JP4683831B2 - Fuel cell container, fuel cell and electronic device - Google Patents

Description

  The present invention relates to a small and highly reliable fuel cell container made of ceramics that accommodates an electrolyte member, a fuel cell using the same, and an electronic device.

  In recent years, development of small fuel cells that operate at a lower temperature than before has been actively conducted. Depending on the type of electrolyte used for the fuel cell, a polymer electrolyte fuel cell (hereinafter referred to as PEFC), a phosphoric acid fuel cell, or a solid electrolyte fuel cell is known. ing.

Among them, PEFC has a low operating temperature of about 80-100 ° C,
(1) The output density is high, and the size and weight can be reduced.
(2) Since the electrolyte is not corrosive and the operating temperature is low, since there are few restrictions on the battery constituent materials from the viewpoint of corrosion resistance, cost reduction is easy.
(3) Since it can be started at room temperature, the startup time is short.
It has excellent features such as For this reason, PEFC takes advantage of the above features and is not only applied to driving power sources for vehicles and cogeneration systems for homes, but also to mobile phones, PDAs (Personal Digital Assistants), laptop computers, digital cameras, The use as a power source for portable electronic devices whose output of a video camera or the like has several W to several tens of W has been considered.

The PEFC is roughly divided, for example, a fuel electrode (cathode) composed of a carbon electrode to which catalyst fine particles such as platinum and platinum-ruthenium are adhered, and an air electrode (anode) composed of a carbon electrode to which catalyst fine particles such as platinum are adhered, A film-like electrolyte member (hereinafter referred to as an electrolyte member) interposed between the fuel electrode and the air electrode is configured. Here, hydrogen gas (H ₂ ) extracted through the reforming unit is supplied to the fuel electrode, while oxygen gas (O ₂ ) in the atmosphere is supplied to the air electrode, Predetermined electric energy is generated (power generation) by the electrochemical reaction, and electric energy that is a driving power source (voltage / current) for the load is generated.

Specifically, when the hydrogen gas to the fuel electrode (H ₂₎ is supplied, as shown in the following chemical equation (1), electrons by the catalyst (e ^-) is separated hydrogen ions (protons; H ⁺ ) Is generated and passes through the electrolyte member to the air electrode side, and electrons (e ⁻ ) are taken out by the carbon electrode constituting the fuel electrode and supplied to the load.

3H ₂ → 6H ⁺ + 6e ⁻ (1)
On the other hand, when air is supplied to the air electrode, as shown in the following chemical reaction formula (2), electrons (e ⁻ ) passing through the load by the catalyst and hydrogen ions (H ⁺ ) passing through the electrolyte member, Reaction with oxygen gas (O ₂ ) in the air produces water (H ₂ O).

6H ⁺ + 3 / 2O ₂ + 6e ⁻ → 3H ₂ O (2)
Such a series of electrochemical reactions (formula (1) and formula (2)) proceeds at a relatively low temperature condition of approximately 80 to 100 ° C., and by-products other than electric power are basically water (H ₂ O) only.

  The ion conductive film (exchange membrane) constituting the electrolyte member is a polystyrene-based cation exchange membrane having a sulfonic acid group, a mixed membrane of fluorocarbon sulfonic acid and polyvinylidene fluoride, and trifluoroethylene grafted on a fluorocarbon matrix. Recently, a perfluorocarbon sulfonic acid membrane (for example, trade name “Nafion” manufactured by DuPont) or the like has been used.

  FIG. 4 is a sectional view showing the structure of a conventional fuel cell (PEFC). In the figure, 21 is a PEFC, 23 is an electrolyte member, 24 and 25 are arranged on the electrolyte member 23 so as to sandwich the electrolyte member, and a pair of porous electrodes having functions as a gas diffusion layer and a catalyst layer, that is, A fuel electrode and an air electrode, 26 is a gas separator, 28 is a fuel flow path, and 29 is an air flow path.

  The gas separator 26 is provided so as to penetrate the separator portion and the gas inflow / outflow frame that form the outer shape of the gas separator 26, the separator portion that separates the fuel passage 28 and the air passage 29, and the separator portion. The electrode member is configured to correspond to the fuel electrode 24 and the air electrode 25 of the electrolyte member 23. A fuel cell stack, which is the smallest unit of a battery, is formed by stacking a large number of gas electrodes 26 so that the fuel electrode 24 and the air electrode 25 of the electrolyte member 23 are electrically connected in series and / or in parallel. A typical PEFC body is a stack in a box.

A fuel gas containing water vapor (a gas rich in hydrogen) is supplied from the reformer to the fuel electrode 24 through the fuel flow path 28 formed in the gas separator 26, and the air electrode 25 is passed through the air flow path 29 to the atmosphere. Is supplied with air as an oxidizing gas, and is generated by a chemical reaction in the electrolyte member 23.
JP 2001-266910 A Special table 2001-507501 gazette

  However, the fuel cell 21 conventionally proposed and developed as such a high-voltage, high-capacity battery is a large-sized and large-sized battery having a stack structure and a large area, and a small battery. Conventionally, the use of the fuel cell has been hardly considered.

  That is, in the conventional gas separator 26 in such a fuel cell 21, the side surface of the electrolyte member 23 is exposed to the outside in a laminate in which the electrolyte member 23 is laminated using the gas separator 26. There is a problem that the fuel cell 21 is easily damaged and it is difficult to ensure the mechanical reliability of the fuel cell 21 as a whole.

  In addition, in order to mount the fuel cell 21 in a portable electronic device, a fuel cell container that is different from conventional large-sized fuels and is excellent in compactness, simplicity, and safety is required. That is, in order to be applied as a portable power source such as a general-purpose chemical battery, in order to shorten the temperature rise to the operating temperature and to reduce the heat capacity, the fuel cell container is reduced in size and height. However, the gas separator 26 occupying most of the heat capacity in the conventional fuel cell 21 is thinned, particularly in the case of the gas separator 26 in which the flow path is formed by cutting on the surface of the carbon plate. Since it becomes brittle, a thickness of several mm is required. Therefore, there is a problem that it is difficult to reduce the size and height.

  Furthermore, the output voltage of the fuel cell 21 is determined by the partial pressure of the gas supplied to the electrodes 24 and 25 on the front and back surfaces of the electrolyte member 23. That is, when the fuel gas supplied to the electrolyte member 23 travels through the gas flow path 28 and is consumed in the power generation reaction, the partial pressure of the fuel gas on the surface of the fuel electrode 24 decreases and the output voltage decreases. In the same manner, when the air also travels through the air flow path 29 and is consumed, the partial pressure of oxygen on the surface of the air electrode 25 decreases, and the output voltage decreases. Accordingly, it is necessary to supply the fuel gas evenly. However, the gas separator 26 of the conventional fuel cell 21 has a flow path formed by cutting on the surface of the carbon plate. Since the groove is narrow, there is a problem that the flow resistance is increased and it is difficult to supply a uniform gas.

  In addition, a combination of the plurality of electrolyte members 23 and the opposed fuel electrode 24, air electrode 25, and gas separator 26 is arbitrarily and efficiently connected in series or in parallel to adjust the overall output voltage and output current. However, in the conventional fuel cell 21, in order to take out electricity from the fuel electrode and the air electrode sandwiching the electrolyte member 23, a method of connecting to the outside or connecting the gas separator 26 as a conductive material is used. There is only a method of connecting them in series, and there is a problem that it is difficult in a small fuel cell.

  The present invention has been completed in view of the above-described problems of the prior art, and an object of the present invention is a small and robust fuel cell container that can accommodate an electrolyte member, An object of the present invention is to provide a highly reliable fuel cell container capable of uniform supply, uniform temperature gradient in the fuel cell container, and highly efficient electrical connection, and a fuel cell using the same.

The fuel cell container of the present invention includes a base body made of ceramics having a concave portion for accommodating an electrolyte member having first and second electrodes on the lower and upper main surfaces, respectively, and the lower main surface of the electrolyte member. One end is disposed on the first fluid flow path formed from the bottom surface of the recess facing the outer surface of the substrate and the bottom surface of the recess facing the first electrode of the electrolyte member, and the other end is the substrate. A first wiring conductor led out to an outer surface of the substrate, a lid body, which is attached to the upper surface around the recess of the base so as to cover the recess, and hermetically seals the recess, and the upper side of the electrolyte member One end is disposed on the lower surface of the lid facing the second electrode of the electrolyte member, the second fluid flow path formed from the lower surface of the lid facing the main surface to the outer surface of the lid, The other end was led to the outer surface of the lid 2 wiring conductors, and at least one of the first fluid channel and the second fluid channel is formed around the opening of the first fluid channel on the bottom surface of the recess or on the lower surface of the lid. around the opening of the second fluid flow path, said first electrode or said second electrode is formed so as to abut, one of the first wiring conductor and the second conductor, the first electrode or The portion formed to be in contact with the second electrode is made of a metallized layer mainly composed of at least one of tungsten and molybdenum, and a gold plating layer is directly applied to the exposed surface. The portions formed on the outer surface of the base and the outer surface of the lid of the wiring conductor and the second wiring conductor are formed of the metallized layer, and a nickel plating layer and a gold plating are formed on the exposed surface. Layer is characterized in that it is sequentially deposited.

  In the fuel cell of the present invention, the electrolyte member is accommodated in the recess of the fuel cell container of the present invention having the above-described configuration, and the lower and upper main surfaces of the electrolyte member are the first and second fluid flow paths. The first and second electrodes are electrically connected to the first and second wiring conductors, respectively, and the upper surface around the recess of the base body The cover is attached to cover the recess.

  The electronic apparatus of the present invention is characterized by having the fuel cell of the present invention as a power source.

  The fuel cell container of the present invention has a base made of ceramics having a concave portion for accommodating an electrolyte member having first and second electrodes on the lower and upper main surfaces, respectively, and an upper surface around the concave portion of the base. Since it has a lid that covers and attaches to the recess and hermetically seals the recess, the fuel cell container is hermetically sealed so that there is no leakage of fluid such as gas, Since it is not necessary to provide a container such as a package in addition to this container, it is possible to obtain a fuel cell that can be operated efficiently, and it is also effective for downsizing. In addition, since a plurality of electrolyte members can be housed in a box formed by a ceramic body having a concave portion on the upper surface and a lid that seals the concave portion, a fuel cell can be obtained. The mechanical reliability of the entire fuel cell is improved without being exposed to the outside and being damaged. In addition to the first and second wiring conductors, one end of which is disposed inside the container constituted by the recess and the lid, unnecessary electrical contact with the electrolyte member itself can be avoided, so that reliability and safety are ensured. High fuel cell can be obtained. Furthermore, by using ceramics as the constituent material of the fuel cell container, it is possible to obtain a fuel cell having excellent corrosion resistance against fluids including various gases.

  Also, a first fluid channel formed from the bottom surface of the recess facing the lower main surface of the electrolyte member to the outer surface of the substrate, and formed from the lower surface of the lid body facing the upper main surface of the electrolyte member to the outer surface of the lid body. Since each of the plurality of fluid flow paths is provided on the inner wall surfaces facing each other across the electrolyte member, the fluid supplied to the electrolyte member The uniform supply performance can be improved. According to such a fluid path, since the fluid flows perpendicularly to the electrolyte member, for example, when the fluid is hydrogen gas and air (oxygen) gas, the electrolyte member has on the lower and upper main surfaces, respectively. Each gas partial pressure supplied to the first and second electrodes does not decrease, and there is an effect that a predetermined stable output voltage can be obtained. Further, since the pressure of the fluid to be supplied, for example, the gas partial pressure is stabilized, the distribution of the internal temperature of the fuel cell container is made uniform, and as a result, the thermal stress generated in the electrolyte member can be suppressed. Reliability can be improved. Furthermore, since each fluid flow path is formed in the base and the lid, each of the flow paths is excellent in hermeticity, and originally two types of raw material fluids (for example, oxygen gas and hydrogen) that should be isolated in the flow path are used. Gas or methanol, etc.) will not function as a fuel cell, and there is no risk of ignition or explosion after a flammable fluid is mixed at a high temperature. A safe fuel cell can be provided.

  At least one of the first fluid channel and the second fluid channel is formed around the opening of the first fluid channel on the bottom surface of the recess or the periphery of the opening of the second fluid channel on the bottom surface of the lid. Since it is formed so as to be in contact with the electrode or the second electrode, the contact area between the first electrode and the first wiring conductor of the electrolyte member and the contact area between the second electrode and the second wiring conductor can be increased and directly applied. Since the increase in electrical resistance and poor contact can be effectively suppressed, a fuel cell having high power generation efficiency can be provided.

In addition, a portion of the first wiring conductor and the second wiring conductor formed so as to be in contact with the first electrode or the second electrode is made of a metallized layer mainly composed of at least one of tungsten and molybdenum and exposed. gold plating layer on the surface to have been deposited directly, the outer surface and portion formed on the outer surface of the cover substrate of the first wiring conductor and the second wiring conductor, on the exposed surface with composed of the metallized layer Since the nickel plating layer and the gold plating layer are sequentially deposited, the portion formed on the outer surface of the base body of the first wiring conductor and the second wiring conductor and the outer surface of the lid body is not in contact with air gas or fuel gas. In, the metallized layer and the gold plating layer can be firmly attached via the nickel plating layer which is the base plating layer. On the other hand, a portion of the first wiring conductor and the second wiring conductor formed so as to be in contact with the first electrode or the second electrode has a metallized layer that hardly dissolves during an electrochemical reaction of air gas or fuel gas, and It is composed of a gold plating layer and can effectively prevent corrosion of the electrode. That is, when a base plating layer such as a nickel plating layer is provided on the metallized layer in a portion of the first wiring conductor and the second wiring conductor formed so as to be in contact with the first electrode or the second electrode, In addition, the base plating layer is likely to melt during the electrochemical reaction of the fuel gas, but by not forming the base plating layer, the connection between the first wiring conductor and the first electrode and the second wiring conductor and the second electrode Can maintain a good connection.

  Further, since the space between the contacted first wiring conductor and the first electrode or between the contacted second wiring conductor and the second electrode is compressed with pressure applied, the first wiring conductor Even if the gold plating layer is directly formed on the metallized layer without forming the base plating layer on the upper surface of the metallized layer of the second wiring conductor, good adhesion can be maintained without peeling off the gold plating layer.

  Further, since the gold plating layer is a very flexible metal, the gold plating layer is made of gold by the compressive force between the abutting first wiring conductor and the first electrode or between the abutting second wiring conductor and the second electrode. The plating layer can be appropriately deformed to fill the gap between the first wiring conductor and the first electrode or between the abutting second wiring conductor and the second electrode without gaps, increasing electrical resistance and poor contact. Can be more effectively suppressed.

  As a result, in the first electrode and the second electrode, there is provided a fuel cell having high power generation efficiency with small electric resistance without hindering the electrochemical reaction of air gas or fuel gas by the dissolved metal ions. Can do.

  In the fuel cell of the present invention, the electrolyte member is accommodated in the recess of the fuel cell container of the present invention, and the lower and upper main surfaces of the electrolyte member are respectively connected to the first and second fluid flow paths. The first and second electrodes are electrically connected to the first and second wiring conductors, respectively, and the lid is attached to the upper surface around the concave portion of the base body. Therefore, the fuel cell container of the present invention as described above has the features of a small, robust, uniform gas supply, uniform temperature gradient in the fuel cell container, and highly efficient electrical connection. A highly reliable fuel cell that can be obtained can be obtained.

  Since the electronic device according to the present invention has the fuel cell according to the present invention as a power source, the electronic device according to the present invention is small, low-profile, and stable over a long period of time with the features of the fuel cell container according to the present invention. Thus, it is possible to obtain an electronic device with excellent safety and convenience.

  In addition, if the fuel cell as a power source is provided with external connection terminals (positive terminal and negative terminal) on at least one of the base and lid, it can be easily electrically connected to the circuit board of the electronic device. And can be freely attached and detached. Therefore, the fuel cell can be easily replaced with a new one without using a facility equipped with special safety equipment, and the convenience of the electronic device can be enhanced.

  Furthermore, since a metal layer can be formed in various shapes and electrical characteristics by a metallization method or the like inside the base of the fuel cell container, an electronic circuit element that functions as a resistance, capacitance, inductance, etc. is provided inside the base. Can be formed. Therefore, for example, when a large capacity capacitor is formed in parallel with the fuel cell, when the current output from the fuel cell becomes insufficient, the insufficient current is compensated to meet the target output current. It is possible to ensure a sufficient current supply. In addition, since a booster circuit can be formed, a voltage necessary for the electronic device can be secured.

  A fuel cell container and a fuel cell according to the present invention will be described below in detail with reference to the accompanying drawings.

  FIG. 1 is a cross-sectional view showing an example of an embodiment of a fuel cell container and a fuel cell using the same according to the present invention. In FIG. 1, 1 is a fuel cell, 2 is a fuel cell container, 3 is an electrolyte member, 4 is a first electrode, 5 is a second electrode, 6 is a base, 7 is a lid, 8 is a first fluid flow path, 9 is a second fluid flow path, 10 is a first wiring conductor, 11 is a second wiring conductor, and 12 is an opening shape.

  The electrolyte member 3 in the present invention faces, for example, the first electrode 4 formed on the lower main surface and the second electrode 5 formed on the upper main surface on both main surfaces of the ion conductive film (exchange membrane). Thus, a fuel electrode (not shown) serving as an anode electrode and an air electrode (not shown) serving as a cathode electrode are integrally formed. And the electric current generated with the electrolyte member 3 can be sent to the 1st electrode 4 and the 2nd electrode 5, and it can take out outside.

  Such an ion conductive film (exchange membrane) of the electrolyte member 3 is made of a perfluorocarbon sulfonic acid resin, for example, a proton conductive ion exchange resin such as a trade name “Nafion” (manufactured by DuPont). Further, the fuel electrode and the air electrode are gas diffusion electrodes in a porous state, and have both functions of a porous catalyst layer and a gas diffusion layer. These fuel electrode and air electrode are constituted by a porous material in which conductive fine particles carrying a catalyst such as platinum, palladium or alloys thereof, for example, carbon fine particles are held by a hydrophobic resin binder such as polytetrafluoroethylene. Has been.

  The first electrode 4 on the lower main surface and the second electrode 5 on the upper main surface of the electrolyte member 3 are a method of hot pressing a carbon electrode with catalyst fine particles such as platinum or platinum-ruthenium on the electrolyte member 3, or Further, it is formed by a method of applying or transferring a mixture of a carbon electrode material with catalyst fine particles such as platinum or platinum-ruthenium and a solution in which an electrolyte material is dispersed onto the electrolyte.

The fuel cell container 2 is composed of a base 6 having a recess and a lid 7, and has a function of mounting the electrolyte member 3 inside the recess and hermetically sealing the aluminum oxide (Al ₂ O ₃ ) body, mullite _{(3Al 2 O 3 · 2SiO 2} ) sintered material, silicon carbide (SiC) sintered material, aluminum nitride (AlN) sintered material, silicon nitride _(Si 3 _{N 4)} sintered material It is formed of a ceramic material such as a glass ceramic sintered body.

The glass ceramic sintered body includes a glass component and a filler component. Examples of the glass component include SiO ₂ —B ₂ O ₃ , SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ , and SiO ₂ —. B ₂ O ₃ —Al ₂ O ₃ —MO system (M represents Ca, Sr, Mg, Ba or Zn), SiO ₂ —Al ₂ O ₃ —M ¹ O—M ² O system (M ¹ and M ² are the same or different and represent Ca, Sr, Mg, Ba or Zn), SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —M ¹ O—M ² O system (provided that M ¹ and M ² is the same as above), SiO ₂ —B ₂ O ₃ —M ³ ₂ O system (where M ³ represents Li, Na or K), SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ — M ³ ₂ O-based (where M ³ is the same as above), Pb-based glass And Bi-based glass.

Examples of the filler component include a composite oxide of Al ₂ O ₃ , SiO ₂ , ZrO ₂ and an alkaline earth metal oxide, a composite oxide of TiO ₂ and an alkaline earth metal oxide, Al ₂ O _3. And composite oxides containing at least one selected from SiO ₂ (for example, spinel, mullite, cordierite) and the like.

  The fuel cell container 2 is composed of a base 6 having a recess and a lid 7, and covers the recess around the recess of the base 6 to attach the lid 7 so that the recess is hermetically sealed. Bonding with metal bonding materials such as silver brazing, bonding with resin materials such as epoxy resin, sealing ring made of iron alloy etc. on the upper surface around the recess, seam weld, electron beam, laser, etc. The lid body 7 is attached to the base body 6 by a welding method or the like. The lid 7 may be formed with a recess similar to the base 6.

  In order to reduce the thickness of the base body 6 and the lid body 7 and to reduce the height of the fuel cell 1, the bending strength, which is mechanical strength, is preferably 200 MPa or more.

  The base body 6 and the lid body 7 are preferably formed of an aluminum oxide sintered body made of a dense material having a relative density of 95% or more, for example. In that case, for example, first, a rare earth oxide powder or a sintering aid is added to and mixed with the aluminum oxide powder to prepare a raw material powder of the aluminum oxide sintered body. Next, an organic binder and a dispersion medium are added to the raw material powder of this aluminum oxide sintered body, mixed to form a paste, and from this paste, an organic binder is added to the raw material powder by a press blade method, press molding, rolling molding, etc. Thus, a green sheet having a predetermined thickness is produced. Then, through this green sheet, through holes as the first fluid flow path 8 and the second fluid flow path 9 are formed by a punching method using a mold, a drilling method using a micro drill, a drilling method using laser light irradiation, and the like. A through hole for arranging the first wiring conductor 10 and the second wiring conductor 11 is formed.

The first wiring conductor 10 and the second wiring conductor 11, in order to prevent oxidation, that is formed by tungsten and / or molybdenum. In that case, for example, ₃ to 20 parts by mass of Al ₂ O ₃ and 0.5 to 5 parts by mass of Nb ₂ O ₅ with respect to 100 parts by mass of tungsten and / or molybdenum powder as inorganic components. A conductor paste is prepared by adding. The conductor paste is filled into the through hole of the green sheet to form a via conductor as a through conductor.

  In these conductor pastes, in order to improve the adhesion of the substrate 6 and the lid 7 to the ceramic, aluminum oxide powder or the same composition powder as the ceramic component forming the substrate 6 and the lid 7 is used. It is also possible to add 0.05 to 2% by volume.

  The formation of the first wiring conductor 10 and the second wiring conductor 11 on the surface layer and the inner layer of the base body 6 and the lid body 7 is the same as before or after forming the via conductor by filling the through hole with the conductive paste. The conductive paste is formed by printing and applying to a predetermined pattern on the green sheet by a method such as screen printing or gravure printing.

  Then, after aligning and laminating and pressure-bonding a predetermined number of sheet-like molded bodies filled with conductive paste, the laminated body is heated at a maximum firing temperature of 1200 to 1500 ° C., for example, in a non-oxidizing atmosphere. To obtain the target ceramic base 6, lid 7, first wiring conductor 10, and second wiring conductor 11.

  Moreover, it is preferable that the base | substrate 6 and the cover body 7 which consist of ceramics shall be 0.2 mm or more in thickness. If the thickness is less than 0.2 mm, the strength tends to decrease. Therefore, cracks and the like tend to occur in the base body 6 and the lid body 7 due to the stress generated when the lid body 7 is attached to the base body 6. . On the other hand, if the thickness exceeds 5 mm, it will be difficult to reduce the thickness and height, making it unsuitable as a fuel cell to be mounted on a small portable device, and increasing the heat capacity. It tends to be difficult to quickly set an appropriate temperature corresponding to the conditions.

  The first wiring conductor 10 and the second wiring conductor 11 are electrically connected to the first electrode 4 and the second electrode 5 of the electrolyte member 3, respectively, and the current generated by the electrolyte member 3 is supplied to the fuel cell container 2. It functions as a conductive path for taking it out.

  The first wiring conductor 10 is formed such that one end is disposed at a portion of the bottom surface of the recess of the base 6 facing the first electrode 4 of the electrolyte member 3 and the other end is led out to the outer surface of the base 6. The first wiring conductor 10 is formed integrally with the base body 6 as described above, and protrudes by 10 μm or more from the bottom surface of the recess of the base body 6 so that the first wiring conductor 10 can be easily brought into contact with the first electrode 4. It is desirable to form so as to. In order to obtain this height, as described above, the printing conditions may be set to be thick when the conductor paste is formed by printing and coating. In addition, it is desirable that a plurality of first wiring conductors 10 be arranged opposite to the first electrode 4 to reduce electrical loss due to the first wiring conductors 10. The diameter is preferably 50 μm or more.

  The second wiring conductor 11 is formed such that one end is disposed on the lower surface of the lid 7 facing the second electrode 5 of the electrolyte member 3 and the other end is led out to the outer surface of the lid 7. . Similar to the first wiring conductor 10, the second wiring conductor 11 is also formed integrally with the lid body 7, and the concave portion of the lid body 7 is provided so that the second wiring conductor 11 can be easily brought into contact with the second electrode 5. It is desirable to form so that it may protrude 10 micrometers or more from the bottom face. In order to obtain this protruding height, the printing conditions may be set to be thick when the conductor paste is formed by printing and coating as described above. A plurality of second wiring conductors 11 are preferably arranged opposite to the second electrode 5 to reduce the electrical loss due to the second wiring conductors 11. The through-hole of the lid 7 of the second wiring conductor 11 is φ50 μm. It is preferable to set it as the above diameter.

  The first and second wiring conductors 10 and 11 and the first and second electrodes 4 and 5 are electrically connected to each other by sandwiching the electrolyte member 3 between the base 6 and the lid body 7. What is necessary is just to carry out by the structure of making the 2nd wiring conductors 10 and 11 and the 1st and 2nd electrodes 4 and 5 press-contact and electrically connecting.

  In addition, a first fluid channel 8 and a second fluid channel 9 are disposed on the bottom surface of the recess of the base 6 facing the first electrode 4 and the second electrode 5 and the bottom surface of the lid body 7, respectively. The first fluid channel 8 is formed over the outer surface of the base 6, and the second fluid channel 9 is formed over the outer surface of the lid 7. The first and second fluid flow paths 8 and 9 are formed of electrolyte members such as a reformed gas rich in a fuel gas, such as hydrogen, or an oxidizing gas, such as air, by through holes or grooves formed in the base body 6 and the lid body 7, respectively. 3 is provided as a passage for the fluid supplied to 3 or as a passage for the fluid discharged from the electrolyte member 3 after the reaction, such as water generated by the reaction.

  The through holes or grooves formed in the base body 6 and the lid body 7 as the first fluid flow path 8 and the second fluid flow path 9 are configured so that fluid such as fuel gas or oxidizing gas is evenly supplied to the electrolyte member 3. Depending on the specifications of the fuel cell 1, the diameter and number of through holes, or the width, depth and arrangement of the grooves may be determined.

  In the fuel cell container 2 and the fuel cell 1 of the present invention, the first fluid channel 8 and the second fluid channel 9 preferably have a diameter of 0.1 mm in order to allow fluid to flow through the electrolyte member 3 with uniform pressure. It is preferable that the holes have the above diameters and are arranged with a constant interval.

  In this way, the first fluid flow path 8 is made to face the lower main surface on which the first electrode 4 of the electrolyte member 3 is formed, and the second fluid flow is made to face the upper main surface on which the second electrode 5 is formed. By forming the passage 9, fluid can be exchanged between the lower and upper main surfaces of the electrolyte member 3 and the first and second fluid flow paths 8, 9, and the fluid is supplied through the respective flow paths. Will be discharged. For example, in the case of supplying a gas as a fluid, it is possible to prevent the partial pressure of the gas supplied to the first electrode 4 and the second electrode 5 of the electrolyte member 3 from decreasing, and a predetermined stable output voltage. Can be obtained. Further, since the supplied gas partial pressure is stabilized, the internal pressure of the fuel cell 1 is made uniform, and as a result, the thermal stress generated in the electrolyte member 3 can be suppressed, so that the reliability of the fuel cell 1 is improved. Can be made.

  In the present invention, at least one of the first fluid channel 8 and the second fluid channel 9 is the second fluid flow around the opening of the first fluid channel 8 on the bottom surface of the recess or the lower surface of the lid 7. The first electrode 4 or the second electrode 5 of the first wiring conductor 10 and the second wiring conductor 11 is formed around the opening of the path 9 so as to contact the first electrode 4 or the second electrode 5. The portion formed so as to come into contact with is made of a metallized layer and the gold plating layer 11a is directly attached to the exposed surface thereof, and the outer surface of the base 6 of the first wiring conductor 10 and the second wiring conductor 11 and The portion formed on the outer surface of the lid body 7 is made of a metallized layer, and a nickel plating layer 11b and a gold plating layer 11a are sequentially deposited on the exposed surface.

  As a result, the metallized layer and the gold plating layer 11a are formed on the outer surface of the base body 6 and the outer surface of the lid body 7 of the first wiring conductor 10 and the second wiring conductor 11 and the portions that do not come into contact with air gas or fuel gas. Can be firmly applied via the nickel plating layer 11b which is the base plating layer. On the other hand, portions of the first wiring conductor 10 and the second wiring conductor 11 that are formed so as to come into contact with the first electrode 4 or the second electrode 5 are melted during an electrochemical reaction of air gas or fuel gas. It consists of a difficult metallized layer and a gold plating layer 11a, and can effectively prevent corrosion of the electrode. In addition, since the pressure is applied between the contacted first wiring conductor 10 and the first electrode 4 or between the contacted second wiring conductor 11 and the second electrode 5, Even if the gold plating layer 11a is directly formed on the metallized layer without forming the base plating layer on the upper surfaces of the metallized layers of the first wiring conductor 10 and the second wiring conductor 11, the gold plating layer 11a is not peeled off and has good adhesion. Can be maintained.

  Further, since the gold plating layer 11a is a very flexible metal, it is between the abutting first wiring conductor 10 and the first electrode 4 or between the abutting second wiring conductor 11 and the second electrode 5. The gold plating layer 11a is appropriately deformed by the compressive force, so that the space between the first wiring conductor 10 and the first electrode 4 or the contact between the second wiring conductor 11 and the second electrode 5 can be filled without any gap. In addition, the increase in electrical resistance and poor contact can be more effectively suppressed.

  As a result, in the first electrode 4 and the second electrode 5, the electrochemical reaction of the air gas or the fuel gas is not hindered by the dissolved metal ions, and the fuel cell 1 having high electric power generation efficiency with small electric resistance is obtained. Can be provided.

Further, a hygroscopic material may be applied to the inner wall of the first fluid channel 8 or the second fluid channel 9, and water vapor or water generated by an electrochemical reaction in the electrolyte member 3 is absorbed by the hygroscopic material. Therefore, the blockage of the first and second fluid flow paths 8, 9 serving as air flow paths can be effectively prevented. Therefore, it is possible to effectively prevent the surfaces of the electrodes of the first and second electrodes 4 and 5 from being covered with water (H ₂ O), and in the atmosphere through the first and second fluid flow paths 8 and 9. Therefore, air can be effectively supplied as an oxidizing gas, so that an electrochemical reaction in the electrolyte member 3 can be promoted and highly efficient power generation can be performed.

As the hygroscopic material, a material that easily absorbs water (H ₂ O) such as silica gel, alumina, white clay, activated carbon, paper, wood powder may be used. In particular, inorganic powder such as silica gel, alumina, white clay, etc. is pulverized. Since it is easy to adjust the absorption area of water (H ₂ O) by adjusting the size of the powder by, for example, it is preferable in that the desired moisture absorption characteristics can be easily obtained.

  When the hygroscopic material is applied to the inner walls of the first fluid channel 8 and the second fluid channel 9, the air flow uniformity as the oxidizing gas from the atmosphere through the first and second fluid channels 8, 9 is maintained. In addition, it is preferable to apply a hygroscopic material to all of the first and second fluid flow paths 8 and 9, and the thickness of the hygroscopic material is affected by pressure loss when supplying air as an oxidizing gas. Since it is necessary to make it small, the thickness which becomes an area of 10% or less with respect to the opening area in the cross section of the 1st and 2nd fluid flow paths 8, 9 is preferable.

Furthermore, in order to promote the evaporation of moisture from the hygroscopic material by the air flow, it is preferable to apply the hygroscopic material to the entire inner walls of the first and second fluid flow paths 8 and 9. Thus, when the fuel cell container 2 and the fuel cell 1 of the present invention are used for a small type such as a portable direct methanol fuel cell (DMFC), for example, 10 ml of methanol can be operated for several tens of hours. At the same time, the amount of water (H ₂ O) produced is as small as 1 ml per 1 g of methanol consumed. For this reason, the water (H ₂ O) absorbed by the hygroscopic material has a water amount that can be sufficiently evaporated by blowing air using a fan, and can be continuously operated.

  With the above configuration, a small and robust fuel cell container 2 capable of accommodating the electrolyte member 3 as shown in FIG. 1 is obtained, and the fuel cell 1 of the present invention capable of high efficiency control is obtained.

  Next, the electronic apparatus of the present invention having the fuel cell 1 as a power source will be described.

  Since the electronic device of the present invention has the fuel cell 1 as a power source as described above, it is small, low-profile, and has a long period of time with the features of the fuel cell container 2 of the present invention as described above. An electronic device with excellent safety and convenience that can be stably operated can be obtained.

  Further, when the fuel cell 1 having a power source is provided with terminals for external connection (a positive terminal and a negative terminal) on at least one of the base body 6 and the lid body 7, the circuit board of the electronic device can be easily electrically connected. Connection is possible and attachment / detachment is free. Therefore, the fuel cell 1 can be easily replaced with a new one without using a facility equipped with special safety equipment, and the convenience of the electronic device can be enhanced.

  Furthermore, since a metal layer can be formed in various shapes and electrical characteristics by the metallization method or the like inside the base 6 of the fuel cell container 2, electrons functioning as resistance, capacitance, inductance, etc. inside the base 6. Circuit elements can be formed. Therefore, for example, when a large capacity capacitor is formed in parallel with the fuel cell 1 and the current output from the fuel cell 1 becomes insufficient, the insufficient current is compensated and the target output current is compensated. It is possible to ensure a current supply according to the above. In addition, since a booster circuit can be formed, a voltage necessary for the electronic device can be secured.

  In addition, when forming resistance, a capacitance, and an inductance in the inside of the base | substrate 6 in this way, it is preferable that the base | substrate 6 consists of glass ceramics.

  Specifically, the electronic device of the present invention includes portable electronic devices such as mobile phones, PDAs (Personal Digital Assistants), toys such as digital cameras, video cameras, and game machines, and notebook PCs (personal computers). ) And other portable printers, fax machines, televisions, communication equipment, audio-video equipment, electric appliances such as electric fans, and electronic equipment such as electric tools.

  In recent years, these electronic devices have been added with a function of displaying a moving image using a liquid crystal display device or the like. Such a video display consumes a large amount of power, so that an electronic device using a conventional storage battery cannot be operated in a short time, whereas the electronic device of the present invention supplies a very long time power. The fuel cell 1 that can be used is mounted, and even if a moving image is displayed, long-time operation is possible.

  For example, in the case of a mobile phone, a central processing unit (CPU), a control unit, a random access memory (RAM), a read-on memory (ROM), an input unit for inputting data operated by a user to the CPU, The antenna, the signal received by the antenna is demodulated and supplied to the control unit, the radio unit that modulates the signal supplied from the control unit and transmitted from the antenna, and the sound is generated based on the ringing signal from the control unit A speaker, a light emitting diode (LED) that is turned on, off, or blinking under the control of the control unit, a display unit that displays information by a signal from the control unit, a vibrator that vibrates by a drive signal from the control unit, and a user The voice signal from the control unit is transmitted to the control unit, the voice signal from the control unit is converted into voice and output, and the power source that supplies power to each unit The fuel cell 1 and the fuel cell container 2 of the present invention are incorporated in the power supply unit, so that the fuel cell 1 and the fuel cell container 2 are excellent in compactness, simplicity and safety, The power supply can be supplied for a long time by the uniform supply and high-efficiency electrical connection, so that the mobile phone can be reduced in size, height and weight.

  Also, considering that recent mobile phones are sufficient in terms of miniaturization and low profile, in the space generated by miniaturizing and reducing the height of the fuel cell 1 in this way, for example, a camera or video Electronic components having functions other than the telephone function such as the above can be newly incorporated, and further multi-function can be performed.

  Further, instead of newly incorporating electronic components, an impact absorbing material, an impact preventing member or the like can be provided so as to protect the main electronic circuit. In this case, it is also possible to have a structure that can make the impact resistance when a shock is applied to the mobile phone main body due to dropping or the like, the waterproofness when used in rain, etc. stronger than before.

  In addition, by making it possible to reduce the size of the electric circuit inside the mobile phone body, there are fewer restrictions on the external shape of the mobile phone body, for example, making the mobile phone a shape that is easy for an elderly person or child to grip. It becomes possible to make the outer shape excellent in design.

  Further, when the fuel cell 1 and the fuel cell container 2 are detachable as described above, if the spare fuel cell 1 and the fuel cell container 2 are prepared, the battery runs out. Can be easily replaced with the spare fuel cell 1 and the fuel cell container 2 or the fuel cell 1 can be taken out and refueled or exchanged, so that the telephone conversation can be continued. Therefore, it is more convenient than a conventional battery that uses a storage battery as a power source.

  In addition, since the replaced (used) fuel cell 1 can be reused immediately by replenishing fuel, it is more convenient than charging, and resources can be used effectively. In addition, there is an advantage that it can be used in an emergency such as a long-term power outage due to a natural disaster or the like or outdoors.

  In the case of a notebook PC (personal computer), a personal computer main body, a first housing containing a keyboard for inputting predetermined data to the personal computer main body, data input by the keyboard, or a personal computer And a second housing containing a display for displaying data processed by the main body, the second housing is attached to the first housing so as to be openable and closable, and power is supplied to each part. The power supply unit is configured to be provided in the first housing, and the fuel cell 1 and the fuel cell container 2 are incorporated in the power supply unit. In this case, similar to the above-described mobile phone, the fuel cell 1 and the fuel cell container 2 incorporated in the electronic device of the present invention are excellent in compactness, simplicity and safety, and are evenly supplied with fuel and highly efficient electrical connection. This makes it possible to supply power for a long time with a small-sized, low-profile, light-weight and multi-functional notebook PC (personal computer), and supports larger displays and higher resolutions. In addition, it is possible to supply a large current stably over a long period of time, a notebook PC (personal computer) with high convenience such as easy-to-see display and low weight and volume burden when carrying can do.

  When the fuel cell 1 and the fuel cell container 2 are detachable from the power source, the spare fuel cell 1 and the fuel cell container 2 of the present invention are prepared. In a situation where only a secondary battery such as a mobile body is used, there is an advantage that it is possible to supply power for a long time as compared with the conventional case. Further, even when used in a public place as described above, since it is excellent in safety, it can be used without being restricted and is extremely convenient.

  It should be noted that the present invention is not limited to the embodiments described above, and various modifications can be made without departing from the scope of the present invention. For example, the first fluid channel 8 and the second fluid channel 9 may be provided with an inlet from the side surface of the base body 6 or the lid body 7 in order to reduce the thickness of the entire fuel cell 1. According to this, it is effective in reducing the size especially for portable electronic devices. Furthermore, about the 1st and 2nd wiring conductors 10 and 11, you may arrange | position so that the other end derived | led-out to the outer surface of the base | substrate 6 and the cover body 7 may be pulled out to the side surface of the same side, respectively. According to this, wiring and flow paths can be gathered on one side surface of the fuel cell 1, facilitating miniaturization and protection of the joint to the outside, enabling a highly reliable design, The fuel cell 1 can operate stably for a period.

  A plurality of electrolyte members 3 are accommodated in the recesses of the base 6 and are electrically connected by the first and second wiring conductors 10 and 11 to obtain a high voltage or large current output as a whole. You may do it.

  In addition, as shown in a cross-sectional view in FIG. 2 as another example of the fuel cell container and the fuel cell according to the present invention, at least one of the first fluid channel 8 ′ and the second fluid channel 9 ′ is provided. A plurality of groove-shaped openings having the same length and the same width are formed at equal intervals so as to face the lower main surface or the upper main surface of the electrolyte member 3 on the bottom surface of the recess or the lower surface of the lid 7 '. The opening 13, the connecting portion 14 that connects one end and the other end of the plurality of openings formed inside the base body 6 ′ or the lid body 7 ′, and the base body 6 ′ or the lid body from one of the connecting portions 14. A base 6 having a recess, and a fluid introduction part 15 formed over the outer surface of 7 'and a fluid discharge part (not shown) formed from the other side to the base 6' or the outer surface of the lid 7 '. The electrolyte member 3 is accommodated in the recess of the first and second electrodes , 5 first and second wiring conductors 10 ', 11' may be respectively electrically connected to the.

According to this, it is easy to supply the fluid to the openings 13 formed into a plurality of grooves by the fluid introduction part 15 and the connecting part 14, and the plurality of groove-like openings in the openings 13 have the same length. Since the same width is formed at equal intervals, the distance from the introduction portion 15 to the discharge portion is shortened and the flow path resistance is reduced even when the fluid inflow rate is high. As a result, the uniform supply performance of the fluid supplied to the electrolyte member 3 can be improved, and water (H ₂ O) generated by a chemical reaction when the air supplied as the oxidizing gas from the atmosphere is taken in and out continuously. Thus, it can be removed by drying.

  FIG. 3 is a cross-sectional view showing still another example of an embodiment of a fuel cell container of the present invention and a fuel cell using the same, and an electrolyte is provided in each of the recesses of the base 6 ″ having a plurality of recesses. While accommodating the member 3, the 3rd wiring conductor 16 is arrange | positioned over the edge part of an adjacent recessed part, and between the 1st electrode 4 of the some electrolyte member 3, or between the 1st electrode 4 and the 2nd electrode 5 The first wiring conductor 10 ″ and the second wiring conductor 11 ″ are electrically connected to each other so as to take out the output as a whole to the electrolyte member 3 disposed at both ends. May be.

  According to this, since the first to third wiring conductors 10 ″, 11 ″, 16 can be freely wired three-dimensionally, a plurality of electrolyte members 3 can be arbitrarily connected in series or in parallel. . As a result, the overall output voltage and output current can be adjusted efficiently, and thus the fuel cell container 2 "that can take out the electricity electrochemically generated by the electrolyte member 3 to the outside. And a fuel cell 1 ″.

(A) is sectional drawing which shows an example of embodiment of the fuel cell using the container for fuel cells of this invention, (b) is a principal part expanded sectional view of the fuel cell of (a). It is sectional drawing which shows the other example of embodiment of the fuel cell using the container for fuel cells of this invention. It is sectional drawing which shows the other example of embodiment of the fuel cell using the container for fuel cells of this invention. It is sectional drawing of the conventional fuel cell.

Explanation of symbols

1, 1 ′, 1 ″: fuel cell 2, 2 ′, 2 ″: fuel cell container 3: electrolyte member 4: first electrode 5: second electrode 6, 6 ′, 6 ″: substrate 7, 7 ′, 7 ": Lids 8, 8 ', 8": First fluid flow paths 9, 9', 9 ": Second fluid flow paths 10, 10 ', 10": First wiring conductors 11, 11', 11 " : Second wiring conductor 12: opening shape 13: opening 14: connecting portion 15: introducing portion 16: third wiring conductor

Claims (3)

A base made of ceramics having a recess on the upper surface for accommodating an electrolyte member having first and second electrodes on the lower and upper main surfaces, respectively, and a bottom surface of the recess facing the lower main surface of the electrolyte member A first fluid channel formed over the outer surface of the base, and a first wiring in which one end is disposed on the bottom surface of the recess facing the first electrode of the electrolyte member and the other end is led to the outer surface of the base A conductor, a lid that covers and attaches to the upper surface of the base around the recess, and seals the recess hermetically; and the lid that faces the upper main surface of the electrolyte member. One end is disposed on the second fluid flow path formed from the lower surface to the outer surface of the lid, the lower surface of the lid facing the second electrode of the electrolyte member, and the other end on the outer surface of the lid A second wiring conductor led out , At least one of the first fluid channel and the second fluid channel is a periphery of the opening of the first fluid channel on the bottom surface of the recess or the opening of the second fluid channel on the lower surface of the lid. A periphery is formed so as to contact the first electrode or the second electrode, and of the first wiring conductor and the second wiring conductor, contact the first electrode or the second electrode. The formed portion is made of a metallized layer mainly composed of at least one of tungsten and molybdenum, and a gold plating layer is directly applied to the exposed surface thereof. The first wiring conductor and the second wiring conductor The portions formed on the outer surface of the base body and the outer surface of the lid body are composed of the metallized layer, and a nickel plating layer and a gold plating layer are sequentially deposited on the exposed surface. Container for a fuel cell according to claim. The electrolyte member is accommodated in the recess of the fuel cell container according to claim 1, and each fluid flows between the lower and upper main surfaces of the electrolyte member between the first and second fluid flow paths. The lid is disposed so as to be able to communicate, and the first and second electrodes are electrically connected to the first and second wiring conductors, respectively, and the upper surface of the base around the concave portion covers the concave portion and the lid A fuel cell comprising a body attached thereto. An electronic apparatus comprising the fuel cell according to claim 2 as a power source.

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