JP5233148B2 - Solid oxide fuel cell - Google Patents

Description

  The present invention relates to a solid oxide fuel cell operating with a fuel gas and an oxidant gas.

A fuel cell is a cell that can directly convert chemical energy generated when fuel is oxidized into electric energy while continuously supplying fuel from the outside and exhausting combustion products. The types of fuel cells are classified according to the electrolyte, and those using metal oxides having ion conductivity for the electrolyte are called solid oxide fuel cells. Various types of solid oxide fuel cells have been proposed. For example, in Patent Document 1, a fuel electrode (anode) is formed on a porous support substrate, and the fuel electrode is formed on the fuel electrode. A solid oxide fuel cell is disclosed in which an electrolyte is formed and an air electrode (cathode) is formed on the electrolyte.
Japanese Patent Laid-Open No. 11-11309

  By the way, in the fuel cell as described above, it is possible to supply the hydrocarbon gas directly as the fuel gas, but by introducing the hydrocarbon gas directly, carbon deposition occurs on the fuel electrode, and the electrode structure There is a problem that durability is lowered by causing destruction or a decrease in electrode activity. At present, a reformer is placed outside the fuel cell to reform hydrocarbon gas and improve it. The hydrogen generated by the quality is fed into the fuel cell. At that time, the reformed gas (hydrogen-rich gas) generated by the reformer contains a trace amount of components such as carbon monoxide that are not directly involved in power generation, such as carbon monoxide, as impure components. As a result, further improvement in durability is a problem.

  The present invention has been made to solve the above problems, and an object of the present invention is to provide a solid oxide fuel cell that can efficiently use fuel gas and improve output and durability.

The present invention is a solid oxide fuel cell to which a fuel gas and an oxidant gas are supplied, and has been made in order to solve the above-mentioned problem. Hydrogen separation capable of selectively permeating hydrogen from the supplied gas a membrane, wherein disposed on the hydrogen separation membrane, and at least one through hole is formed the support, is disposed in the through hole of the support Rutotomoni, a fuel electrode covering the upper surface of the support An electrolyte disposed on the fuel electrode, and an air electrode disposed on the electrolyte, wherein the fuel electrode is configured to be separated from an oxidant gas supplied to the air electrode. .

  According to this configuration, the reformed gas (hydrogen-rich gas) generated through the reformer usually contains a trace amount of components that are not directly involved in power generation, such as carbon monoxide, as an impure component. Since the fuel electrode is disposed on the hydrogen separation membrane and separated from the oxidant gas supplied to the air electrode, the fuel gas supplied to the fuel electrode passes through the hydrogen separation membrane. It will be supplied to the fuel electrode. At this time, since hydrogen is separated from the fuel gas by the hydrogen separation membrane and supplied to the fuel electrode, it is possible to efficiently supply the necessary hydrogen to the fuel electrode and poison the impure component electrode. The possibility of this is also reduced. As a result, the output and durability of the battery can be improved.

  The material constituting the hydrogen separation membrane is mainly selected from the platinum group, vanadium group, etc., for example, can be selected from palladium, ruthenium, vanadium, niobium, tantalum, etc., and these can be laminated. it can. The hydrogen permeable membrane may be a porous or dense layer. For example, when it is formed of a dense layer, it is preferable to form at least one through hole. If it does in this way, the water which generate | occur | produced at the fuel electrode can be extracted through a through-hole. In addition, the support, each electrode, and the electrolyte can have various shapes, such as a plate shape, a sheet shape, and a block shape. The planar shape is not only rectangular but also various shapes such as a polygonal shape and a circular shape. It can be shaped.

  Further, when a conductive metal is used as the support, the mechanical strength is advantageously improved. Further, since the fuel electrode is disposed in the through hole of the support, the contact area between the fuel electrode and the conductive metal is increased, the current collection effect is improved, and high output can be expected. However, it is not always necessary to use a conductive metal as the support. That is, if the above-described materials are used as the hydrogen separation membrane, the support also functions as a current collector. Therefore, the support only needs to have heat resistance at the operating temperature of the fuel cell, and is inexpensive to be insulating at such operating temperature. It is also possible to use a simple metal. Therefore, the range of material selection is expanded, and the cost can be reduced.

  In the battery, the periphery of the electrolyte can be connected to the support, and the fuel electrode can be accommodated in a space formed by the electrolyte, the support, and the hydrogen separation membrane. By doing so, the fuel electrode is separated so as not to come into contact with the oxidant gas, and can be reliably operated without a gas leak. However, since the fuel electrode only needs to be separated from the oxidant gas, the fuel electrode can be separated by, for example, a sealing material in addition to connecting the peripheral portion of the electrolyte and the support.

  An object of the present invention is to provide a solid oxide fuel cell that efficiently uses fuel gas and can improve output and durability.

  Hereinafter, an embodiment of a solid oxide fuel cell according to the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view of a solid oxide fuel cell according to this embodiment.

  As shown in FIG. 1, the solid oxide fuel cell according to this embodiment includes a support substrate (support) 2, a fuel electrode 3, an electrolyte 4, and an air electrode 5 arranged in this order on a hydrogen separation membrane 1. It is configured by being. More specifically, a plurality of through holes 21 are formed in the support substrate 2, and the thin-film hydrogen separation membrane 1 is disposed on the lower surface of the support substrate 2 so as to close the through holes 21. The fuel electrode 3 is filled in the through-hole 21 of the support substrate 2, contacts the hydrogen separation membrane 1, and covers the upper surface of the support substrate 2. A thin-film electrolyte 4 is disposed on the upper surface of the fuel electrode 3. The electrolyte 4 covers the upper surface of the fuel electrode 3, and its peripheral edge extends to the upper surface of the support substrate 2. That is, the fuel electrode 3 is accommodated in a space surrounded by the hydrogen separation membrane 1, the support substrate 2, and the electrolyte 4, so that the fuel electrode 3 is not exposed to the outside. A thin-film air electrode 5 is formed on the electrolyte 4 thus formed. The fuel electrode 3 and the air electrode 5 are porous and gas permeable, and the hydrogen separation membrane 1, the support substrate 2, and the electrolyte 4 are densely formed so as not to transmit gas. However, as will be described later, the hydrogen separation membrane has a plurality of through holes (not shown) for draining water.

  Subsequently, materials constituting the fuel cell will be described. The hydrogen separation membrane 1 is mainly selected from a platinum group, a vanadium group, and the like, and can be made of a metal or a metal oxide such as palladium, ruthenium, vanadium, niobium, and tantalum, for example. These may be a single layer or may be laminated in a plurality of layers. For example, when a gas such as carbon monoxide and hydrogen are mixed and contacted or passed through the hydrogen separation membrane 1, only hydrogen is separated.

  As a material which comprises the support substrate 2, it should just be comprised with the material which consists of a metal and a metal oxide. For example, Fe, Ti, Cr, Cu, Ni, and Ag can be used as the metal material, and one kind may be used alone, or two or more kinds may be alloyed. For example, stainless steel heat-resistant materials can be used, and specifically, austenitic stainless steel and ferritic stainless steel can be used. As the metal oxide material, a heat resistant and strong material such as alumina can be used.

  As the material of the electrolyte 4, those known as electrolytes for solid oxide fuel cells can be used. For example, ceria oxide (GDC) doped with samarium or gadolinium, lanthanum doped with strontium or magnesium An oxygen ion conductive ceramic material such as a galide oxide, zirconia oxide (YSZ) containing scandium or yttrium can be used.

  The fuel electrode 3 and the air electrode 5 can be formed of a ceramic powder material. The average particle size of the powder used at this time is preferably 10 nm to 100 μm, more preferably 50 nm to 50 μm, and particularly preferably 100 nm to 10 μm. In addition, an average particle diameter can be measured according to JISZ8901, for example.

  As the fuel electrode 3, for example, a mixture of a metal catalyst and a ceramic powder material made of an oxide ion conductor can be used. As the metal catalyst used at this time, a material that is stable in a reducing atmosphere, such as nickel, iron, cobalt, or a noble metal (platinum, ruthenium, palladium, etc.) and has hydrogen oxidation activity can be used. In addition, as the oxide ion conductor, one having a fluorite structure or a perovskite structure can be preferably used. Examples of those having a fluorite structure include ceria-based oxides doped with samarium, gadolinium, and the like, and zirconia-based oxides containing scandium and yttrium. In addition, examples of those having a perovskite structure include lanthanum galide oxides doped with strontium and magnesium. Among the above materials, it is preferable to form the fuel electrode 2 with a mixture of an oxide ion conductor and nickel. The mixed form of the ceramic material made of the oxide ion conductor and nickel may be a physical mixed form, or may be a powder modification to nickel or a nickel modification to ceramic material. Good. Moreover, the ceramic material mentioned above can be used individually by 1 type or in mixture of 2 or more types. Moreover, the fuel electrode 3 can also be comprised using a metal catalyst alone.

As the ceramic powder material forming the air electrode 5, for example, a metal oxide made of Co, Fe, Ni, Cr, Mn or the like having a perovskite structure or the like can be used. Specifically, (Sm, Sr) CoO ₃ , (La, Sr) MnO ₃ , (La, Sr) CoO ₃ , (La, Sr) (Fe, Co) O ₃ , (La, Sr) (Fe, Co , Ni) O _{3 and the} like, and (La, Sr) (Fe, Co) O ₃ is preferable. The ceramic material mentioned above can be used individually by 1 type or in mixture of 2 or more types.
The fuel electrode 3 and the air electrode 5 can be formed by, for example, a wet coating method or a dry coating method. Examples of the wet coating method include a screen printing method, an electrophoresis (EPD) method, a doctor blade method, a spray coating method, an ink jet method, a spin coating method, and a dip coating method. At that time, the fuel electrode 3 and the air electrode 5 need to be made into a paste, and are formed by adding the appropriate amount of a binder resin, an organic solvent, etc. with the above-described material as a main component. More specifically, it is preferable to add a binder resin or the like so that the main component is 50 to 95% by weight in the mixing of the main component and the binder resin. Examples of dry coating methods include vapor deposition, sputtering, ion plating, chemical vapor deposition (CVD), electrochemical vapor deposition, ion beam, laser ablation, and atmospheric pressure plasma deposition. Alternatively, it can be formed by a low pressure plasma film forming method or the like.

  The electrolyte 4 can be formed by the same technique as the fuel electrode 3 and the air electrode 5 described above, but if formed by a dry coating method or a sol-gel method, the electrolyte 4 is more general than the wet coating method. In addition, a dense metal oxide film can be formed at a low temperature. The hydrogen separation membrane 1 can be formed by a surface treatment technique for coating a metal thin film such as plating. The thickness of the hydrogen separation membrane is 1 to 20 μm, preferably 1 to 10 μm. When the thickness is less than 1 μm, the strength of the film is insufficient, and when the thickness exceeds 20 μm, the hydrogen permeation performance is deteriorated. Moreover, although the film thickness of the fuel electrode 3 and the air electrode 5 is formed so that it may become 5-100 micrometers, it is preferable to set it as 20-50 micrometers. The film thickness of the electrolyte 4 is preferably 1 to 100 μm, and more preferably 5 to 50 μm.

  Next, a method for manufacturing the fuel cell will be described with reference to FIG. FIG. 2 is an explanatory diagram of a method for manufacturing a fuel cell according to this embodiment. The following method is an example using the method described above. First, the support substrate 2 made of the above-described material is prepared. A plurality of through holes 21 are formed in the support substrate 2 in advance. Then, the through hole 21 of the support substrate 2 is sealed with a thermally decomposable resin, and the hydrogen separation membrane 1 is coated on one surface of the support substrate 2 by plating or the like, and then the resin is decomposed and removed by heat treatment. Then, the hydrogen separation membrane 1 is disposed on the support substrate 2 in which the through holes 21 are formed (FIG. 2A). Next, the fuel electrode 2 is formed on the upper surface of the support substrate 2 by screen printing or the like. Here, first, the fuel electrode paste made of the above-described material is printed on the support substrate 2. At this time, the fuel electrode paste is applied so as to fill the through holes 21 and cover the upper surface of the support substrate 2. And it dries and sinters for a predetermined time, and forms the fuel electrode 3 (FIG.2 (b)). Subsequently, an electrolyte 4 is formed so as to cover the fuel electrode 3 by dipping or the like. At this time, the periphery of the electrolyte 4 is brought into contact with the support substrate 1, and the fuel electrode 3 is accommodated between the hydrogen separation membrane 1 and the electrolyte 4 (FIG. 2 (c)). Subsequently, the air electrode paste made of the above-described material is applied onto the electrolyte 4 by screen printing, and dried and sintered for a predetermined time to obtain the porous air electrode 5. The fuel cell shown in FIG. 1 is completed through the above steps.

  The fuel cell configured as described above generates power as follows. First, a fuel gas composed of a reformed gas (hydrogen rich gas) reformed by a reformer is introduced into the hydrogen separation membrane 1. When the fuel gas contacts the hydrogen separation membrane 1, hydrogen is separated here. The separated hydrogen passes through the hydrogen separation membrane 1 and contacts the fuel electrode 3. In parallel with this, an oxidant gas such as air is supplied to the air electrode 5. At this time, since the periphery of the fuel electrode 3 is covered with the hydrogen separation membrane 1 and the dense electrolyte 4, the oxidant gas does not contact the fuel electrode 3, and the hydrogen supplied to the fuel electrode 3 is not There is no leakage to the air electrode 5 side. Thus, since the fuel electrode 3 and the air electrode 5 are in contact with hydrogen and oxidant gas, respectively, oxygen ion conduction through the electrolyte 4 occurs between the fuel electrode 3 and the air electrode 5, and power generation is performed. The water generated at the fuel electrode 3 is discharged to the outside through a through hole formed in the hydrogen separation membrane 1.

  As described above, according to the present embodiment, since the fuel gas is supplied to the fuel electrode 3 through the hydrogen separation membrane 1, hydrogen is separated by the hydrogen separation membrane 1 and supplied to the fuel electrode 3. For this reason, it becomes possible to supply hydrogen required for the fuel electrode 3 efficiently, and the output and durability of the battery can be further improved.

  The embodiment of the present invention has been described above, but the present invention is not limited to this, and various modifications can be made without departing from the spirit of the present invention. For example, it is not necessary to increase the thickness of the fuel electrode 3 until the upper surface of the support substrate 2 is covered. As shown in FIG. 3, the fuel electrode 3 is thinner than the support substrate 2 and is disposed in the through hole 21. Also good. In this case, the electrolyte 4 has a structure that enters the through hole 21 from the upper surface of the support substrate 2.

  Moreover, in the said embodiment, the peripheral part of the electrolyte 4 is connected with the support substrate 2, and the fuel electrode 3 is accommodated in the space between the hydrogen separation membrane 1 and the electrolyte 4, For example, as shown in FIG. In addition, the glass seal 6 can be disposed on the peripheral edge of the electrolyte 4, and thereby the peripheral edge of the electrolyte 4 and the support substrate 2 can be connected. Even in such a configuration, the fuel electrode 3 can be separated from the oxidant gas as in the above embodiment.

  Further, in the manufacturing method described above, the support substrate 2 in which the through holes 21 are formed in advance is prepared. However, after preparing a substrate in which the through holes 21 are not formed and placing the substrate on the hydrogen separation membrane 1, etching or the like is performed. Through holes can also be formed. Further, the support substrate 2 does not necessarily have conductivity, and may be a material that becomes insulative at the battery operating temperature, such as general SUS. That is, it is only necessary to have heat resistance at the operating temperature, thereby expanding the range of material selection and reducing the cost.

1 is a cross-sectional view showing an embodiment of a solid oxide fuel cell according to the present invention. It is a figure which shows the manufacturing method of the fuel cell of FIG. It is sectional drawing which shows the other example of the fuel cell of FIG. FIG. 6 is a cross-sectional view showing still another example of the fuel cell in FIG. 1.

Explanation of symbols

1 Hydrogen separation membrane 2 Support substrate (support)
21 Through-hole 3 Fuel electrode 4 Electrolyte 5 Air electrode

Claims (2)

A solid oxide fuel cell to which a fuel gas and an oxidant gas are supplied,
A hydrogen separation membrane capable of selectively permeating hydrogen from the supplied gas;
A support disposed on the hydrogen separation membrane and having at least one through hole formed thereon;
Rutotomoni disposed in the through hole of the support, and a fuel electrode covering the upper surface of the support,
An electrolyte disposed on the fuel electrode;
An air electrode disposed on the electrolyte, and
The fuel electrode is a solid oxide fuel cell configured to be separated from an oxidant gas supplied to the air electrode. 2. The solid oxide according to claim 1, wherein a peripheral portion of the electrolyte is connected to the support, and the fuel electrode is accommodated in a space formed by the electrolyte, the support, and a hydrogen separation membrane. Physical fuel cell.

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