JP2007180023A - Solid-oxide fuel cell power generator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid-oxide fuel cell power generator which uses a simple structure eliminating the need for closeness, and directly gasifies a solid fuel to make it available as a cell fuel for electric generation. <P>SOLUTION: This solid-oxide fuel cell power generator contains solid-oxide fuel cells C1 and C2, each having a plane solid electrolyte substrate 1 on which a cathode electrode layer 2 and an anode electrode layer 3 have been formed. In addition, it contains a pair of fuel cells with a solid fuel F between the anode electrode layers of the solid-oxide fuel cells C1 and C2, and provides a heat supply unit for heating the pair of fuel cells. The solid fuel is directly gasified by this heating to produce fuel seeds which feed to the anode electrode layer for electric generation by the solid-oxide fuel cell. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a power generator using a solid oxide fuel cell, and more particularly, to provide a solid fuel between two solid oxide fuel cells having a solid electrolyte substrate on which a cathode electrode layer and an anode electrode layer are formed. The present invention relates to a solid electrolyte fuel cell power generator capable of generating electric power by converting a solid fuel into a gas phase by using a simple structure that can be sandwiched and heated and does not require sealing.

In recent years, various power generation type fuel cells have been developed, and among these, there are solid oxide fuel cells using a solid electrolyte. As an example of this solid oxide fuel cell, there is one using a fired body made of stabilized zirconia to which yttria (Y ₂ O ₃ ) is added as an oxygen ion conduction type solid electrolyte layer. A cathode electrode layer is formed on one surface of the solid electrolyte layer, and an anode electrode layer is formed on the opposite surface. Oxygen or an oxygen-containing gas is supplied to the cathode electrode layer side. The fuel gas is supplied.

In this fuel cell, oxygen (O ₂ ) supplied to the cathode electrode layer is ionized into oxygen ions (O ²⁻ ) at the boundary between the cathode electrode layer and the solid electrolyte layer, and this oxygen ion is converted into a solid electrolyte. The layer is conducted to the anode electrode layer and reacts with, for example, methane (CH ₄ ) gas supplied to the anode electrode layer, where water (H ₂ O), carbon dioxide (CO ₂ ), hydrogen (H ₂ ) , Carbon monoxide (CO) is produced. In this reaction, since oxygen ions release electrons, a potential difference is generated between the cathode electrode layer and the anode electrode layer. Therefore, if lead wires are attached to the cathode electrode layer and the anode electrode layer, electrons in the anode electrode layer flow to the cathode electrode layer side via the lead wires, and power is generated as a fuel cell. The driving temperature of this fuel cell is about 1000 ° C.

  However, in this type of fuel cell power generator, an oxygen or oxygen-containing gas supply chamber must be prepared on the cathode electrode layer side, and a separate chamber separated from the fuel gas supply chamber on the anode electrode layer side. In addition, since it is exposed to an oxidizing atmosphere and a reducing atmosphere at high temperatures, it is difficult to improve the durability of the fuel cell.

  On the other hand, a solid oxide fuel cell having a cathode electrode layer and an anode electrode layer formed on opposite surfaces of the solid electrolyte layer is formed, and this fuel cell is mixed with fuel gas, for example, methane gas and oxygen gas. A type of fuel cell has been developed in which an electromotive force is generated between the cathode electrode layer and the anode electrode layer in the mixed fuel gas. In this type of fuel cell, the principle of generating an electromotive force between the cathode electrode layer and the anode electrode layer is the same as that of the fuel cell of the separate chamber type described above, but the whole solid oxide fuel cell Can be made into a single type chamber to which a mixed fuel gas is supplied, and the durability of the fuel cell can be improved.

  However, this power generator using a single-chamber fuel cell must also be driven at a high temperature of about 1000 ° C., so there is a risk of explosion of the mixed fuel gas. In order to avoid this danger, when the oxygen concentration is lower than the ignition limit, the carbonization of fuel such as methane progresses and the battery performance deteriorates. For this reason, a single-chamber fuel cell power generator that can use a mixed fuel gas having an oxygen concentration that can prevent the progress of carbonization of the fuel while preventing the explosion of the mixed fuel gas has been proposed (for example, Patent Document 1). See).

  On the other hand, this proposed fuel cell power generator was of a type in which a plurality of solid oxide fuel cells housed in a chamber were stacked to form a solid oxide fuel cell in a flame, Alternatively, there has been proposed an apparatus that is disposed in the vicinity of the solid oxide fuel cell and generates electric power by holding the solid oxide fuel cell at its operating temperature by the heat of flame.

  By the way, the above-mentioned single-chamber fuel cell power generator employs a confidential sealing structure instead of the need for a strict separation of fuel and air, unlike the conventional solid oxide fuel cell power generator. I have to. Then, a plurality of plate-like solid oxide fuel cells are stacked and connected using an interconnect material having heat resistance and high electrical conductivity so as to be driven at a high temperature, and the electromotive force is increased. Therefore, a single-chamber fuel cell power generator using a plate-like solid oxide fuel cell has a large structure and has a problem of increasing costs. Also, when operating this single-chamber fuel cell power generator, the temperature is gradually raised to a high temperature to prevent the solid oxide fuel cell from cracking. It ’s time consuming.

  On the other hand, in the solid oxide fuel cell in the above-described power generation apparatus, a form in which a flame is directly used is employed, and the fuel cell in this form accommodates the solid electrolyte fuel cell in a sealed container. It is not necessary and has the feature of being an open type. Therefore, in this fuel cell, since the electromotive time can be shortened and the structure is simple, it can be said that this fuel cell is advantageous in reducing the size and weight of the fuel cell and reducing the cost. In terms of direct use of the flame, it can be incorporated into a general combustion device, an incinerator, or the like, and is expected to be used as a power supply device.

  However, in the fuel cell power generator of this embodiment, since the anode electrode layer is formed on the outer surface of the tubular solid electrolyte layer (see, for example, Patent Document 2), the flame is mainly formed in the lower half of the anode electrode layer. As a result, the entire surface of the anode electrode layer formed on the outer surface of the tubular solid electrolyte layer cannot be used effectively. Therefore, the power generation efficiency was low.

  Therefore, a power generation device using a solid oxide fuel cell with improved power generation efficiency has been proposed (see, for example, Patent Document 3). This proposed power generator is shown in FIG. A specific configuration of the solid oxide fuel cell C used here will be described. The solid oxide fuel cell C is provided with a cathode electrode layer 2 on one surface side of the solid electrolyte substrate 1 and an anode electrode layer 3 on the other surface side, and is formed in a flat plate shape as a whole.

  Since the cathode electrode layer 2 and the anode electrode layer 3 are thus formed on the flat solid electrolyte substrate 1, the anode electrode layer 3 is exposed to the flame f generated by the gas burner 4. Then, the anode electrode layer 3 side becomes a fuel-rich state, and the cathode electrode layer 2 inevitably goes to the atmosphere side, and becomes an oxygen-rich state. The generated output is taken out between the lead wire L1 attached to the cathode electrode layer 2 and the lead wire L2 attached to the anode electrode layer 3.

Therefore, as compared with the case of the tubular solid electrolyte fuel cell, the solid oxide fuel cell C is formed in a flat plate shape, so that it is possible to apply a flame without unevenness. Since it is arranged toward the flame side, it is easy to effectively use, for example, hydrocarbons, hydrogen, radicals (OH, CH, C ₂ , O ₂ H, CH ₃ ) present in the flame as fuel species. is doing.

  In the solid oxide fuel cell power generator described above, the flame f generated by the gas burner directly exposes the anode electrode layer 3 so that the flame f maintains the operating temperature of the solid oxide fuel cell C. And a supply source of fuel species necessary for power generation of the solid oxide fuel cell. Here, the flame f is generated by the combustion of the premixed gas. However, as shown in FIG. 13, the solid oxide fuel may be generated by burning the solid fuel to generate the flame f. The battery can also be applied to a power generator.

  The solid oxide fuel cell C shown in FIG. 12 can be used as the solid oxide fuel cell C used in the power generation apparatus of FIG. Electrolyte substrate 1, cathode electrode layer (air electrode layer) 2 and anode electrode layer (fuel electrode layer) 3 formed on both surfaces thereof are formed. The solid oxide fuel cell C is placed on top of the combustion device 5.

  The combustion apparatus 5 includes a combustion chamber in which the solid fuel F can be stored, and a holding body 6 such as a grate for holding the solid fuel is provided in the combustion chamber. In FIG. 13, a wood material is supplied as a solid fuel. And the upper part of the combustion apparatus 5 is equipped with the flame opening part which supports the solid oxide fuel cell C, makes the anode electrode layer 3 face a combustion chamber, and is exposed with a flame. Further, a solid fuel supply opening for supplying the solid fuel F into the combustion chamber is opened in the front surface of the combustion device 5, and an air intake for supplying air to the lower side of the solid fuel holder 6 is also provided. The entrance opening is also opened.

  As the solid fuel, in addition to the wood material, for example, wood material chips or pellets, paraffin, olefin, alcohol and the like can be easily obtained. Here, the solid fuel F is supplied into the combustion chamber of the combustion device 5, and a flame f is generated by the combustion of the solid fuel. The generated flame f hits the anode electrode layer 3 of the solid oxide fuel cell C facing the opening, and outside air is supplied to the cathode electrode layer 2. As a result, the radical component in the flame f reacts with oxygen in the air, and an electromotive force is generated between the lead wire L1 and the lead wire L2, thereby functioning as a power generator using the solid oxide fuel cell. .

JP 2003-92124 A JP-A-6-196176 JP 2004-139936 A

  Incidentally, in the above-described power generation apparatus using a solid oxide fuel cell, gas phase fuel is usually supplied to the fuel electrode. In the case of a solid oxide fuel cell housed in a single-chamber power generator, a mixed fuel gas is supplied, and in the case of a solid oxide fuel cell power generator for direct flame use, the anode electrode layer The combustion gas or the unburned gas contained in the flame generated by the combustion of the gaseous fuel or the solid fuel is supplied.

  However, if a fuel gas to be included in a mixed gas supplied to the apparatus is generated from solid fuel as in the case of a power generation apparatus using a single chamber, it takes time and energy, and a special generation apparatus must be prepared. . In addition, in the case of a solid oxide fuel cell power generator that uses flame directly, it is easier and simpler than the case of a power generator using a single chamber, in that a flame obtained by burning solid fuel is used for power generation. In addition, although it is advantageous that the solid fuel can be vaporized in the apparatus, there are problems in the stabilization of the flame by the combustion of the solid fuel and the efficiency of supplying the fuel to the fuel electrode. And since a combustion device must be provided in the power generation device, there is a problem in miniaturization of the power generation device, and it is impossible to increase the power generation output.

  In view of this, the present invention provides a solid fuel sandwiched between two solid oxide fuel cells each having a solid electrolyte substrate on which a cathode electrode layer and an anode electrode layer are formed, so that the fuel cell pair can be heated and sealed. It is an object of the present invention to provide a solid oxide fuel cell power generator capable of generating power by using a simple structure that does not require the fuel as fuel for a fuel cell while directly vaporizing the solid fuel.

  In order to solve the above problems, in the solid oxide fuel cell power generator of the present invention, the first and second solid oxide fuel cells each having a solid electrolyte substrate on which a cathode electrode layer and an anode electrode layer are formed; A heat supply device for heating the first and second solid oxide fuel cells, the anode electrode layer of the first solid oxide fuel cell, and the second solid oxide fuel cell. Solid fuel was sandwiched between the anode electrode layer.

  And the 1st fuel cell pair by the said 1st solid oxide fuel cell and the said 2nd solid oxide fuel cell which pinched | interposed the said solid fuel is accommodated in a heat insulation container, The lower part of this heat insulation container WHEREIN: A heat supply device was arranged, and air was supplied from the lower part.

  The first fuel cell pair is disposed vertically, the heat supply device is disposed below the fuel cell pair, and the plurality of sets of the first fuel cell pairs are spaced from each other. Then, the pressure fixing member that is housed in the heat insulating container and maintains the interval is inserted between the plurality of pairs of fuel cells.

  Also, a high thermal conductor layer is formed on the inner surface of the heat insulating container, and only the first solid oxide fuel cell and the second solid oxide fuel cell are disposed above the fuel cell pair. The second fuel cell pair according to is arranged.

  The heat supply device supplies heat from the flame to the fuel cell pair, and the heat supply device is an anode electrode layer of a solid oxide fuel cell disposed below the first fuel cell pair. It was decided to supply a flame that would be exposed directly.

  The solid fuel used in the present invention is made by adhering finely pulverized organic solids dispersed in water to a heat-resistant net with a substantially constant thickness and a size matching the surface shape of the anode electrode layer. It was decided to be made into a flat plate shape.

  Further, in the solid oxide fuel cell power generator according to the present invention, each of the first and second solid oxide fuel cells is formed from the edge of the cathode electrode layer at the entire peripheral edge of the solid electrolyte substrate. An oxide frame that covers the edge of the anode electrode layer and has a predetermined width from the edge, and has a mesh-like metal or wire on at least one of the cathode electrode layer and the anode electrode layer. The metal-like metal is embedded or fixed, and each of the oxide frames has a holding portion for holding the solid oxide fuel cell.

  The mesh-like metal or wire-like metal embedded or fixed in the cathode electrode layer and the anode electrode layer is a first collector electrode and a second collector electrode, and the first collector electrode and the second collector electrode. The power generation output is taken out from the lead wire connected to the electrode.

  The mesh-like metal or wire-like metal is extended and embedded in the oxide frame, and the oxide frame is made of a solid electrolyte material or porous. .

  The holding portion has a plurality of holes, and the first and second solid oxide fuel cells have a guide rail provided on a holding frame in a heat insulating container inserted into each of the holes. The solid fuel is vertically disposed in the heat insulating container, and the solid fuel is vertically inserted between the first solid oxide fuel cell and the second solid oxide fuel cell in the heat insulating container. did.

  The guide rail includes a pressure fixing member that presses and contacts the solid fuel between the first and second solid oxide fuel cells, and the pressure fixing member is configured to replace the guide rail when the solid fuel is replaced. The holding portion has holes provided at the four corners of the oxide frame, and the guide rail is inserted into each of the holes.

  In the solid oxide fuel cell power generator of the present invention, the solid fuel is engaged with a holding rod in the heat insulating container by an engagement tool provided at the upper end of the heat-resistant net to which the solid fuel is attached. By doing so, it was inserted vertically between the first solid oxide fuel cell and the second solid oxide fuel cell in the heat insulating container.

  Further, in the solid oxide fuel cell power generator of the present invention, the solid fuel is supported by a lower guide rail provided on a holding frame in a heat insulating container at the lower end of the heat-resistant net to which the solid fuel is attached. The surface direction is regulated by the upper guide rail provided on the holding frame, and the gas is inserted vertically between the first solid oxide fuel cell and the second solid oxide fuel cell in the heat insulating container. I decided to do it.

  As described above, according to the solid oxide fuel cell power generator of the present invention, a solid fuel is provided between two solid oxide fuel cells having a solid electrolyte substrate on which a cathode electrode layer and an anode electrode layer are formed. Since the fuel cell pair can be heated, a simple structure that does not require sealing can be used to generate power as fuel for the fuel cell while vaporizing the solid fuel.

  Further, according to the solid oxide fuel cell power generator of the present invention, in the heat insulating container containing a plurality of fuel cell pairs of two solid oxide fuel cells sandwiching the solid fuel, heat conduction is provided on the inner wall surface thereof. Since the plate is provided, the heat supplied to the lower part of each fuel cell pair is quickly conducted upward and heated not only from the lower part of each fuel cell pair, but also from the side above each fuel cell pair. It is heated and the occurrence of thermal shock during heating can be mitigated, and the start-up of the power generation drive can be accelerated.

  In addition, two solid oxide fuel cells not sandwiched with solid fuel are arranged vertically above each fuel cell pair, the anode electrode layers face each other, and the cathode electrode layer faces the outside. Therefore, the anode electrode layer is supplied with unused fuel species generated by the solid fuel of the corresponding fuel cell pair disposed below, and can maintain a fuel-rich state and cannot be fully utilized. This makes it possible to effectively use the fuel type and improve the utilization efficiency of the solid fuel.

  Further, according to the solid oxide fuel cell power generator of the present invention, a flame by a burner that can be easily handled is applied to a heat supply device that heats a fuel cell pair composed of two solid oxide fuel cells sandwiched between solid fuels. Can be used. Furthermore, the characteristic that a solid oxide fuel cell can directly generate power by being exposed to a flame can be used. A solid oxide fuel cell is interposed between a flame and a fuel cell pair, and the solid oxide fuel cell is formed by a flame. Since the fuel cell is heated to generate power with the fuel species contained in the flame and can be used as a heating source for the fuel cell pair, a simple heat supply device can be configured.

  Further, in the solid oxide fuel cell power generator according to the present invention, the organic solid matter finely pulverized and dispersed in water has a substantially constant thickness on a heat-resistant net and a size matching the surface shape of the anode electrode layer. Since the plate-shaped solid fuel was made by adhering to the electrode, stable contact could be realized between the anode electrode layers of the fuel cell pair, and the solid fuel could be exchanged easily.

  Hereinafter, an embodiment of a power generation device using a solid oxide fuel cell according to the present invention will be described with reference to the drawings. FIG. 1 shows the basic configuration of the solid oxide fuel cell power generator of this embodiment.

  In the power generation apparatus using the solid oxide fuel cell shown in FIG. 13, the solid fuel is burned in the combustion apparatus to generate a flame. This flame heated the solid oxide fuel cell and supplied fuel species to the anode electrode layer. Therefore, in the present embodiment, instead of burning a solid fuel to generate a flame, the solid fuel is heated to flameless combustion, and the fuel type generated by the flameless combustion is directly selected as a solid oxide fuel cell. The anode electrode layer can be supplied.

  As shown in FIG. 1, two solid oxide fuel cells C1 and C2 each having a solid electrolyte substrate 1 on which a cathode electrode layer 2 and an anode electrode layer 3 are formed and formed in a flat plate shape, Each anode electrode layer 3 is disposed inside, and a plate-like solid fuel F is inserted between each anode electrode layer 3. The solid fuel F is sandwiched between the solid oxide fuel cells C1 and C2, and a fuel cell pair in contact with each electrode layer is formed.

  In the basic configuration shown in FIG. 1, although not shown, the fuel cell pair is heated from below the fuel cell pair placed in the atmosphere. At this time, an electric furnace to which air is supplied may be used as the heat supply device for the fuel cell pair. In this case, the fuel cell pair is accommodated therein. Further, the heat supply device may simply be a gas burner capable of generating a flame or an electric heater.

  Here, since the solid fuel F is conveniently sandwiched between the solid oxide fuel cells C1 and C2 formed in a flat plate shape, a solid fuel F that can be formed in a flat plate shape is suitable. Therefore, as the solid fuel F, an easily available wood board, plywood board, paper, chip aggregate of wood material, pellets, or the like is preferable.

  In FIG. 1, the fuel cell pair is arranged vertically, but is not necessarily perpendicular, and any arrangement method, for example, as long as air or an oxygen-containing gas is supplied to the cathode electrode layer 2, for example, It may be arranged horizontally. The heat supply device only needs to be able to maintain the operating temperature required for power generation by the solid oxide fuel cell, and at this operating temperature, the above-described solid fuel can be burned flamelessly to generate fuel species.

  A solid oxide fuel cell used for the power generator of this embodiment will be described. As the solid oxide fuel cells C1 and C2 used here, those similar to the configuration of the solid oxide fuel cell C shown in FIGS. 12 and 13 can be adopted.

  The solid oxide fuel cells C1 and C2 are formed in a flat plate shape, and the cathode electrode layer 2 and the anode electrode layer 3 are arranged on one side and the other side of the solid electrolyte substrate 1, respectively. When directed to the fuel species supply side, the cathode electrode layer 2 is directed to the opposite side, and the fuel-rich state and the oxygen-rich state can be distinguished. As a result, the solid oxide fuel cells C1 and C2 remain open, and the cathode electrode layer 2 can easily use oxygen in the atmosphere and can maintain an oxygen-rich state.

For the solid electrolyte substrate 1, for example, a known material can be adopted, and the following materials can be used.
a) YSZ (yttria-stabilized zirconia), ScSZ (scandia-stabilized zirconia), zirconia-based ceramics doped with Ce, Al, and the like b) SDC (samaria doped ceria), GDC (gadria doped ceria), etc. Ceria-based ceramics c) LSGM (lanthanum gallate), bismuth oxide-based ceramics

For the anode electrode layer 3, for example, a known material can be adopted, and the following materials can be used.
d) Cermet of nickel and yttria-stabilized zirconia-based, scandia-stabilized zirconia-based, or ceria-based (SDC, GDC, YDC, etc.) ceramics e) Conductive oxide as a main component (50 to 99% by weight) (Hereinafter referred to as a conductive oxide is, for example, nickel oxide in which lithium is dissolved)
f) The materials listed in d) and e) include metals composed of platinum group elements and rhenium, or those containing about 1 to 10% by weight of oxides thereof, among which d) e) is preferred.

  Since the sintered body mainly composed of the conductive oxide of e) has excellent oxidation resistance, the power generation efficiency is increased due to the increase in the electrode resistance of the anode electrode layer, which is caused by the oxidation of the anode electrode layer. It is possible to prevent a phenomenon such as reduction, inability to generate power, or peeling of the anode electrode layer from the solid electrolyte layer. As the conductive oxide, nickel oxide in which lithium is dissolved is suitable. Furthermore, high power generation performance can be obtained by blending a metal composed of a platinum group element or an oxide thereof with the materials listed in the above d) and e).

  A known material can be used for the cathode electrode layer 2, for example, a manganic acid compound (for example, lanthanum strontium manganite) of a Group 3 element of the periodic table such as lanthanum to which strontium (Sr) is added. , Gallic acid compounds, or cobalt acid compounds (for example, lanthanum strontium cobaltite, samarium strontium cobaltite), and the like.

  The cathode electrode layer 2 and the anode electrode layer 3 are both formed of a porous body, but the solid electrolyte substrate 1 in the solid oxide fuel cells C1 and C2 used in this embodiment is also formed in a porous shape. . As in the prior art, the solid electrolyte substrate 1 of the solid oxide fuel cell used in the present embodiment may be densely formed, but it has low thermal shock resistance and cracks are caused by rapid temperature changes. It was easy. In general, since the solid electrolyte layer is formed thicker than the anode electrode layer and the cathode electrode layer, the cracks in the solid electrolyte layer are triggered, and the entire solid oxide fuel cell is cracked. It had become.

  Since the solid electrolyte substrate is made porous, even if a sudden temperature change occurs due to heating of the heat supply device during power generation, there is no cracking, etc., even for heat cycles with a large temperature difference. Improves impact. Moreover, even if it is porous, when its porosity is less than 10%, no significant improvement in thermal shock resistance was observed, but when it is 10% or more, good thermal shock resistance was seen, and 20% The above is more preferable. This is presumably because, when the solid electrolyte layer is porous, thermal expansion due to heating is relaxed at the voids.

  The solid oxide fuel cells C1 and C2 are manufactured as follows, for example. First, the material powder of the solid electrolyte layer is mixed at a predetermined blending ratio and formed into a flat plate shape. Then, the board | substrate as a solid electrolyte layer is made by baking and sintering this. At this time, solid electrolyte layers having various porosity can be prepared by adjusting the kind and blending ratio of the material powder such as the pore forming agent, the firing temperature, the firing time, the firing conditions such as the pre-firing. A solid oxide fuel cell is manufactured by applying a paste to be a cathode electrode layer on one surface side of the substrate as a solid electrolyte layer thus obtained and applying a paste to be an anode electrode layer on the other surface side, followed by firing. be able to.

  In addition, the solid oxide fuel cell can be further improved in durability as described below. As a method for improving the durability, a mesh metal is embedded or fixed to the cathode electrode layer 2 and the anode electrode layer 3 in the flat solid oxide fuel cells C1 and C2. As a method of embedding, the material (paste) of each layer is applied to the solid electrolyte layer, and the mesh metal is embedded in the applied material, followed by firing. As a method of fixing, the mesh metal may be bonded and sintered without being completely embedded with the material of each layer.

  As the mesh metal, a metal having excellent thermal resistance and harmony of thermal expansion coefficient with the cathode electrode layer and the anode electrode layer embedded or fixed thereto is preferable. Specifically, a mesh made of a metal made of platinum or an alloy containing platinum can be used. SUS300 (304, 316, etc.) or SUS400 (430, etc.) stainless steel may be used, which are advantageous in terms of cost.

  Further, instead of using a mesh-like metal, a wire-like metal may be embedded or fixed in the anode electrode layer and the cathode electrode layer. The wire-like metal is made of the same metal as the mesh-like metal, and the number and arrangement shape thereof are not limited.

  By embedding or fixing mesh-like metal or wire-like metal in the anode electrode layer or cathode electrode layer, the solid electrolyte substrate cracked due to thermal history etc. will be reinforced so that it will not fall apart and collapse. Furthermore, the mesh-like metal and the wire-like metal can electrically connect the cracked portions.

  Although the case where the solid electrolyte substrate is made porous has been described so far, the solid electrolyte substrate of the fuel cell according to the present embodiment can use a dense structure, and in this case, in particular, In order to cope with cracks due to thermal history, it is an effective means to embed or embed mesh metal or wire metal in the cathode electrode layer and the anode electrode layer.

  The mesh metal or wire metal may be disposed on both the anode electrode layer and the cathode electrode layer, or may be disposed on either one of them. Moreover, you may arrange | position combining a mesh-like metal and a wire-like metal. When cracking occurs due to thermal history, power generation can be continued without lowering its power generation capability, as long as at least the anode electrode layer is embedded with a mesh metal or wire metal. Since the power generation capacity of the solid electrolyte fuel cell depends largely on the effective area of the anode electrode layer as the fuel electrode, it is preferable to dispose at least the mesh-like metal or wire-like metal in the anode electrode layer.

  Although not shown in FIG. 1, each of the solid oxide fuel cells C1 and C2 used in the power generation apparatus of this embodiment has a cathode electrode as shown in FIGS. Each of the layer 2 and the anode electrode layer 3 is provided with lead wires L1 and L2 for extracting an electromotive force. Depending on how the lead wires L1 and L2 are connected, the solid oxide fuel cells C1 and C2 are electrically connected in parallel or in series.

  Next, FIG. 2 shows a solid oxide fuel cell power generator according to a first embodiment using the basic configuration of the present invention shown in FIG. In this first embodiment, a plurality of pairs of fuel cell pairs in which a solid fuel is sandwiched between two solid oxide fuel cells are vertically arranged in the heat insulating container 7 at a predetermined interval. . In the example of FIG. 2, three pairs of fuel cells are arranged.

  The first fuel cell pair is formed by a solid fuel F1 and solid oxide fuel cells C1 and C2, and the second fuel cell pair is formed by a solid fuel F2 and solid oxide fuel cells C3 and C4, The third fuel cell pair is formed of a solid fuel F3 and solid oxide fuel cells C5 and C6. Although not shown in the lower part of the heat insulation container 7, heat for heating each fuel cell pair is supplied from a heat supply device.

  Since the lower part of the heat insulating container 7 is open to the atmosphere, the air is heated by the heat supply device, naturally rises between each fuel cell pair, and the solid oxide fuel cell constituting each fuel cell pair Air is supplied to the cathode electrode layer to form an oxygen-rich state. Therefore, each fuel cell pair needs to be arranged at a predetermined interval in order to secure an air passage. In addition, although the upper part of the heat insulation container 7 of FIG. 2 is a completely open state, the upper part may be closed to provide an opening through which exhaust gas and rising air pass.

On the other hand, solid fuels F1 to F3, by being heated from below, is a flameless combustion state, hydrocarbons, hydrogen, radicals _{(OH, CH, C 2,} O 2 H, CH 3) fuel species such as appear. Since the solid fuels F1 to F3 are arranged in contact with the anode electrode layer of the solid oxide fuel cell, the fuel species generated from the solid fuels F1 to F3 are directly connected to the solid oxide in each fuel cell pair. Is supplied to the anode electrode layer of the fuel cell, and the anode electrode layer is maintained in a fuel-rich state.

  Next, a specific example of the solid oxide fuel cell power generator according to the first embodiment shown in FIG. 2 is shown in FIG. In the case of FIG. 2, in order to maintain the cathode electrode layer of the solid oxide fuel cell constituting each fuel cell pair in an oxygen-rich state, each fuel cell pair has a predetermined interval in order to secure an air passage. There was a need to be placed. Therefore, the specific example shown in FIG. 3 includes specific means for securing a predetermined interval between each fuel cell pair.

  The solid oxide fuel cell power generator shown in FIG. 3 is an example in which the power generator shown in FIG. 2 has the same configuration, and as a specific means for securing a predetermined interval, Elastic members E <b> 1 to E <b> 4 are inserted between each fuel cell pair and between the fuel cell pair and the inner wall surface of the heat insulating container 7. The elastic members E1 to E4 have a role of holding each fuel cell pair while pressing them, such as a spring, for example. When the burned solid fuel held between the fuel cell pair is replaced with a new solid fuel, the fuel cell pair can be easily detached from the heat insulating container.

  Next, a second embodiment of the solid oxide fuel cell power generator according to the present invention is shown in FIG. The solid oxide fuel cell power generator of the second embodiment is based on the same configuration as that of the power generator of the first embodiment shown in FIG. 2, but the second embodiment is different from the first embodiment. The point is that a burner that generates a flame is used as a heat supply device provided in the lower part of the heat insulating container 7.

  In the solid oxide fuel cell power generator shown in FIG. 2 as well, a burner that generates a flame can be used as the heat supply device, and each flame is heated to the operating temperature by this flame, and Solid fuel can be burned without flame, and a power generation function can be achieved. However, it is inevitable that the solid fuel burns at the portion where the flame directly exposes the solid fuel, that is, at the lower end of the solid fuel. Therefore, in the power generation apparatus of the second embodiment, it is important to note that each fuel cell pair only needs to be heated to maintain the operating temperature, and the solid oxide fuel cell itself has a power generation function based on direct flame use. At this time, the fact that the solid oxide fuel cell becomes a heating element is utilized.

  The power generator of the second embodiment shown in FIG. 4 is based on the configuration of the power generator of the first embodiment shown in FIG. 2 and FIG. Physical fuel cells C7 and C8 and a burner 4 for supplying a flame f to the fuel cells are provided. A premixed gas is supplied to the burner 4, and a flame f is generated by combustion of the premixed gas.

  The solid oxide fuel cells C7 and C8 are arranged so that the anode electrode layer 3 formed thereon is exposed by the flame f generated by the burner 4. Although FIG. 4 shows a case where two solid oxide fuel cells are provided, one solid oxide fuel cell may be arranged horizontally. Further, the flame f may be surrounded by a plurality of solid oxide fuel cells, but the flame f may be a heating source so that the fuel cell pair is not directly exposed.

  In the power generator of the second embodiment shown in FIG. 4, two solid oxide fuel cells C7 and C8 have the anode electrode layer 3 inside, and close the upper end portion to make a space inside. Form. In this space, the flame f generated in the burner 4 is supplied, and the two solid oxide fuel cells C7 and C8 are heated by the flame f, and the heated solid oxide fuel cells are used as fuel cells. It becomes a heat source for heating the pair. Further, the flame f directly supplies the anode electrode layer 3 of the solid oxide fuel cells C7 and C8 to supply the fuel species, and contributes to power generation of the solid oxide fuel cells C7 and C8. With such a configuration of the heat supply device, the generated flame f can be used effectively.

  Next, FIG. 5 shows a third embodiment of the solid oxide fuel cell power generator according to the present invention. The power generator according to the third embodiment is based on the configuration of the solid oxide fuel cell power generator according to the second embodiment shown in FIG. 4, and the third embodiment is different from the second embodiment. The heat conductive plate 8 is disposed on the inner wall surface of the heat insulating container 7, and a plurality of solid oxide fuel cells are disposed on the upper side of each fuel cell pair.

  As shown in FIG. 5, since the heat conduction plate 8 is provided on the inner wall surface of the heat insulating container 7, the heat supplied to the lower part of each fuel cell pair is quickly conducted upward, so that each fuel cell pair In addition to heating from the lower part of the fuel cell, it is also heated from the side above each fuel cell pair, so that the occurrence of thermal shock during heating can be mitigated, and the start-up of the power generation drive can be accelerated. it can. Note that this heat conducting plate can be applied to the power generation device of the first embodiment shown in FIGS. 2 and 3, and further to the power generation device of the second embodiment shown in FIG.

  Further, as shown in FIG. 5, in the power generation device of the third embodiment, on the upper side of each fuel cell pair, two sheets of solid fuel are not sandwiched corresponding to each of the first fuel cell pair. Solid oxide fuel cells are arranged vertically. Solid oxide fuel cells C11 and C21 are arranged corresponding to the first fuel cell pair formed by the solid fuel F1 and the solid oxide fuel cells C1 and C2, and the solid fuel F2 and the solid oxide fuel cell are arranged. For the second fuel cell pair formed by C3 and C4, solid oxide fuel cells C31 and C41 are arranged and formed by solid fuel F3 and solid oxide fuel cells C5 and C6 Solid oxide fuel cells C31 and C41 are arranged for the third fuel cell pair.

  Each of the two solid oxide fuel cells disposed on the upper portion of the heat insulating container 7 has the anode electrode layers facing each other and the cathode electrode layer is on the outside, like the corresponding fuel cell pair. . By arranging the solid oxide fuel cells C11 to C61 in this way, for example, the anode electrode layers of the solid oxide fuel cells C11 and C21 are made of solid fuel of a corresponding fuel cell pair disposed below. The generated unused fuel species are supplied, and the fuel rich state can be maintained. Then, heated air is supplied from below to the cathode electrode layers of the solid oxide fuel cells C11 and C21, and an oxygen-rich state can be obtained. The same applies to the other solid oxide fuel cells C31 to C61.

  In the case of the first embodiment shown in FIGS. 2 and 3 and the case of the second embodiment shown in FIG. 4, the fuel species generated from the solid fuel sandwiched between the fuel cell pairs are used in the solid oxide fuel cell. If you can't, it will dissipate to the top. Therefore, in the power generation apparatus of the third embodiment shown in FIG. 5, a plurality of solid oxide fuel cells are arranged corresponding to each fuel cell pair. The fuel type that could not be used will be used effectively, and the fuel use efficiency can be improved. In addition, the fuel cell pair in which the solid fuel is not sandwiched can be arranged in the power generator of the first embodiment shown in FIGS. 2 and 3, and the fuel utilization efficiency is improved as in the case of the third embodiment. can do.

  In the power generators according to the first to third embodiments described above, as a solid fuel F sandwiched between two solid oxide fuel cells formed in a flat plate shape, a wooden board and a veneer board that can be easily obtained. As mentioned above, paper, wood chip assemblies or pellets are suitable. Here, the specific example that the solid fuel F can be used in another form will be described below with reference to FIG.

  FIG. 6 shows a manufacturing process of the solid fuel F. First, as shown in FIG. 6A, for example, organic solids such as raw garbage are stored in a stirring container 10 together with water, and the organic solids are pulverized by stirring. Next, as shown in FIG. 6 (b), the bottom plate of the stirring vessel 10 is replaced with a heat-resistant net M such as metal, the moisture in the vessel is extracted, and a solid fuel layer made of pulverized organic solids is formed. Adhere. Then, as shown in FIG. 6C, a flat solid fuel F in which an organic solid is attached to the heat-resistant net is completed.

  Here, the moisture makes the organic solid matter easy to stir, and the pulverized organic solid matter is matched on the net with a uniform thickness and the shape of the anode electrode layer of the solid oxide fuel cell. It is useful to attach. Even if the solid fuel F is completely dried, it retains its shape when attached to the net and can be used for power generation. Even if moisture remains in the solid fuel F, it can be used for power generation. can do. In the case where the solid fuel F is in such a raw dry state, it is confirmed that the reforming as the fuel proceeds with the moisture, and therefore, the solid fuel in the raw dry state is preferably used. In addition, the method of producing the solid fuel is not limited to garbage, and can also be applied to paper, a chip aggregate of wood, or a pellet.

  In the above, it demonstrated centering on the method of arrangement | positioning of the solid oxide fuel cell in the heat insulation container of the electric power generating apparatus which concerns on 1st thru | or 3rd embodiment. Next, a specific example relating to the mounting of the solid oxide fuel cell in the heat insulating container will be described by taking the solid oxide fuel cell power generator according to the first embodiment shown in FIG. 3 as an example. Here, FIG. 7 shows a solid oxide fuel cell having a configuration suitable for mounting in the heat insulating container.

  In the solid oxide fuel cell C shown in FIG. 7 (a), mesh-like metal or wire-like metals m1 and m2 are arranged in a size exceeding the range of the cathode electrode layer 2 and the anode electrode layer 3. Is the case. This solid oxide fuel cell C is based on the configuration of the solid oxide fuel cell C shown in FIG. 12, and the same reference numerals are given to the same portions.

  Here, an experiment was conducted on the generation of cracks in the solid electrolyte substrate due to the heating flame by changing the manner of disposing the mesh metal in the solid oxide fuel cell. In addition, the cathode electrode layer and the anode electrode layer in the above-described solid oxide fuel cell are usually formed of a porous material and are thinner than the solid electrolyte substrate, so that they can be ignored in terms of heat conduction. In this experiment, a solid electrolyte substrate made of SDC and having a diameter of 20 mm and a thickness of 0.2 mm and having no cathode electrode layer and no anode electrode layer was prepared.

  Here, a) a solid electrolyte substrate that does not fix the mesh metal on both sides, b) two types of solid electrolyte substrates that have a mesh metal with a diameter of 15 mm fixed on both sides, c) only on one side, and Two types of solid electrolyte substrates having a mesh metal having a diameter of 20 mm fixed on both surfaces, d) a solid electrolyte substrate having a mesh metal having a diameter of 15 mm fixed to one surface, and a mesh metal having a diameter of 20 mm fixed to the other surface, Each was formed.

  Therefore, in the experiment, a preheated flame generated by a burner is exposed to the central portion of one side of each solid electrolyte substrate formed in a) to d) to form a high-heat portion having a diameter of about 10 mm in the initial stage. The crack was observed. In the case of a), a crack is generated in the central portion of the solid electrolyte substrate, and in the case of b), a crack is generated in the peripheral portion of the solid electrolyte substrate on the outer periphery of the mesh metal, but c) and d In the case of), no cracks occurred on the entire surface of the solid electrolyte substrate.

The thermal conductivity of the solid electrolyte substrate is about 2 [Wm ⁻¹ K], whereas when the mesh metal is platinum, the thermal conductivity is about 72 [Wm ⁻¹ K]. In the case of SUS304 stainless steel, it is about 16.3 [Wm ⁻¹ K], and in the case of SUS430 stainless steel, it is about 26.3 [Wm ⁻¹ K].

  From this, considering the occurrence of cracks described above, the thermal conductivity of the mesh metal is higher than that of the solid electrolyte substrate. Therefore, in the portion where the mesh metal exists, the heat propagation to the solid electrolyte substrate. It is clear that there is little thermal shock. Therefore, if the mesh metal is disposed on the entire surface of at least one surface of the solid electrolyte substrate, the substrate will not crack even if the substrate is exposed directly and suddenly.

  Therefore, in the solid oxide fuel cell shown in FIG. 7A, based on the above knowledge, the cathode electrode layer and the anode electrode are suppressed in order to suppress the occurrence of cracks in the solid electrolyte substrate due to the rapid heating by the flame. A mesh-like metal or a wire-like metal extending beyond the layer was arranged. As an example of the solid oxide fuel cell of FIG. 7A, mesh metal or wire metals m1 and m2 extending over the entire surface of the solid electrolyte substrate 1 beyond the cathode electrode layer 2 and the anode electrode layer 3 are disposed. showed that.

  The configuration of the solid oxide fuel cell shown in FIG. 7A is the same as that of the solid oxide fuel cell C shown in FIG. 12, and the solid electrolyte substrate 1, the cathode electrode layer 2, and the anode electrode layer 3 are the same. In the cathode electrode layer 2, mesh metal or wire metal m1 is embedded or fixed. On the other hand, mesh-like metal or wire-like metal m2 is also embedded in or fixed to the anode electrode layer 3. Here, in the solid oxide fuel cell C of FIG. 7A, it extends beyond the formation range of the cathode electrode layer 2 and the anode electrode layer 3 to the outside of the solid electrolyte substrate 1. In addition, an oxide frame 11 having a predetermined width is formed in the outer spreading portion, and mesh-like metal or wire-like metal m2 is embedded and fixed.

  According to the experimental example described above, the arrangement of the mesh metal or wire metal of the solid oxide fuel cell shown in FIG. Correspondingly, the thermal shock caused by the rapid heating by the flame was alleviated, and the occurrence of cracks in the entire solid electrolyte substrate could be suppressed. In this case, the oxide frame 11 prevents the short circuit between the electrodes and has an effect as a countermeasure for suppressing cracks in the solid oxide fuel cell, and plays a role of reinforcement. And this oxide frame 11 becomes a holding | maintenance part when mounting | wearing with a solid oxide fuel cell in a heat insulation container.

  In addition, when a mesh metal is provided on only one side in c), an effect as a measure for suppressing cracks in the solid electrolyte substrate can be obtained. Further, when mesh-like metal or wire-like metals m1 and m2 are used as extraction electrodes for power generation output, as shown in FIG. 7A, the ends of mesh-like metal or wire-like metals m1 and m2 are oxidized. Although it is extended so as to be exposed from the object frame body 11, when a separate extraction electrode is provided on the mesh metal or the wire metal m 1, m 2, those end portions are in the oxide frame 11. It is assumed that it is embedded in.

  On the other hand, FIG. 7B shows the same configuration as the solid oxide fuel cell C shown in FIG. 7A, but the oxide oxide frame 11 holds the solid oxide fuel cell. An example in which a hole is provided is shown. In the oxide frame 11 shown in FIG. 7B, in order to hold the solid oxide fuel cell C vertically arranged in the heat insulating container, the through-hole H1 through which the guide rail provided horizontally is inserted. , H2 are provided.

  Here, since the mesh-like metal or the wire-like metals m1 and m2 are embedded in the oxide frame 11, when the guide rail is inserted into the holes H1 and H2, the mesh-like metal or the wire-like metal m1. And m2 are devised so as not to be short-circuited. For example, avoiding the position where the holes H1 and H2 are provided, the mesh metal or the wire metals m1 and m2 may be embedded, or the inner surfaces of the holes H1 and H2 may be insulated. Note that the oxide frame may be made of a solid electrolyte material, may be formed of a ceramic adhesive, or may be formed of a porous material.

  Next, a specific example of mounting using the solid oxide fuel cell including the oxide frame described above will be described with reference to FIGS. First, FIG. 8 shows a mounting example in the solid oxide fuel cell power generator of this embodiment using the solid oxide fuel cell C shown in FIG. 7B.

  In FIG. 8, two solid oxide fuel cells C1 and C2 are held in a form in which a solid fuel F is sandwiched. Here, for convenience of explanation, one set of fuel cell pairs is representatively shown. For the solid fuel F, two solid fuels F1 and F2 prepared by the procedure shown in FIG. 6 are used. These heat-resistant nets M are overlapped so as to be on the inside to form one solid fuel F. This solid fuel F is held in contact between the anode electrode layers of the solid oxide fuel cells C1 and C2. Note that the solid fuel F may be one of the solid fuels F1 and F2.

  To mount the solid oxide fuel cells C1 and C2 vertically in a heat insulating container (not shown in FIG. 8, corresponding to reference numeral 7 in FIGS. 2 to 5) with the solid fuel F sandwiched therebetween, Guide rails G1 and G2 attached to a holding frame provided in the heat insulating container are used. The guide rail G1 is inserted into a through hole provided in the upper part of each oxide frame of the solid oxide fuel cells C1 and C2, and the guide rail G2 is provided in the lower part of each oxide frame. Is inserted into the through hole.

  Each of the guide rails G1 and G2 is provided with fixtures N11 to N22 such as nuts and chucks that can slide or move on the guide rail and are fixed on the guide rail. Each of these fixtures holds the oxide frame through the spring bodies S11 to S22. In FIG. 8, in a state where the guide rails G1 and G2 are inserted through the through holes of the oxide frame bodies of the solid oxide fuel cells C1 and C2, the fixing tools N11 to N22 are respectively connected to the spring bodies S11 to S22. Then, the solid oxide fuel cell C1, the solid fuel F, and the solid oxide fuel cell C2 are held in a stacked state. The fixing member and the spring body form a pressure fixing member of the solid oxide fuel cell.

  The spring bodies N11 to N22 not only hold the solid oxide fuel cell C1, the solid fuel F, and the solid oxide fuel cell C2 in stable contact with each other, but also generate fuel species from the solid fuel F during power generation. Even when the volume of the solid fuel F decreases due to the release of the solid fuel F, the anode electrode layer of the solid oxide fuel cell has a role of pressing against the solid fuel F, and the fuel species supply to the anode electrode layer is stabilized.

  Further, the heat-resistant net M of the solid fuel F shown in FIG. 8 is held by being engaged with the guide rails G1 and G2, but the heat-resistant net is not subjected to insulation measures. May be. Further, FIG. 8 shows one set of fuel cell pairs sandwiching the solid fuel F, but a plurality of sets of the one set of fuel cells can be mounted in a heat insulating container. In this case, the cathode electrode layer of the solid oxide fuel cell may be provided with a spacer for spacing a predetermined distance from the cathode electrode layer of another pair of adjacent fuel cells.

  FIG. 8 shows a case where a pair of fuel cells sandwiching a solid fuel is vertically installed in a heat insulating container, that is, a case where the solid oxide fuel cell is in a power generation state. The situation at the time of exchange was shown. FIG. 9 shows a state in which each of the fixtures N11 to N22 is operated and slid or moved on the guide rails G1 and G2.

  As a result, the compressed state of the spring bodies S11 to S22 is released, and a gap is formed between the solid oxide fuel cell C1, the solid fuel F, and the solid oxide fuel cell C2. Here, when a gap is formed between each of the solid oxide fuel cell C1, the solid fuel F, and the solid oxide fuel cell C2, the used solid fuel is taken out and a new solid fuel F is inserted. . Next, each of the fixtures N11 to N22 may be operated to fix the spring bodies S11 to S22 at the compressed positions.

  Next, another mounting example of the solid fuel F is shown in FIG. The mounting example of FIG. 10 is shown by a vertical plane in the heat insulating container of the power generation apparatus, and the same structure as that of the solid oxide fuel cell of FIG. 8 is used for the solid oxide fuel cells C1 and C2. The oxide frame 11 is provided with four through holes H1 to H4. Guide rails G1 to G4 are individually inserted into the through holes.

  In the mounting of the solid fuel shown in FIG. 8 or FIG. 9, the heat-resistant net to which the solid fuel is attached is directly engaged with the guide rail. On the other hand, in the solid fuel mounting example shown in FIG. 10, a holding rod G5 different from the guide rail is prepared in the heat insulating container, and the hook 12 attached to the heat resistant net M of the solid fuel F is provided. The solid fuel F was held so as to be hooked on the holding rod G5.

  The solid fuel F is not engaged with the guide rails G1 to G4, but is held while its movement in the surface direction is restricted by the guide rails G1 to G4. Since the hook 12 is detachable from the holding rod G5, the replacement work of the solid fuel F is easily performed.

  On the other hand, another mounting example of the solid fuel F is shown in FIG. The mounting example of FIG. 11 is shown by a vertical plane in the heat insulating container of the power generation device, similarly to the case of FIG. 10, and the solid oxide fuel cells C1 and C2 include the solid oxide fuel cell of FIG. The same structure is used, and the oxide frame 11 is provided with four through holes H1 to H4. Guide rails G1 to G4 are individually inserted into the through holes.

  Here, as shown in FIG. 10, the through holes H1 to H4 are provided at the four corners of the oxide frame of the solid oxide fuel cell. In the mounting example of FIG. H1 and H4 are provided at the upper corners of the oxide frame, and the lower through holes H2 and H3 are shifted inward from the lower corners.

  Here, as shown in FIG. 11, the solid fuel F is held with the lower end portion of the heat-resistant net M of the solid fuel F in direct contact with the guide rails G <b> 2 and G <b> 3. In this case, the solid fuel F is held while its movement in the surface direction is restricted by the guide rails G1 and G4. When the solid fuel F is exchanged, it can be inserted between the guide rails G1 and G4 from above, and the exchange operation of the solid fuel F is easily performed.

  In the mounting example of the solid fuel shown in FIG. 11, the arrangement interval of the lower guide rails G2 and G3 is such that the anode electrode layer of the solid oxide fuel cell is solid when the fuel cell pair is held by the pressure fixing member. The number of guide rails in the lower portion can be appropriately selected by adjusting so as to be properly pressed against the fuel.

  As described above, the solid oxide fuel cell power generator that generates power using the fuel species generated from the solid fuel by heating the fuel cell pair in which the solid fuel is sandwiched between the two solid oxide fuel cells. Although the embodiment has been described, examples of the solid oxide fuel cell power generator according to the present invention will be described below.

A mixture containing samarium-doped ceria (Ce _0.8 Sm _0.2 O _1.9 , SDC) powder, polyvinyl butyral and dibutyl phthalate was slurried by a ball mill method to produce a green sheet having a thickness of about 0.2 mm, and punched into a disk shape A plate was created. Thereafter, the plate was fired at 1300 ° C. in the atmosphere to obtain a solid electrolyte substrate having a diameter of about 15 mm.

  A 50 wt% mixture paste of samarium strontium cobaltite (SSC) and SDC is printed on one surface of the solid electrolyte substrate, and a 15:45:40 weight ratio mixture paste of NiO—CoO—SDC is printed on the other surface. Was printed, a platinum mesh welded with a platinum wire (# 80) was embedded, and fired at 1200 ° C. in the atmosphere.

  About 0.5 g of wood pieces are sandwiched between a pair of solid oxide fuel cells produced in this manner so that the anode electrode layer faces, and a spring made from both cathode electrode layers can be pressed with a ceramic tube. Housed inside. This tube was inserted into an electric furnace to evaluate the power generation function. Here, the current could be taken out for about 20 minutes at a maximum of 44 mA at 690 ° C.

  Similarly, 8 sheets of paper (about 0.4 g) having a thickness of 0.3 mm were sandwiched between a pair of solid oxide fuel cells, and the power generation function was evaluated. Here, the current could be taken out for about 15 minutes at a maximum of 86 mA at 620 ° C.

It is a figure explaining the basic composition concerning the solid oxide fuel cell power generator by the present invention. 1 is a diagram for explaining a first embodiment of a solid oxide fuel cell power generator according to the present invention. FIG. It is a figure explaining the specific example of the solid oxide fuel cell electric power generating apparatus of 1st Embodiment. It is a figure explaining 2nd Embodiment of the solid oxide fuel cell electric power generating apparatus by this invention. It is a figure explaining 3rd Embodiment of the solid oxide fuel cell electric power generating apparatus by this invention. It is a figure explaining the preparation procedure of the solid fuel which can be used for the solid oxide fuel cell power generator by this invention. It is a figure explaining the specific example of the solid oxide fuel cell which can be used for the solid oxide fuel cell power generator by this invention. It is a figure explaining the example of mounting of the solid oxide fuel cell in the solid oxide fuel cell power generator by the present invention. It is a figure explaining replacement | exchange of the solid fuel in the mounting example of the solid oxide fuel cell shown in FIG. It is a figure explaining the other example of mounting | wearing of the solid fuel in the solid oxide fuel cell electric power generating apparatus by this invention. It is a figure explaining another example of mounting of the solid fuel in the solid oxide fuel cell power generator by the present invention. It is a figure explaining the solid oxide fuel cell power generator which generates electric power by flame direct use. It is a figure explaining the solid oxide fuel cell power generator which directly utilizes the flame by combustion of a solid fuel.

Explanation of symbols

1 Solid electrolyte substrate 2 Cathode electrode layer (air electrode layer)
3 Anode electrode layer (fuel electrode layer)
4 Burner 7 Thermal insulation container 8 Heat conduction plate 10 Stirring container 11 Oxide frame 12 Hook C, C1 to C8, C11 to C61 Solid oxide fuel cell f Flame F, F1 to F3 Solid fuel G1 to G5 Guide rail H1 -H4 hole m1, m2 Metal mesh / metal wire M Heat-resistant net N11-N22 Nut S11-S22 Spring body

Claims (19)

First and second solid oxide fuel cells having solid electrolyte substrates on which a cathode electrode layer and an anode electrode layer are formed;
A heat supply device for heating the first and second solid oxide fuel cells,
A solid oxide fuel cell comprising a solid fuel sandwiched between the anode electrode layer of the first solid oxide fuel cell and the anode electrode layer of the second solid oxide fuel cell. Power generation device. A first fuel cell pair comprising the first solid oxide fuel cell and the second solid oxide fuel cell sandwiching the solid fuel is housed in a heat insulating container;
2. The solid oxide fuel cell power generator according to claim 1, wherein the heat supply device is disposed at a lower portion of the heat insulating container, and air is supplied from the lower portion. The first fuel cell pair is disposed vertically in the insulated container;
The solid oxide fuel cell power generator according to claim 32, wherein the heat supply device is disposed below the first fuel cell pair.   4. The solid oxide fuel cell power generator according to claim 3, wherein the plurality of sets of the first fuel cell pairs are stored in the heat insulating container while maintaining a space therebetween.   5. The solid oxide fuel cell power generator according to claim 4, wherein the pressure fixing member that holds the gap is inserted between the plurality of first fuel cell pairs.   The solid oxide fuel cell power generator according to any one of claims 3 to 5, wherein a high thermal conductor layer is formed on an inner surface of the heat insulating container.   7. The second fuel cell pair comprising only the first solid oxide fuel cell and the second solid oxide fuel cell is disposed above the first fuel cell pair. The solid oxide fuel cell power generator according to any one of the above.   The solid oxide fuel cell power generator according to any one of claims 1 to 7, wherein the heat supply device supplies heat from a flame to the first fuel cell pair.   9. The solid oxide type according to claim 8, wherein the heat supply device supplies a flame that directly exposes an anode electrode layer of a solid oxide fuel cell disposed below the first fuel cell pair. Fuel cell power generator.   The solid fuel is made into a flat plate by adhering finely pulverized organic solids dispersed in water to a heat-resistant net with a substantially constant thickness and a size that matches the surface shape of the anode electrode layer. The solid oxide fuel cell power generator according to any one of claims 1 to 9, wherein Each of the first and second solid oxide fuel cells is coated from the edge of the cathode electrode layer to the edge of the anode electrode layer at the entire periphery of the solid electrolyte substrate. Having an oxide frame having a predetermined width from the edge;
A mesh-like metal or a wire-like metal is embedded or fixed on the entire surface of at least one of the cathode electrode layer and the anode electrode layer,
The solid oxide fuel cell power generator according to any one of claims 1 to 10, wherein each of the oxide frames includes a holding unit that holds the solid oxide fuel cell. .   The mesh-like metal or wire-like metal embedded or fixed in the cathode electrode layer and the anode electrode layer is a first collector electrode and a second collector electrode, and the first collector electrode and the second collector electrode. The solid oxide fuel cell power generator according to claim 11, wherein a power generation output is taken out from a lead wire connected to the electrode.   The solid oxide fuel cell power generator according to claim 12, wherein the mesh metal or wire metal is embedded in the oxide frame.   The solid oxide fuel cell power generator according to any one of claims 11 to 13, wherein the oxide frame is made of a solid electrolyte material or is made porous. The holding portion has a plurality of holes,
The first and second solid oxide fuel cells are vertically arranged in the heat insulating container by inserting guide rails provided in a holding frame in the heat insulating container into each of the holes,
The solid fuel is inserted vertically between the first solid oxide fuel cell and the second solid oxide fuel cell in the heat insulating container. A solid oxide fuel cell power generator according to claim 1. The guide rail includes a pressure fixing member that sandwiches and presses the solid fuel between the first and second solid oxide fuel cells,
16. The solid oxide fuel cell power generator according to claim 15, wherein the pressure fixing member is movable along the guide rail when the solid fuel is replaced. The holding part has holes provided at four corners of the oxide frame,
The solid oxide fuel cell power generator according to claim 15 or 16, wherein the guide rail is inserted into each of the holes.   The solid fuel is obtained by engaging an engagement tool provided at an upper end portion of the heat-resistant net attached with the solid fuel with a holding rod in the heat insulation container, so that the first solid oxide is contained in the heat insulation container. The solid oxide fuel cell power generator according to any one of claims 11 to 14, wherein the solid oxide fuel cell power generator is vertically inserted between the fuel cell and the second solid oxide fuel cell.   The solid fuel is supported by a lower guide rail provided at a holding frame in a heat insulating container at the lower end of the heat-resistant net to which the solid fuel is adhered, and the surface direction is regulated by the upper guide rail provided at the holding frame. 15, and is inserted vertically between the first solid oxide fuel cell and the second solid oxide fuel cell in the heat insulating container. The solid oxide fuel cell power generator according to item.

Images