JP2005135889A - Fuel battery cell and fuel battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel battery cell and a fuel battery, capable of maintaining a high power generating property for a long time by suppressing lowering of the power generation properties of the fuel cell, by preventing exfoliation of an oxygen electrode (A) and a reaction preventive layer (C), or of an oxygen electrode (B) and a solid electrolyte. <P>SOLUTION: The oxygen electrode 34 has a two-layered structure, a first-layer oxygen electrode 34a adjacent to the reaction-preventing layer 37 made denser than a second-layer oxygen electrode 34b, and consists of a mixed component with particles having ion conductivity as well as electron conductivity and particles having electron conductivity, particles constituting the reaction preventing layer 37 and particles of the first-layer oxygen electrode 34a containing the same components, and the second layer oxygen electrode 34b consisting of particles having electron conductivity. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a solid oxide fuel cell and a fuel cell.

In recent years, various fuel cells in which a stack of fuel cells is accommodated in a storage container have been proposed as next-generation energy.
FIG. 3 shows a cell stack of a conventional solid oxide fuel cell, in which a plurality of fuel cells (1a, 1b) are aligned and assembled, and one fuel cell 1a and the other fuel cell. A current collecting member 5 made of metal felt is interposed between the cell 1b and the fuel electrode 7 of one fuel cell 1a and the oxygen electrode 11 of the other fuel cell 1b are electrically connected. It was.
The fuel battery cell (1a, 1b) is configured by sequentially providing a solid electrolyte 9 and an oxygen electrode 11 made of conductive ceramics on the outer peripheral surface of a fuel electrode 7 made of a cylindrical metal. The fuel electrode 7 exposed from the electrode 11 is provided with an interconnector 12 so as not to be connected to the oxygen electrode 11 and is electrically connected to the fuel electrode 7.

The interconnector 12 is dense and is conductive ceramics that is dense in order to reliably shut off the fuel gas flowing inside the fuel electrode 7 and the oxygen-containing gas flowing outside the oxygen electrode 11, and hardly changes in quality by the fuel gas and oxygen-containing gas. Is used.
The electrical connection between one fuel battery cell 1a and the other fuel battery cell 1b is performed by connecting the fuel electrode 7 of one fuel battery cell 1a via the interconnector 12 and the current collecting member 5 provided on the fuel electrode 7. This is done by connecting to the oxygen electrode 11 of the other fuel cell 1b. The fuel cell is configured by housing the cell stack in a storage container, and generates power at about 1000 ° C. by flowing fuel (hydrogen) through the fuel electrode 7 and flowing air (oxygen) through the oxygen electrode 11.

In such a fuel cell, in general, the fuel electrode 7 is made of Ni and ZrO ₂ (YSZ) containing Y ₂ O ₃ , and the solid electrolyte 9 is ZrO ₂ (YSZ) containing Y ₂ O _3. The oxygen side electrode 11 is composed of a LaMnO ₃ composite oxide. In recent years, in order to prevent diffusion of elements from the oxygen electrode 11 to the solid electrolyte 9, a reaction preventing layer containing Ce is formed between the solid electrolyte 9 and the acid cord 11.
However, in the conventional fuel cell, when the oxygen electrode 11 is baked on the solid electrolyte 9 or the reaction preventing layer, the interface resistance between the oxygen electrode 11 and the solid electrolyte 9 or the reaction preventing layer is high, and power generation is performed for a long time. However, there is a problem that the performance of the fuel cell is lowered.
As a method for solving the above-described problem, a structure in which coarse particles are connected in a three-dimensional network has been proposed for the purpose of increasing the three-phase interface in the upper layer portion of the oxygen electrode 11 (two patents). Reference 1).

JP 2002-289248 A

However, even if the oxygen electrode 11 has the two-layer structure, the mechanical strength of the lower layer oxygen electrode and the solid electrolyte 9 or the reaction preventing layer is weak, and when power is generated for a long time, the oxygen electrode 11 and the solid electrode 9 are solid. Peeling occurs at the interface with the electrolyte 9 or the reaction preventing layer, thereby causing a decrease in the performance of the fuel cell, or oxygen ions obtained by volume diffusion at the oxygen electrode in the lower layer are interface portions between the oxygen electrode particles. However, there was a problem that the ions could not be exchanged smoothly and the output could not be extracted sufficiently.
The present invention prevents the occurrence of exfoliation of the oxygen electrode (A) and the reaction preventing layer (C) or prevents the exfoliation of the oxygen electrode (B) and the solid electrolyte, and suppresses a decrease in power generation performance to achieve high power generation performance. It aims at providing the fuel cell and fuel cell which can be maintained over a long period of time.

The fuel cell according to the first aspect of the present invention is a fuel cell in which an oxygen electrode (A) is provided on one side of a solid electrolyte via a reaction preventing layer (C) and a fuel electrode is provided on the other side. (A) is a two-layer structure, the oxygen electrode (A1) of the first layer adjacent to the reaction preventing layer (C) is denser than the oxygen electrode (A2) of the second layer, The particles constituting the reaction preventing layer (C) and the oxygen in the first layer are composed of a mixed component of particles (A11) having ion conductivity and electron conductivity and particles (A12) having electron conductivity. The electrode (A1) particles (A11) contain the same component, and the second layer oxygen electrode (A2) is composed of particles having electron conductivity.
In such a fuel cell, since the particles constituting the reaction preventing layer (C) and the particles (A11) of the first layer oxygen electrode (A1) contain the same component, the oxygen electrode ( When A) is fired or formed by heat treatment, the particles constituting the reaction preventing layer and the oxygen electrode (A1) particles (A11) are easily bonded to each other, and the oxygen electrode (A) and the reaction preventing layer ( The mechanical joint strength with C) is increased, and peeling can be prevented.
Further, in the first layer oxygen electrode (A1), oxygen ions generated by the diffusion of the oxygen electrode raw material are particles having electron conductivity and ion conductivity that exist between the particles (A12) having electron conductivity ( By using A11) as a bypass and moving to the particle (A12) having the electron conductivity of the next oxygen electrode (A1), the polarization resistance is reduced and high power generation capability is exhibited.

In the fuel battery cell of the first aspect of the present invention,
1. 1. The oxygen electrode (A2) in the second layer is formed by connecting porous coarse particles in which a large number of conductive ceramic fine particles are aggregated in a three-dimensional network. The composite comprising the particles constituting the reaction preventing layer (C) and the particles (A11) of the oxygen electrode (A1) of the first layer each comprising CeO ₂ and Sm ₂ O ₃ represented by the general formula (1) it is an oxide _{(CeO 2) 1-x (} SmO 3/2) x (1)
(1) In the formula, x is in the range of 0 <x ≦ 0.3.
3. The oxygen electrode (A1) in the first layer is composed of 10 to 30% by mass of particles (A11) having ion conductivity and electron conductivity and 70 to 90% by mass of particles (A12) having electron conductivity 4 . The thickness of the first layer oxygen electrode (A2) is desirably 3 to 20 μm.

The fuel cell of the second aspect of the present invention is a fuel cell in which the oxygen electrode (B) is provided on one side of the solid electrolyte and the fuel electrode is provided on the other side, and the oxygen electrode (B) has a two-layer structure. Thus, the first layer oxygen electrode (B1) adjacent to the solid electrolyte is denser than the second layer oxygen electrode (B2), and particles having ion conductivity and electron conductivity ( B11) and a particle having electron conductivity (B12), and the oxygen electrode (B2) in the second layer is composed of particles having electron conductivity.
In such a fuel cell, the bonding strength of the oxygen electrode to the solid electrolyte can be improved.
The fuel cell of the present invention is characterized in that the fuel cell is housed in a housing container. In such a fuel cell, as described above, since the bonding strength to the oxygen electrode to the solid electrolyte can be improved, long-term reliability can be improved.

  As described above in detail, in the fuel battery cell of the present invention, the oxygen electrode has a two-layer structure composed of specific components, thereby preventing the oxygen electrode (A) and the reaction preventing layer (C) from peeling off. Alternatively, the occurrence of peeling between the oxygen electrode (B) and the solid electrolyte can be prevented, and high power generation performance can be maintained over a long period of time by suppressing a decrease in power generation performance of the fuel cell.

The fuel cell according to the first aspect of the present invention is a fuel cell in which an oxygen electrode (A) is provided on one side of a solid electrolyte via a reaction preventing layer (C) and a fuel electrode is provided on the other side. (A) is a two-layer structure, the oxygen electrode (A1) of the first layer adjacent to the reaction preventing layer (C) is denser than the oxygen electrode (A2) of the second layer, The particles constituting the reaction preventing layer (C) and the oxygen in the first layer are composed of a mixed component of particles (A11) having ion conductivity and electron conductivity and particles (A12) having electron conductivity. The electrode (A1) particles (A11) contain the same components, and the second layer oxygen electrode (A2) is composed of particles having electron conductivity.
The fuel battery cell according to the first aspect is as follows.
FIG. 1 is a perspective view of the fuel cell according to the first embodiment. In FIG. 1, a fuel cell indicated by reference numeral 30 includes a conductive support substrate 31 having a shape having a pair of flat surfaces extending in parallel and arcuate connection surfaces on both sides of the flat surface. . A plurality of fuel gas passages 31 a are formed at appropriate intervals inside the conductive support substrate 31. The fuel cell 30 has a structure in which various members are provided on the conductive support substrate 31. doing.

As is understood from the shape shown in FIG. 1, the conductive support substrate 31 is provided with a fuel electrode 32 so as to cover one surface of the flat portion and the arc-shaped connection surfaces on both sides. A dense solid electrolyte 33 is laminated so as to cover the fuel electrode 32, and an oxygen electrode 34 is interposed on the solid electrolyte 33 via a reaction preventing layer 37 so as to face the fuel electrode 32. Are stacked. An interconnector 35 is formed on the other flat surface where the fuel electrode 32 and the solid electrolyte 33 are not stacked. As is clear from FIG. 1, the fuel electrode 32 and the solid electrolyte 33 extend to both sides of the interconnector 35 and are configured so that the surface of the conductive support substrate 31 is not exposed to the outside.
Moreover, about the fuel cell of this invention as mentioned above, the cross section of the site | part engaged in electric power generation is shown in FIG.
In the fuel cell having the above structure, the portion of the fuel electrode 32 facing the oxygen electrode 34 operates as a fuel electrode to generate electric power. That is, an oxygen-containing gas such as air is allowed to flow outside the oxygen electrode 34, and a fuel gas (hydrogen) is allowed to flow through the gas passage 31 a in the conductive support substrate 31, and the oxygen electrode 34 is heated to a predetermined operating temperature. Electric power is generated by causing an electrode reaction at the fuel electrode 32.
The current generated by such power generation is collected via an interconnector 35 attached to the conductive support substrate 31.

In the fuel battery cell 30 of the present invention having the above-described structure, the conductive support substrate 31 is gas permeable so as to allow the fuel gas to permeate to the fuel electrode 32 and is collected via the interconnector 35. It is required to be conductive in order to conduct electricity. At the same time, in order to avoid the disadvantages caused by simultaneous firing, it is necessary to conduct conductivity from an iron group metal component and a specific rare earth oxide. It is desirable that the support substrate 31 be configured.
The iron group metal component is for imparting conductivity to the conductive support substrate 31, and may be an iron group metal alone, or an iron group metal oxide, an iron group metal alloy or alloy oxide. It may be. The iron group metals include iron, nickel, and cobalt, and any of them can be used in the present invention. However, Ni and / or NiO are stable in the fuel gas, are easily available, and are inexpensive. Is preferably contained as an iron group component.
The rare earth oxide component is used to bring the thermal expansion coefficient of the conductive support substrate 31 close to the thermal expansion coefficient (about 10.8 × 10 ⁻⁶ / ° C.) of the solid electrolyte 33, and Y, Lu, Yb, Tm, Er , Ho, Dy, Gd, Sm, and Pr are preferably rare earth oxides containing at least one element selected from the group consisting of. In particular, Y ₂ O ₃ and Yb ₂ O ₃ are preferable from the viewpoints that there is almost no solid solution or reaction with iron group metal oxides and that the thermal expansion coefficient is almost the same as that of the solid electrolyte 33.
In the present invention, the iron group component described above is included in the conductive support substrate 31 in an amount of 65 to 35% by volume, particularly in that the thermal expansion coefficient of the conductive support substrate 31 is approximated to that of the solid electrolyte 33. The rare earth oxide is preferably contained in the conductive support substrate 31 in an amount of 35 to 65% by volume. The conductive support substrate 31 may contain other metal components and oxide components as long as required characteristics are not impaired.
In addition, since the conductive support substrate 31 is required to have fuel gas permeability, it is usually preferable that the open porosity is 30% or more, particularly 35 to 50%. Further, the conductivity of the conductive support substrate 31 is preferably 300 S / cm or more, and particularly preferably 440 S / cm or more.

In the present invention, the fuel electrode 32 causes an electrode reaction, and is formed of a well-known porous conductive ceramic. For example, it can be formed from ZrO _{2 in which a} rare earth element is dissolved or CeO ₂ in which a rare earth element is dissolved, and Ni and / or NiO.
The content of ZrO ₂ in which the rare earth element in the fuel electrode 32 is dissolved is preferably in the range of 35 to 65% by volume, and the content of Ni or NiO is preferably 65 to 35% by volume. . Further, the open porosity of the fuel electrode 32 is preferably 15% or more, particularly preferably in the range of 20 to 40%, and the thickness thereof is preferably 1 to 30 μm.
For example, if the thickness of the fuel electrode 32 is too thin, the performance may be deteriorated, and if it is too thick, there is a risk of causing inconvenience such as separation due to a difference in thermal expansion between the solid electrolyte 33 and the fuel electrode 32.
Further, in the example of FIG. 1, the fuel electrode 32 extends to both sides of the interconnector 35, but it is sufficient that the fuel electrode 32 is formed at a position facing the oxygen electrode 34. For example, the fuel electrode 32 may be formed only in the flat portion on the side where the acid side electrode 34 is provided. Furthermore, the fuel electrode 32 can be formed over the entire circumference of the conductive support substrate 31.

The solid electrolyte 33 provided on the outer surface of the fuel electrode 32 is a dense ceramic made of partially stabilized or stabilized ZrO ₂ containing 3 to 15 mol% of Y and / or rare earth elements such as Sc and Yb. It is used. As the rare earth element, Y is preferable from the viewpoint of availability and price. The thickness of the solid electrolyte 9 is preferably 10 to 100 μm from the viewpoint of preventing gas permeation, and particularly preferably 10 to 50 μm from the viewpoint of reducing electric resistance.

The reaction preventing layer 37 formed between the solid electrolyte 33 and the oxygen electrode 34 preferably contains Ce as an element, and in particular, a composite oxidation composed of CeO ₂ and Sm ₂ O ₃ represented by the general formula (1). It is desirable to be a thing.
(CeO ₂ ) _1-x (SmO _3/2 ) _x (1)
In the CeO ₂ in which Sm ₂ O ₃ is dissolved, x is preferably 0 <x ≦ 0.3 in the formula (1). In particular, z is 0.1 from the viewpoint of reducing electric resistance. Preferably, CeO ₂ (SDC) in which Sm ₂ O _{3 of} ≦ x ≦ 0.2 mol% is dissolved.
Furthermore, in order to enhance the effect of blocking or suppressing the diffusion of elements diffusing from the oxygen electrode (A) to the solid electrolyte, oxides of other rare earth elements may be included.

Moreover, it is preferable to produce the reaction prevention layer 37 using the powder in which the aggregation degree of the ceramic powder was adjusted to 5-35. Thereby, baking shrinkage can be controlled and peeling of a solid electrolyte and generation | occurrence | production of a crack can be prevented. In particular, it is desirable to adjust the aggregation degree to 5 to 15 in that the power generation performance can be prevented from being lowered.
That is, when the aggregation degree of the ceramic powder forming the reaction preventing layer 37 is adjusted to 5 to 35, peeling and cracking between the reaction preventing layer 37 and the solid electrolyte are effective even when the reaction preventing layer 37 is retrofitted. Can be suppressed.
In addition, the degree of aggregation is obtained by the following formula.
Aggregation degree = (particle diameter determined by laser light scattering method) / (pseudo sphere diameter determined from specific surface area)
When the degree of aggregation is large, since the primary particles in the aggregated particles are very small and the sintering activity is high, the sintering between the primary particles proceeds faster than the sintering between the aggregated particles. As a result, the shrinkage of the aggregated particles proceeds, the overall shrinkage is delayed, and cracks such as gaps are formed between the aggregated particles such as stone walls.
On the other hand, since the solid electrolyte raw material has a particle size of 0.5 to 3 μm in consideration of co-sintering with the support, the solid electrolyte in contact with the reaction preventing layer 37 is pulled by the firing shrinkage of the reaction preventing layer. As a result, cracks such as stone walls and peeling occur. When the degree of agglomeration is small, sintering of primary particles, sintering between the agglomerated particles, and sintering of the solid electrolyte start almost simultaneously, so that a uniform sintered body is obtained.
Further, in order to effectively block the element diffusing from the oxygen electrode (A) to the solid electrolyte, the thickness of the reaction preventing layer is preferably 1 to 20 μm.

The oxygen electrode (A) 34 has a two-layer structure as shown in FIG. 1, and the oxygen electrode (A1) 34a of the first layer includes ceramic particles (A11) having ion conductivity and electron conductivity. It consists of a mixed component with the ceramic particle (A12) which consists of a perovskite type oxide which has electronic conductivity.
As the ceramic particles (A11) having ion conductivity and electron conductivity, composite oxidation comprising CeO ₂ and Sm ₂ O ₃ is preferable, and composite oxidation comprising CeO ₂ and Sm ₂ O ₃ represented by the general formula (1). More preferably, it is a product.
(CeO ₂ ) _1-x (SmO _3/2 ) _x (1)
In the case of CeO ₂ in which Sm ₂ O ₃ is dissolved, x is preferably 0 <x ≦ 0.3 in the formula (1), and x is preferably 0.1 from the viewpoint of reducing electrical resistance. Particularly preferred is CeO ₂ (SDC) in which Sm ₂ O _{3 of} ≦ x ≦ 0.2 mol% is dissolved.

Since this SDC is a mixed conductor having ion conductivity and electron conductivity, a so-called three-phase interface is formed by being mixed with a perovskite oxide.
The general formula (1) is the same as the component forming the reaction preventing layer (C), but in the first aspect of the present invention, the ceramic particles (A11) form the reaction preventing layer (C). Even if it is the same as the component, the same effect can be obtained, but from the point of improving the effect of preventing peeling between the oxygen electrode (A) and the reaction preventing layer (C), the same composition is used. More preferably.
Ceramic particles (A12) comprising a perovskite oxide having electron conductivity include transition metal perovskite oxides, particularly LaMnO ₃ oxides, LaFeO ₃ oxides, LaCoO ₃ oxides having La at the A site. At least one of these is suitable, and LaFeO ₃ -based oxides are particularly suitable because they have high electrical conductivity at an operating temperature of about 600 to 1000 ° C. In the perovskite oxide, Sr and the like may exist together with La at the A site, and Co and Mn may exist together with Fe at the B site.
The oxygen electrode (A1) 34a must have a certain degree of gas permeability. Therefore, the open porosity is preferably 20% or less, particularly preferably in the range of 5 to 20%.

The oxygen electrode (A2) 34b of the second layer is composed of ceramic particles having electronic conductivity formed by connecting porous coarse particles in which a large number of conductive ceramic fine particles are aggregated in a three-dimensional network, A conductive ceramic made of a so-called ABO ₃ type perovskite oxide can be preferably used. Among the ABO ₃ type perovskite type oxides, it is desirable that the ABO ₃ type perovskite type oxide is composed of at least one kind of porous conductive ceramics of LaMnO ₃ type material, LaFeO ₃ type material and LaCoO ₃ type material. The oxygen electrode 34 is more preferably LaFeO ₃ based material because it has high electrical conductivity at a relatively low temperature of about 600 to 1000 ° C. The composite oxide represented by the general formula (2) It is particularly desirable that
_{La y Sr 1-y Co z} Fe 1-z O 3 (2)
(2) In the formula, y and z are ranges of 0.5 ≦ y ≦ 0.7 and 0.2 ≦ z ≦ 0.8, respectively.
The oxygen electrode (A2) must have gas permeability. Therefore, the perovskite oxide having conductivity that forms the oxygen electrode (A2) has an open porosity of 20% or more, particularly 30 to 30%. It is preferable to be in the range of 50%.

Moreover, it is desirable that the oxygen electrode (A1) of the first layer is composed of 10 to 30% by mass of the perovskite oxide having electron conductivity and 70 to 90% by mass of the component constituting the reaction preventing layer (C). When the amount is less than 10% by mass of the perovskite oxide, the bypass ability for transferring oxygen ions to the oxygen electrode particles is insufficient, and when it exceeds 30% by mass, the oxygen electrode performance tends to be lowered.
The thickness of the first layer oxygen electrode (A1) is preferably 3 to 20 μm, particularly preferably 5 to 10 μm, from the viewpoint of current collection and ion conductivity.
The thickness of the second layer oxygen electrode (A2) is preferably 35 to 85 μm.
Thereby, high power generation performance can be obtained in the initial stage. In particular, when the thickness is 40 to 60 μm, high power generation performance can be maintained.
The ratio (A1 / A2) of the porosity of the first layer oxygen electrode (A1) to the porosity of the second layer oxygen electrode (A2) is preferably 0.5 or less. Thereby, it becomes easy to supply oxygen which is one of the fuels to the electrochemical reaction field. When the porosity ratio exceeds 0.5, oxygen as one of the fuel is hardly supplied to the electrochemical reaction field, and the resistance component of the cell is increased. In particular, when the porosity ratio (A1 / A2) is in the range of 0.01 to 0.3, oxygen is smoothly supplied to the electrochemical reaction field.

The interconnector 35 provided on the conductive support substrate 31 at the position facing the oxygen side electrode 34 is made of conductive ceramics, but is in contact with the fuel gas (hydrogen) and the oxygen-containing gas. It must have reducibility and oxidation resistance. For this reason, lanthanum chromite perovskite oxides (LaCrO ₃ oxides) are generally used as the conductive ceramics. Further, in order to prevent leakage of the fuel gas passing through the inside of the conductive support substrate 31 and the oxygen-containing gas passing through the outside of the conductive support substrate 31, such conductive ceramics must be dense, for example, 93% or more In particular, it is preferable to have a relative density of 95% or more.
The thickness of the interconnector 35 is preferably 10 to 200 μm from the viewpoint of preventing gas leakage and electric resistance. That is, if the thickness is smaller than this range, gas leakage is likely to occur, and if the thickness is larger than this range, the electric resistance is large, and the current collecting function may be reduced due to a potential drop. .

A P-type semiconductor 39 is preferably provided on the outer surface (upper surface) of the interconnector 35. That is, in the cell stack assembled from this fuel cell, a conductive current collecting member is connected to the interconnector 35. However, if the current collecting member is directly connected to the interconnector 35, the potential drops due to non-ohmic contact. Becomes larger, and the current collecting performance decreases.
However, by connecting the current collecting member to the interconnector 35 via the P-type semiconductor 39, the contact between the two becomes an ohmic contact, the potential drop can be reduced, and the deterioration of the current collecting performance can be effectively avoided. It becomes.
As such a P-type semiconductor, a transition metal perovskite oxide can be exemplified. Specifically, those having higher electronic conductivity than LaCrO ₃ oxides constituting the interconnector 35, for example, LaMnO ₃ oxides and LaFeO ₃ oxides in which Mn, Fe, Co, etc. exist at the B site P-type semiconductor ceramics made of at least one of LaCoO ₃ -based oxides can be used. In general, the thickness of the P-type semiconductor 39 is preferably in the range of 30 to 100 μm.
The interconnector 35 can also be provided directly on the flat portion of the conductive support substrate 33 on the side where the solid electrolyte 33 is not provided, but a bonding layer 36 having a composition similar to that of the fuel electrode 32 is also provided on this portion. It is also possible to provide the interconnector 35 on the bonding layer 36. That is, the fuel electrode 32 can be provided over the entire circumference of the conductive support substrate 31, and the interconnector 35 can be provided on the fuel electrode 32. That is, when the interconnector 35 is provided on the conductive support substrate 31 via the fuel electrode 32 and the bonding layer 36, the potential drop at the interface between the conductive support substrate 31 and the interconnector 35 is suppressed. Is advantageous.

The method for producing the fuel cell according to the first aspect of the present invention will be described.
First, a slurry is prepared by mixing an iron group metal such as Ni or its oxide powder, a rare earth oxide powder such as Y ₂ O ₃ , an organic binder, and a solvent, and extrusion molding is performed using this slurry. Thus, a conductive support substrate molded body is prepared and dried. In addition, you may use the calcined body which calcined the conductive support substrate molded object at 900-1000 degreeC as a conductive support substrate molded object.
Next, for example, NiO and YSZ raw materials are weighed and mixed according to a predetermined preparation composition. Thereafter, an organic binder and a solvent are mixed with the mixed powder to prepare a fuel electrode slurry.

Further, a slurry obtained by adding toluene, a binder, and a commercially available dispersant to a ZrO ₂ powder in which a rare earth element is solid-solubilized is formed into a sheet shape by, for example, forming a thickness of 10 to 50 μm by a method such as a doctor blade. A solid electrolyte molded body is prepared. The slurry for fuel electrode is applied on the obtained sheet-shaped solid electrolyte molded body, and is laminated on the conductive support substrate molded body. The fuel electrode slurry may be applied to a predetermined position of the conductive support substrate molded body and dried, and the solid electrolyte molded body to which the fuel electrode slurry is applied may be laminated on the conductive support substrate molded body.
Further, for example, CeO ₂ powder in which Sm ₂ O ₃ is dissolved is heat-treated at 800 to 900 ° C. for 2 to 6 hours, and then wet pulverized to adjust the aggregation degree to 5 to 35. In particular, it is desirable to adjust the aggregation degree to 5 to 15 in that the power generation performance can be prevented from being lowered. Wet crushing was performed by ball milling for 10 to 20 hours.
After adjusting the degree of aggregation, toluene was added as a solvent to prepare a slurry for the reaction preventing layer, and this slurry was applied on the solid electrolyte molded body to form a coating film for the reaction preventing layer. In addition, a sheet-like reaction prevention layer molded body may be produced and laminated on the solid electrolyte molded body.
In addition, an interconnector material (for example, LaCrO ₃ -based oxide powder), an organic binder and a solvent are mixed to prepare a slurry, and an interconnector sheet is prepared and laminated on the exposed surface of the conductive support substrate molded body. .

Next, the above-mentioned laminated molded body was subjected to binder removal treatment and co-fired at 1400 to 1600 ° C. in an oxygen-containing atmosphere. In addition, a slurry containing the powder for oxygen electrode (for example, LaFeO ₃ oxide powder), the above-mentioned powder for reaction preventing layer having a coagulation degree and a solvent is applied on the reaction preventing layer by dipping or the like, and dried To do.
Next, a slurry containing an oxygen electrode powder (for example, LaFeO ₃ oxide powder), a solvent, and a pore increasing agent is applied onto the first layer oxygen electrode by dipping or the like.
If necessary, a slurry containing a P-type semiconductor layer material (for example, LaFeO ₃ -based oxide powder) and a solvent is applied to a predetermined position of the obtained sintered body by dipping or the like, and baked at 1000 to 1300 ° C. Thus, the fuel cell 30 of the present invention having the structure shown in FIG. 1 is manufactured.
In the fuel cell of the present invention, the first layer oxygen electrode is formed on the reaction prevention layer using the mixed powder of the oxygen electrode powder and the reaction prevention layer powder. The electrode reaction preventing layer powder and the particles in the reaction preventing layer are reliably bonded, and the first oxygen electrode can be firmly baked on the reaction preventing layer.
In the above example, the reaction preventing layer is formed on the surface of the solid electrolyte and the oxygen electrode is formed on the surface. However, when the reaction preventing layer is not formed, that is, the oxygen electrode is directly formed on the surface of the solid electrolyte. Even in this case, the bonding strength of the oxygen electrode to the solid electrolyte can be improved.

The first embodiment of the present invention will be specifically described with reference to the following example.
First, NiO powder having an average particle size of 0.5 μm and Y ₂ O ₃ powder having an average particle size of 0.9 μm are calcined and reduced, and the volume ratio of Ni is 48% by volume and Y ₂ O ₃ is 52% by volume. Thus, the clay prepared with an organic binder and a solvent was molded by an extrusion molding method, dried and degreased to prepare an electrode support substrate molded body.
Next, a slurry in which an Ni powder having an average particle size of 0.5 μm, a ZrO ₂ powder in which a rare earth element is dissolved, an organic binder, and a solvent is mixed is prepared, applied to the electrode support substrate molded body by a screen printing method, and dried. Thus, a coating layer for the fuel electrode layer was formed. Next, a slurry obtained by mixing ZrO ₂ powder in which 8 mol% of scandium is dissolved, an organic binder, and a solvent is used to prepare a sheet for a solid electrolyte layer by a doctor blade method. Affixed to the coating layer for the fuel electrode layer and dried.
Next, the laminated molded body in which the electrode supporting substrate molded body, the coating layer of the fuel electrode layer, and the solid electrolyte molded body were laminated was calcined at 1000 ° C.

Next, a complex oxide containing 85 mol% of CeO ₂ and 15 mol% of Sm ₂ O ₃ (hereinafter referred to as SDC15) was pulverized for 24 hours with a vibration mill, then subjected to calcination at 900 ° C. for 4 hours, and again with a ball mill. Crushing treatment was performed, and the degree of aggregation of powder (pseudospherical particle size calculated from particle size / specific surface area by laser diffraction) was adjusted to 13-16. The slurry for the reaction preventing layer prepared by adding and mixing an acrylic binder and toluene to the powder for the reaction preventing layer is applied to the surface of the obtained solid calcined body by a screen printing method. did.
Also, a slurry in which a LaCrO ₃ oxide, an organic binder, and a solvent were mixed was prepared, and this was laminated on the exposed electrode supporting substrate molded body, and co-fired at a firing temperature of 1485 ° C. in an oxygen-containing atmosphere. .
Next, La _0.6 Sr _0.4 Co _0.8 Fe _0.2 O ₃ powder having an average particle diameter of 0.8 μm and SDC 15 prepared to a degree of aggregation of 13 to 16 were mixed at a ratio shown in Table 1, The obtained slurry was printed on the surface of the reaction preventing layer of the laminate, dried at 130 ° C., and then La _0.6 Sr _0.4 Co _0.8 Fe _0.2 O ₃ powder, isopropyl alcohol, Is spray-coated on the first oxygen electrode layer that has been printed and coated to form an oxygen-side electrode molded body, which is baked at 1050 ° C. to form an oxygen electrode layer. A cell was produced.

The size of the produced fuel cell is 25 mm × 200 mm, the thickness of the electrode support substrate is 3 mm, the open porosity is 35%, the thickness of the fuel electrode layer is 10 μm, the thickness of the solid electrolyte layer is 32 μm, the relative density Was 97%, and the thickness of the reaction preventing layer was 5 μm.
Next, hydrogen gas was allowed to flow inside the fuel cell, and the electrode support substrate and the fuel electrode layer were subjected to reduction treatment at 850 ° C.
A fuel gas was circulated through the fuel gas channel of the obtained fuel cell, an oxygen-containing gas was circulated outside the cell, and the fuel cell was heated to 850 ° C. using an electric furnace, and a power generation test was performed. The power generation characteristics at this time were confirmed. Moreover, it took out from the power generating furnace 500 hours after power generation, and the peeling state from the reaction prevention layer of an oxygen electrode was observed visually. These results are shown in Table 1.

From Table 1, sample No. 1 that does not form the oxygen electrode of the first layer is obtained. In 1, the reaction field for surface diffusion is small, and the power density is low because it relies on the volume diffusion of the second layer. Sample Nos. 2 and 4 that do not contain SDC in the first layer have a low output density because the surface diffusion in the first layer has a small number of reaction fields inside the oxygen electrode and is not fully utilized. Sample No. 1 containing no SDC in the first layer was used. In 1, 2, and 4, a part of the oxygen electrode was peeled off from the reaction preventing layer after 500 hours.
The first layer contains SDC, and oxygen ions supplied by volume diffusion in the second layer and air supplied to the first layer through the gaps in the second layer are used to diffuse oxygen into the reaction field by surface diffusion. Sample No. 5.7.7.8.1.112.14.15.17.18.18.2.21 with a balanced sending mechanism shows high output characteristics. The ratio of LSCF is preferably 1: 9 to 3: 7, and the thickness of the first layer is preferably 5 μm to 20 μm. The composition of the LSCF is not particularly affected as long as it is in a temperature range considering the decomposition of Co during baking.

  The fuel cell of the present invention is used as a fuel cell by storing the stack in a storage container.

The perspective view which shows the fuel cell of the 1st aspect of this invention. The cross-sectional view which shows the site | part engaged in the electric power generation of the fuel cell of the 1st aspect of this invention Cross-sectional view showing a cell stack comprising conventional fuel cells

Explanation of symbols

30: Fuel cell 31: Support substrate 31a: Fuel gas passage 32: Fuel electrode 33: Solid electrolyte 34: Oxygen electrode 34a: First layer oxygen electrode (A1)
34b: Second layer oxygen electrode (A2)
35: interconnector 36: bonding layer 37: reaction preventing layer

Claims (7)

  In the fuel cell in which the oxygen electrode (A) is provided on one side of the solid electrolyte via the reaction preventing layer (C) and the fuel electrode is provided on the other side, the oxygen electrode (A) has a two-layer structure, and the reaction is prevented. Particles (A11) in which the first layer oxygen electrode (A1) adjacent to the layer (C) is denser than the second layer oxygen electrode (A2) and have ion conductivity and electron conductivity. ) And particles (A12) having electron conductivity, and the particles constituting the reaction preventing layer (C) and the first layer oxygen electrode (A1) particles (A11) have the same component. A fuel cell comprising: a second layer oxygen electrode (A2) comprising particles having electron conductivity.   The fuel cell according to claim 1, wherein the oxygen electrode (A2) of the second layer is formed by connecting porous coarse particles in which a large number of conductive ceramic fine particles are aggregated in a three-dimensional network. The composite comprising the particles constituting the reaction preventing layer (C) and the particles (A11) of the oxygen electrode (A1) of the first layer each comprising CeO ₂ and Sm ₂ O ₃ represented by the general formula (1) The fuel cell according to claim 1, wherein the fuel cell is an oxide.
(CeO ₂ ) _1-x (SmO _3/2 ) _x (1)
In the formula (1), x is in the range of 0 <x ≦ 0.3.   The oxygen electrode (A1) of the first layer is composed of 10 to 30% by mass of particles (A11) having ion conductivity and electron conductivity and 70 to 90% by mass of particles (A12) having electron conductivity. The fuel cell according to any one of claims 1 to 3, wherein   The fuel cell according to any one of claims 1 to 4, wherein the thickness of the first layer oxygen electrode (A2) is 3 to 20 µm.   In a fuel cell in which an oxygen electrode (B) is provided on one side of a solid electrolyte and a fuel electrode is provided on the other side, the oxygen electrode (B) has a two-layer structure and is adjacent to the solid electrolyte. Particles (B11) in which the oxygen electrode (B1) of the eye is denser than the oxygen electrode (B2) of the second layer and have ion conductivity and electron conductivity, and particles (B12) having electron conductivity And the second layer oxygen electrode (B2) is made of particles having electron conductivity.   7. A fuel cell comprising the fuel cell according to claim 1 housed in a housing container.

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