent are preferable.

  As zeolite, BX, HISIV, R-3 (above, union Showa Co., Ltd. product) etc. are mentioned, Preferably it is BX.

  Examples of the molecular sieve include Zeorum A-3 and Zeorum A-4 (above, manufactured by Tosoh Corporation), and Zeolum A-4 is preferable.

<Circuit configuration>
Next, a circuit configuration for controlling the fuel cell will be described. The output voltage from each power generation cell C is taken out from the protrusions 4 b and 5 b of the first metal layer 4 and the second metal layer 5. The protruding portions 4b and 5b are connected (input) to the circuit portion. The output voltage is preferably boosted to a predetermined voltage by a DC-DC converter (corresponding to a booster circuit). 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. 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. The converter, the circuit unit, and the like are preferably configured as a circuit unit and integrated with the cell holder 6.

<Action and effect>
According to the configuration of the present invention, the water cartridge B that stores water as a reaction solution is configured to be detachable from the cell holder A. In order to guide water to the fuel generating part D, the water is supplied to the gas generating agent through the water absorbing sheet 20c (reaction liquid introducing member). The water absorbing sheet 20c is provided in the fuel generating part D, and can be completely separated from the fuel generating part D when the water cartridge B is removed. Therefore, hydrogen gas is not generated unnecessarily. When the water cartridge B is mounted, the water absorbent sheet 20c is inserted from the outlet 31a formed in the water cartridge B. Thus, since water is supplied to the gas generating agent, hydrogen gas is generated by the reaction between the gas generating agent and water.

[Another embodiment]
(1) In the previous embodiment, an example in which the size of the opening corresponding to the exposed portion of the metal layer is smaller than the size of the opening of the resin has been shown. However, as shown in FIG. It is also possible to make the size of the opening 6a of the resin molded body 6 smaller than the size of the 4 and 5 openings 4a, 5a. In that case, a part (for example, the periphery) of the electrode layers 2 and 3 exposed from the openings 4a and 5a is sealed by the resin molded body 6, so The adhesion between the electrode layers 2 and 3 and the metal layers 4 and 5 can be improved. In order to make the size of the opening 6a of the resin molded body 6 smaller than the size of the openings 4a and 5a, a mold having a convex portion whose upper surface is smaller than the size of the openings 4a and 5a is used. Then, sealing with resin may be performed in a state where the convex portions are in contact with the electrode layers 2 and 3.

  In the above case, the portion corresponding to the opening 6a of the resin molded body 6 cannot be applied to the periphery of the openings 4a and 5a of the metal layers 4 and 5 at the time of molding. For this reason, as shown in FIG.10 (b), by pressurizing parts other than opening 4a, 5a of the metal layers 4 and 5 at the time of shaping | molding, for example using another pin, the 1st metal layer 4 and the 1st The two metal layers 5 can be integrated by the resin molded body 6 in a state of being pressurized from both sides. When such pressurization is performed, a pressurization hole 6b is formed at a portion where the pin or the like is pressed.

  Furthermore, as shown in FIG. 10C, it is also possible to provide the resin molded body 6 with a through hole 6c that does not contribute to power generation. The through-hole 6c is provided with a through-hole in the solid polymer electrolyte layer 1, the electrode layers 2 and 3 and the like, a through-hole 6c smaller than the hole is provided, and the electrode layer 2 is formed by the resin molded body 6 around the through-hole 6c. , 3 etc. are integrated. According to the through-hole 6c, the solid polymer electrolyte layer 1, the electrode layers 2 and 3, and the metal layers 4 and 5 are integrated by the resin molded body 6 around the through-hole 6c, so that the electrode layers 2 and 3 and the metal layer 4 are integrated. , 5 can be increased.

  The through holes 6c that do not contribute to power generation are provided together with the exposed portions of the electrode layers 2 and 3 for power generation. Further, by pressing the portions other than the through hole 6c at the time of molding using, for example, another pin or the like, the resin molded body 6 presses the first metal layer 4 and the second metal layer 5 from both sides. Can be integrated. Also in that case, the pressurizing hole 6b is formed in the portion where the pin or the like is pressed.

  (2) In the previous embodiment, an example in which the size of the exposed portion of the first metal layer and / or the second metal layer is integrated with the resin molded body so that the size of the opening is substantially equal is shown. However, in the present invention, as shown in FIGS. 11A to 11B, a plurality of first metal layers 4 and / or second metal layers 5 are provided by providing one large hole 6 a on one surface. All or a part of the exposed portions may be exposed. FIG. 6 shows only one unit cell for the sake of simplicity.

  Further, by providing two or more large openings 6a on one side, half or less of the plurality of exposed portions of the first metal layer 4 and / or the second metal layer 5 may be exposed. That is, in this invention, you may shape | mold so that two or more exposed parts may be exposed from one opening 6a.

  (3) In the previous embodiment, the first conductive layer and the second conductive layer are formed from the first metal layer and the second metal layer having exposed portions that partially expose the first electrode layer and the second electrode layer. In the present invention, it is possible to use a conductive layer having no exposed portion as the first conductive layer and / or the second conductive layer. In that case, a conductive layer having gas permeability and gas diffusibility can be used. Examples of such a conductive layer include a porous metal layer, a porous conductive polymer layer, a conductive rubber layer, a conductive fiber layer, Examples thereof include conductive paste and conductive paint.

  (4) In the previous embodiment, the example in which the first electrode layer and the second electrode layer are exposed from the opening of the resin molded body is shown. However, in the present invention, the opening of the resin molded body and the first electrode layer or A porous layer may be interposed between the second electrode layer. In order to interpose a porous layer, a porous layer may be provided in advance on the outside of a metal layer or a conductive layer as a laminate used for insert molding. The porous layer and the metal layer or the conductive layer may be bonded in advance, or may be simply laminated.

  Examples of the material forming the porous layer include a porous film, a nonwoven fabric, and a woven fabric that can withstand the temperature at the time of insert molding.

  (5) In the previous embodiment, the example in which the opening for exposing the first electrode layer and the second electrode layer to the outside is provided in the resin molded body, but in the present invention, a gas or liquid is provided inside the resin molded body. It is also possible to provide a flow path for supplying. In that case, an electrode layer can be exposed to the flow path by performing insert molding as described above using a preform with a flow path provided on the inner surface on the side in contact with the conductive layer.

  (6) In the previous embodiment, one first conductive layer of the adjacent unit cells, the other second conductive layer, and the connection portion are formed of a metal layer made of a continuous metal plate. Although an example has been shown, the connecting portion in the present invention may be any as long as it can electrically connect one first conductive layer and the other second conductive layer.

  For example, it is possible to electrically connect one first conductive layer and the other second conductive layer with another member. For example, it is possible to perform solder connection using a member such as a metal wire. Moreover, the member which comprises a connection part, and the conductive layer may be electrically connected by contacting mechanically. For example, it is also possible to electrically connect one first conductive layer and the other second conductive layer by bringing them into contact with the conductive layer using a member such as a metal plate and integrating them with a resin molded body. It is.

  (7) In the previous embodiment, an example in which a plurality of unit cells are arranged in the same plane has been shown, but each unit cell can also be arranged three-dimensionally. For example, each unit cell may be arranged on each side such as two L-shaped sides, two or four sides of a square or rectangle, or two to three sides of a triangle.

  Thus, when each unit cell is arranged three-dimensionally, after three-dimensionally forming at the time of insert formation and using a flexible material to form two-dimensionally at the time of insert formation, this is three-dimensionally formed. There is a method to deform.

  In the former case, a metal plate in which one first conductive layer of the adjacent unit cells, the other second conductive layer, and the connection portion are continuous depends on the angle of the adjacent unit cells. It is preferably refracted. For example, when unit cells are arranged on the four sides of a square (square prism), the metal plate is refracted at an angle of about 90 °.

  Using such a metal plate, inserts are formed in a state in which the laminate constituting the unit cell is arranged on each of the four sides of the mold 10 having a quadrangular prism cavity and electrically connected to each other. By this method, a fuel cell in which unit cells are arranged on the four sides of the quadrangular prism can be manufactured.

  (8) In this embodiment, although the structure which integrates a power generation cell and a resin molding by insert molding was demonstrated, this invention is not limited to this. You may comprise so that the recessed part for arrange | positioning a power generation cell may be formed in a resin molding, and a power generation cell may be fixed to the recessed part by an appropriate method. Moreover, you may employ | adopt the structure which hold | maintains a power generation cell, without using a resin molding.

  (9) Another embodiment of the configuration of the water cartridge B will be described with reference to FIG. 11A is an external perspective view of the water cartridge B, and FIG. 11B is a longitudinal sectional view. As shown in the drawing, the outlet 31a is formed in a slit shape, but unlike the first embodiment, it is formed in two places. The length of the slit is set longer than the width dimension of the water absorbent sheet 20c.

  As shown in the cross-sectional view, a second water absorbing sheet 33 is disposed on the surface of the water absorbing body 32. Accordingly, the second water absorbing sheet 33 faces the outlet 31a. Since the second water absorbent sheet 33 is in contact with the inner wall surface of the inner case member 31 and has an area larger than the area of the outlet 31a, it does not jump out above the outlet 31a. The water absorbent 32 is formed of absorbent cotton or the like and has elasticity. Therefore, the second water absorbent sheet 33 is maintained in a state of being pressed against the inner wall surface of the inner case member 31.

  When the water cartridge B is attached to the cell holder A, the tip of the water absorbent sheet 20 c presses the surface of the second water absorbent sheet 33. Thereby, the water held by the water absorbing body 32 is introduced into the water absorbing sheet 20 c via the second water absorbing sheet 33. In this case, the water coming out of the water absorbing body 32 tends to move only upward. Therefore, if the water absorbing sheet 20c is positioned directly above the water absorbing body 32, the water in the water absorbing body 32 can be easily led to the water absorbing sheet 20c, but the water retained in the region E shown in FIG. Since the water absorbent sheet 20c is not located directly above, there is a possibility that the water absorbent body 32 will not be transmitted to the water absorbent sheet 20c. Therefore, by disposing the second water absorbing sheet 33 over the entire surface of the water absorbing body 32, even the water retained in the region E can be led to the water absorbing sheet 20c via the second water absorbing sheet 33. Can do.

  When the speed at which water is transmitted in the water absorbent sheets 20c and 33 is too high, it is possible to suppress the water from being supplied to the fuel generator D more than necessary by selecting the water that has a low speed at which water is transmitted inside the water absorbent 32. it can. That is, it is considered that the amount of water supply can be controlled by devising the material and shape of the water absorbing body 32.

  (10) In this embodiment, the water stored in the water cartridge B is held in the water absorbing body 32, but the water itself is stored in the storage space inside the inner case member 31 without using the water absorbing body 32. May be. In this case, the width is set so that water does not leak inadvertently from the outlet 31a (maintained by surface tension).

  (11) In the above-described embodiment, the example of the reaction liquid introduction mechanism in which the reaction liquid introduction member is inserted into the outlet (outlet part) formed in the reaction liquid storage cartridge has been described. It is only necessary to provide a reaction liquid introduction mechanism that guides the reaction liquid to the gas generating agent in the fuel generation part via the reaction liquid introduction member provided at one end on the outside, and the reaction liquid introduction member is brought into contact with the outlet part. It may be a reaction liquid introduction mechanism. For example, as shown in FIG. 12, the reaction liquid introduction mechanism includes a surface 20 d at one end of a water absorbent sheet 20 c that is a reaction liquid introduction member, and a sheet-like member 33 having water absorption formed in the reaction liquid storage cartridge 30. It may be in contact with the surface 33a of the lead-out part.

  In this example, in order to make the height of the surface 33 a of the sheet-like member 33 constant, a support portion 34 for supporting the sheet-like member 33 is provided in the water cartridge B. Further, in order to eliminate the need for the top and bottom, a water absorbing body 32 is provided inside the water cartridge B, and the gap between the outlet 31a through which the sheet-like member 33 is exposed and the support portion 34 is reduced.

  On the other hand, the water absorbing sheet 20 c passes through a slit on the bottom surface of the case 25 that houses the hydrogen generating material 20, and a tip portion of which one end is bent is bonded to the bottom surface of the case 25 that houses the hydrogen generating material 20. . The case 25 is provided with a hydrogen discharge port 25a, which is supplied to the power generation cell C held by the resin molded body 6. The air and excess hydrogen existing at the initial stage are released from the opening 6 h of the resin molded body 6. In this example, four power generation cells C (not shown) are arranged on four sides of a side wall of a resin molded body 6 having a square pillar shape whose upper surface is substantially square.

  (12) In the above-described embodiment, the example in which the reaction liquid stored in the reaction liquid storage cartridge is supplied to the hydrogen generation material has been shown. However, in the present invention, the reaction liquid is supplied to the hydrogen generation material without using the reaction liquid storage cartridge. It is also possible to supply For example, a reaction liquid introduction mechanism that guides the reaction liquid to a gas generating agent in the fuel generation part via a reaction liquid introduction member provided at one end outside the fuel generation part on a container containing a reaction liquid such as water It is possible to generate electric power simply by placing the fuel cell provided with

  In the example shown in FIG. 13, water can be supplied to the hydrogen generating material 20 by absorbing water from one end of the water absorbing sheet 20 c provided on the bottom surface of the case 25 using the same fuel cell as in FIG. 12. It is possible to generate power in the power generation cell C with the generated hydrogen.

A Cell holder B Water cartridge C, C1, C2, C3, C4 Power generation cell D Fuel generation part 1 Solid polymer electrolyte layer 2 First electrode layer 3 Second electrode layer 4 First metal layer (first conductive layer)
4a Opening (exposed part)
5 Second metal layer (second conductive layer)
5a Opening (exposed part)
6 resin molded body 6a opening 6e groove 20 hydrogen generating agent 20a porous layer 20b base member 20c water absorbent sheet 22 waterproof seal 31a outlet 60 resin flat plate

Claims (10)

A power generation cell that generates power by supplying fuel gas from one surface and oxygen from the other surface;
A cell holder that forms an internal space with the power generation cell by holding the power generation cell with the one surface facing inward,
A fuel generating unit that is disposed in the internal space of the cell holder and contains a gas generating agent that reacts with a reaction solution to generate a fuel gas;
A fuel cell comprising: a reaction liquid introduction mechanism that guides the reaction liquid to a gas generating agent in the fuel generation part via a reaction liquid introduction member having one end provided outside the fuel generation part. The apparatus further includes a reaction liquid storage cartridge that is detachable from the cell holder and stores the reaction liquid.
The reaction liquid introduction mechanism includes a lead-out portion formed on the reaction liquid storage cartridge, and the reaction liquid introduction member contacts the lead-out portion when the reaction liquid storage cartridge is mounted on the cell holder. Alternatively, a fuel cell in which the reaction liquid is supplied to the gas generating agent through the reaction liquid introduction member by being inserted.   3. The fuel cell according to claim 1, wherein the fuel generating unit contains a hydrogen generating agent that reacts with a reaction solution containing water to generate hydrogen gas.   The fuel cell according to claim 1, wherein the reaction liquid introduction member is a sheet-like member having water absorption.   The reaction liquid introduction mechanism includes a surface of one end of a reaction liquid introduction member that is a sheet-like member having water absorption, and a surface of a lead-out portion that is formed of the sheet-like member having water absorption formed in the reaction liquid storage cartridge. The fuel cell according to claim 2 or 3, wherein   The fuel cell according to any one of claims 2 to 5, wherein a mounting portion of the cell holder and the reaction liquid storage cartridge has a nested structure, and a waterproof seal is provided on the mounting portion.   The said cell holding body comprises a flat box with the said power generation cell, The said power generation cell is arrange | positioned on the single side | surface or both surfaces of the opposing surface of the box. Fuel cell.   The fuel cell according to any one of claims 1 to 7, wherein the plurality of power generation cells are integrally formed with the cell holder by insert molding in a state where a plurality of the power generation cells are electrically connected to each other.   The reaction liquid in the reaction liquid storage cartridge is held by an elastic water absorbing body, and the tip of the reaction liquid introduction member presses the water absorption body when the reaction liquid storage cartridge is mounted. The fuel cell according to item.   The reaction liquid in the reaction liquid storage cartridge is held by a water absorbing body, the surface of the water absorption body is covered with a water absorption sheet, and the tip of the reaction liquid introduction member presses the water absorption body when the reaction liquid storage cartridge is mounted. The fuel cell according to any one of claims 2 to 8.

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