JP4412986B2 - Cell stack and fuel cell - Google Patents

Description

  The present invention relates to a cell stack and a fuel cell, and more particularly, to a cell stack and a fuel cell in which fuel cell cells having gas flow paths therein are arranged at predetermined intervals.

  In recent years, various fuel cells in which a stack of fuel cells is accommodated in a housing have been proposed as next-generation energy.

  A fuel cell is configured by sandwiching a solid electrolyte between an air electrode and a fuel electrode, supplying an oxygen-containing gas to the air electrode, and supplying a gas containing hydrogen or a gas capable of changing to hydrogen to the fuel electrode. Thus, a potential difference is generated between both electrodes facing each other with the solid electrolyte interposed therebetween, and power is generated.

  Various combinations of these fuel cells can be considered depending on the electrolyte and form to be used. In most cases, an oxygen-containing gas and a gas containing hydrogen or a gas that can be changed to hydrogen are supplied to the fuel cell to generate electricity. The point is common.

  In addition, since the amount of power generated per fuel cell is small, the fuel cell is configured by electrically connecting a plurality of fuel cells.

  Therefore, in power generation, it is necessary to supply an oxygen-containing gas and a gas containing hydrogen or a gas that can be changed to hydrogen to a plurality of fuel cells. At the same time, in order to improve the power generation amount and the power generation efficiency, the amount of gas supplied to each fuel cell needs to be the same.

FIG. 5 shows a longitudinal section of a conventional fuel cell, and a dense solid electrolyte 7 and a porous fuel electrode are formed on one main surface of a plate-like air electrode 5 having a gas flow path 4 therein. 9 are sequentially laminated, and an interconnector 11 is formed on the other main surface. By flowing air through the gas flow path 4 of the fuel cell and flowing the fuel gas outside the fuel cell, a potential difference is generated between the fuel electrode 9 and the air electrode 5 via the solid electrolyte 7 to generate power. . A fuel cell is configured by housing a plurality of such fuel cells in a housing (see, for example, Patent Document 1).
Japanese Patent Laid-Open No. 5-36417

However, in the fuel cell described in Patent Document 1, the dimensions of the gas flow path 4 formed inside the air electrode 5 are not recognized at all, and even if a certain amount of air is supplied to the air supply source. In some cases, the gas flow paths 4 of the fuel cells do not flow evenly, and an equal amount of gas cannot be supplied to the fuel cells.

  When the amount of gas supplied to each fuel battery cell is not uniform, the power generation amount of each fuel battery cell varies, and there is a problem that the total power generation amount becomes small. In addition, there are problems such as destruction of fuel cells in which proper gas supply is not performed.

  For example, in the case of an air electrode-supported fuel battery cell as in Patent Document 1, if the oxygen-containing gas supplied to the fuel battery cell is smaller than the design gas amount, the air utilization rate increases. If the air utilization rate becomes too large, oxygen in the air is consumed on the gas supply port side of the fuel cell, and oxygen is not supplied to the gas discharge port side of the fuel cell, so that a so-called air-drying phenomenon occurs.

  When this phenomenon occurs, the air electrode is reduced, resulting in a volume change, and stress associated with the volume change of the air electrode is generated at the interface between the electrolyte and the air electrode co-sintered in the atmosphere. There is a risk of destruction. On the contrary, if the oxygen-containing gas is larger than the design gas amount, the heat in the housing is discharged, and the fuel cell does not become self-supporting, resulting in a decrease in power generation performance.

  On the other hand, in the case of a fuel electrode-supported fuel cell, if the gas containing hydrogen supplied to the fuel cell is smaller than the design gas amount, the fuel utilization rate increases. When the fuel utilization rate becomes excessively large, hydrogen, which is a fuel for the fuel cell reaction, is consumed on the gas supply port side of the fuel cell, and no hydrogen is supplied to the gas discharge port side of the fuel cell, so that so-called fuel depletion occurs. A phenomenon occurs.

  When this phenomenon occurs, the reduced fuel electrode is oxidized, and the portion of the fuel electrode to which hydrogen is not supplied becomes an insulator. When the fuel electrode becomes an insulator, the electric resistance of the fuel cell greatly increases, the electric resistance of the stack composed of a plurality of fuel cells increases, the output greatly decreases, and the characteristics of the entire fuel cell Problem arises.

  Conversely, when the amount of hydrogen-containing gas is larger than the designed amount, there is a problem in that the fuel utilization rate decreases, the amount of hydrogen that does not contribute to power generation increases, and power generation efficiency decreases.

  An object of this invention is to provide the cell stack and fuel cell which can fully exhibit electric power generation performance.

  The inventors set the cross-sectional area of the gas flow path of the fuel battery cell and the length of the gas flow path within a predetermined range, so that the gas is uniformly distributed to the gas flow paths of the plurality of fuel battery cells. In addition, the present inventors have found that the gas can be sufficiently supplied to the cell even at a gas source pressure of about 2 kPa supplied for home use.

The cell stack of the present invention, a fuel cell that having a plurality of gas passages inside a cell stack formed by arranging a plurality at a predetermined interval, each of said gas in a plurality of the fuel cells length of the channel L (mm) are the same, the ratio of the length of each said gas passage at a plurality of the fuel cells L and (mm) and the cross-sectional area ^{D (mm 2) (L /} D) is as well as a 2 from 0 to 300, and wherein all of the variation of the cross-sectional area D of the gas flow path at a plurality of the fuel cells is not more than 20%. In such a cell stack, the length L (mm) of each gas flow path in the plurality of fuel cells is the same, and the length L and the cross-sectional area D (mm ² ) of each gas flow path in the plurality of fuel cells. )) (L / D) is 20 to 300 , and variation in the cross-sectional area D of all the gas flow paths in the plurality of fuel cells is within 20% , so that the gas is kept at a constant pressure. When supplied to the gas flow path of the fuel battery cell, the gas flow path of each fuel battery cell flows sufficiently and evenly, and the power generation performance can be sufficiently exhibited.

If the ratio of the length L and cross-sectional area D of the gas channel (L / D) is greater, for example, if when the flow path length L of the gas flow path is too long and the flow path cross-sectional area D is too small, the cell The pressure loss of the gas flow path in the inside increases, and the primary pressure (source pressure, for example, the supply pressure of city gas sent to the home) necessary for introducing gas into the fuel cell is considerable. If it is not high, a situation occurs in which gas cannot be sent to the fuel cell. The flow rate is regulated by variation of the cross-sectional area D of the gas flow path of the fuel cell, is also generated a situation that no longer supply gas to a portion of the fuel cell.

Conversely, if the ratio of the length L and cross-sectional area D of the gas channel (L / D) is small, for example, when or if the cross-sectional area D flow path length L of the gas flow path is too short too large, Since the amount of gas supplied to the gas flow path of each fuel battery cell is not uniform, the above-described situations such as fuel exhaustion and reduced efficiency occur.

In the present invention, the plurality of fuel cells, by the ratio of the length L and cross-sectional area D of each gas flow path (L / D) and 20 to 300, the gas supply pressure is a environment 2kPa However, the gas can be uniformly and sufficiently supplied to the plurality of fuel cells, and the power generation performance can be sufficiently exhibited. Further, since the variation in the cross-sectional area D of all the gas flow paths in the plurality of fuel cells is within 20%, the gas can be supplied uniformly to the gas flow paths formed in each fuel battery cell. Thus, variation in the power generation amount of each fuel battery cell can be suppressed, and a decrease in the power generation amount, a decrease in power generation efficiency, and even the worst-case fuel cell cell destruction can be prevented.

Here, in the cell stack of the present invention, it cross-sectional area D of the gas flow path is in the range of 0.5～7.5Mm ^2, the length L of the gas passage is in the range of 100~300mm It is desirable. Thereby, even when the city gas having a low pressure of 2 kPa or less is used as the reformed gas, the gas can be derived through the gas flow path of the fuel cell without pressurizing the gas.

Furthermore, the cell stack of the present invention is characterized in that fuel gas is supplied to the gas flow path of the fuel cell at a pressure of 2 kPa or less. When supplying city gas or propane gas as fuel gas to the fuel cell, the pressure of such gas is 2 kPa or less. Therefore, even if fuel gas of 2 kPa or less is supplied to the fuel cell, each gas flow path the ratio between the length L and cross-sectional area D of the (L / D) by a 20 to 300, can flow reliably gas channel of the fuel cell.

  The fuel cell of the present invention is characterized in that a plurality of the cell stacks are housed in a housing. Since each fuel cell has a gas flow path that can sufficiently exhibit power generation performance, the fuel cell of the present invention having a plurality of fuel cells has good power generation performance.

  The fuel cell of the present invention is characterized in that gas is supplied from a gas chamber provided in the housing to a gas flow path of a fuel cell of the cell stack. In such a fuel cell, the gas flows sufficiently and evenly from the gas chamber through the gas flow paths of the plurality of fuel cells, so that the power generation performance can be improved.

  Furthermore, the fuel cell of the present invention has a manifold in the housing, a cell stack is provided in the manifold, and gas in the manifold is led out through a gas flow path of the fuel cell. In such a fuel cell, the gas in the manifold flows sufficiently and evenly through the gas flow path of the fuel cell, and the power generation performance can be improved.

  The fuel cell of the present invention is used for distributed power generation. For example, since a fuel cell used for a household fuel cell system having a power generation performance of about 1 kW or a fuel cell system for a store having a power generation performance of 7 kW or less is required to be small and inexpensive, a gas pressurizing device In the present invention, a gas having a pressure of 2 kPa or less can be sufficiently and evenly supplied to the fuel battery cell without providing the gas.

  In the cell stack of the present invention, when gas is supplied to the gas flow path of the fuel cell at a constant pressure, the gas flow of each fuel battery cell flows sufficiently and evenly, and the power generation performance can be sufficiently exhibited.

  In addition, the fuel cell of the present invention includes, for example, a plurality of fuel cells that are erected on the manifold without providing a special gas distribution mechanism due to a gas pressure difference between the gas chamber in the manifold and the gas flow path of the fuel cell. Since the gas can be evenly distributed, it can contribute to high-efficiency power generation of the fuel cell, and is also useful for improving the structural reliability and reducing the cost.

  FIG. 1 shows a fuel cell of the present invention. Reference numeral 31 denotes a housing (housing) having a heat insulating structure. Inside the housing 31, a cell stack 35 in which a plurality of fuel cells 33 are gathered, an oxygen-containing gas supply pipe 39 disposed from above the cell stack 35, and a cell stack 35 are provided. A heat exchange unit 41 is accommodated. In FIG. 1, the oxygen-containing gas supply pipe 39 is indicated by a broken line.

  The housing 31 includes a frame body 31a made of a heat-resistant metal and a heat insulating material 31b provided on the inner surface of the frame body 31a.

  In the cell stack 35, for example, as shown in FIG. 2, a plurality of fuel cells 33 are arranged in two rows, and the electrodes of the two adjacent outermost fuel cell cells 33 are connected by a conductive member 42. Thus, the plurality of fuel cells 33 arranged in two rows are electrically connected in series.

  Specifically, as shown in FIG. 3, the fuel cell includes a plate-shaped porous conductive support (hereinafter referred to as a support substrate) 33 a having a plate-like cross section as a whole. A porous fuel-side electrode 33b is provided so as to cover the flat main surface of the support substrate 33a and the curved side surfaces at both ends, and is dense so as to cover the fuel-side electrode 33b. A solid electrolyte 33c is stacked, and an oxygen-side electrode 33d is sequentially stacked on the solid electrolyte 33c. An intermediate film 33e, an interconnector 33f, and a current collecting film 33g are sequentially laminated on the flat main surface of the other side of the support substrate 33a opposite to the oxygen side electrode 33d.

  The fuel cell has a plate-like cross section and a columnar shape as a whole, and six linear gas flow paths 34 are formed through the support substrate 33a inside thereof in the axial direction. Yes.

  That is, the fuel cell 33 has a cross-sectional shape including an arc-shaped portion B provided at both ends in the width direction and a pair of flat portions A that connect these arc-shaped portions B. It is flat and formed substantially in parallel. One of the flat portions A of these fuel cells 33 is configured by forming a fuel side electrode 33b, a solid electrolyte 33c, and an oxygen side electrode 33d on one main surface of the support substrate 33a, and the other flat portion A. Is configured by forming an intermediate film 33e, an interconnector 33f, and a current collecting film 33g on the other main surface of the support substrate 33a.

  The solid electrolyte 33c extends from one main surface of the support substrate 33a to the other main surface via the side surfaces on both sides, and overlaps the interconnector 33f.

  The portion where the fuel side electrode 33b, the solid electrolyte 33c, and the oxygen side electrode 33d overlap is the power generation unit. This power generation part may be formed up to the arcuate part B. In the fuel cell 33, the power generation part formed in the flat part A is the main power generation part.

  In addition, it is desirable that the arc-shaped portion B has a curved surface in order to relieve the thermal stress generated due to heating and cooling accompanying power generation.

  In addition, it is desirable that the major dimension of the support substrate 33a (the distance between the side surfaces of the support substrate that forms the arc-shaped portion) is 15 to 40 mm, and the minor diameter dimension (the distance between the main surfaces that forms the flat portion) is 2 to 10 mm. The distance between the main surfaces of the support substrate 33a is particularly preferably 8 mm or less, and more preferably 5 mm or less. In addition, although the shape of the support substrate 33a is expressed as a plate shape, it can also be expressed as an elliptical shape or a flat shape by changing the major axis dimension and the minor axis dimension.

  The fuel cell has an oxygen side electrode composed of a dense solid electrolyte and porous conductive ceramics sequentially laminated on the outer surface of a fuel side electrode mainly composed of metal, and a fuel on the opposite side of the oxygen side electrode. An interconnector may be formed on the outer surface of the side electrode, and the fuel side electrode may be used as a support.

  As shown in FIG. 2, a current collecting member 43 made of metal felt and / or a metal plate is interposed between one fuel cell 33 and the other fuel cell 33. A cell stack 35 is configured by electrically connecting the support substrate 33a to the oxygen-side electrode 33d of the other fuel cell 33 via an interconnector 33f and a current collecting member 43 provided on the support substrate 33a. Yes.

  This support substrate 33a is composed mainly of a rare earth element oxide composed of one or more selected from Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm and Pr, and Ni and / or NiO. It is desirable to do.

The intermediate film 33e formed between the support substrate 33a and the interconnector 33f is composed mainly of ZrO ₂ containing Ni and / or NiO and a rare earth element. The Ni conversion amount of the Ni compound in the intermediate film 33e is preferably 35 to 80% by volume, more preferably 50 to 70% by volume, based on the total amount. By setting Ni to 35% by volume or more, the conductive path by Ni is increased, the conductivity of the intermediate film 33e is improved, and the voltage drop is reduced. Moreover, by making Ni 80 volume% or less, the thermal expansion coefficient difference between the support substrate 33a and the interconnector 33f can be made small, and generation | occurrence | production of the crack of both interface can be suppressed.

  In addition, the thickness of the intermediate film 33e is preferably 20 μm or less, and more preferably 10 μm or less from the viewpoint that the potential drop is reduced.

The thermal expansion coefficient of the medium rare earth element or heavy rare earth element oxide is smaller than the thermal expansion coefficient of ZrO ₂ containing Y ₂ O ₃ of the solid electrolyte 33c, and the thermal expansion coefficient of the support substrate 33a as a cermet material with Ni. Can be brought close to the thermal expansion coefficient of the solid electrolyte 33c, and cracking of the solid electrolyte 33c and separation of the solid electrolyte 33c from the fuel side electrode 33b can be suppressed. By using a heavy rare earth element oxide having a small thermal expansion coefficient, the amount of Ni in the support substrate 33a can be increased, and the heavy rare earth element oxide is also used from the viewpoint that the electrical conductivity of the conductive support 33a can be increased. It is desirable.

  The light rare earth elements La, Ce, Pr, and Nd oxides may be medium rare earth elements, heavy rare earth elements as long as the sum of the thermal expansion coefficients of the rare earth element oxides is less than the thermal expansion coefficient of the solid electrolyte 33c. There is no problem even if it is contained in addition to the elements.

  Moreover, the raw material cost can be significantly reduced by using a complex rare earth element oxide containing a plurality of inexpensive rare earth elements in the course of purification. Also in that case, it is desirable that the thermal expansion coefficient of the complex rare earth element oxide is less than the thermal expansion coefficient of the solid electrolyte 33c.

  Further, it is desirable to provide a current collecting film 33g made of a P-type semiconductor, for example, a transition metal perovskite oxide, on the surface of the interconnector 33f. If a current collector 43 made of metal is disposed directly on the surface of the interconnector 33f, the potential drop increases due to non-ohmic contact. In order to make ohmic contact and reduce the potential drop, it is necessary to connect the current collector film 33g made of a P-type semiconductor to the interconnector 33f, and it is desirable to use a transition metal perovskite oxide that is a P-type semiconductor. . The transition metal perovskite oxide is preferably made of at least one of a lanthanum-manganese oxide, a lanthanum-iron oxide, a lanthanum-cobalt oxide, or a composite oxide thereof.

The fuel side electrode 33b provided on the main surface of the support substrate 33a is composed of Ni and ZrO _{2 in} which a rare earth element is dissolved. The thickness of the fuel side electrode 33b is desirably 1 to 30 μm. By setting the thickness of the fuel side electrode 33b to 1 μm or more, a three-layer interface as the fuel side electrode 33b is sufficiently formed. Further, by setting the thickness of the fuel side electrode 33b to 30 μm or less, it is possible to prevent interface peeling due to a difference in thermal expansion from the solid electrolyte 33c.

The solid electrolyte 33c provided on the main surface of the fuel side electrode 33b is made of a dense ceramic made of partially stabilized or stabilized ZrO ₂ containing 3 to 15 mol% of a rare earth element such as Y. As the rare earth element, Y or Yb is desirable because it is inexpensive.

  The thickness of the solid electrolyte 33c is desirably 10 to 100 μm. Gas permeation can be prevented by setting the thickness of the solid electrolyte 33c to 10 μm or more. Moreover, the increase in a resistance component can be suppressed by making the thickness of the solid electrolyte 33c into 100 micrometers or less.

The oxygen side electrode 33d is made of a lanthanum-manganese oxide, lanthanum-iron oxide, lanthanum-cobalt oxide of a transition metal perovskite oxide, or at least one porous oxide of a composite oxide thereof. It is composed of conductive ceramics. The oxygen side electrode 33d is preferably a (La, Sr) (Fe, Co) O ₃ system in terms of high electrical conductivity in the middle temperature range of about 800 ° C. The thickness of the oxygen-side electrode 33d is desirably 30 to 100 μm from the viewpoint of current collection.

  The interconnector 33f is a dense body for preventing leakage of fuel gas and oxygen-containing gas inside and outside the support substrate 33a, and the inner and outer surfaces of the interconnector 33f are in contact with the fuel gas and oxygen-containing gas. It has reduction resistance and oxidation resistance.

  The thickness of the interconnector 33f is desirably 30 to 200 μm. By setting the thickness of the interconnector 33f to 30 μm or more, gas permeation can be completely prevented, and by setting it to 200 μm or less, an increase in resistance component can be suppressed.

Between the end of the interconnector 33f and the end of the solid electrolyte 33c, for example, a bonding layer made of Ni and ZrO _{2 in} which Y ₂ O ₃ is dissolved is interposed in order to improve the sealing performance. Also good.

 As shown in FIG. 1, the lower ends of the plurality of fuel cells 33 are supported and fixed to the top plate 50 a of the fuel gas manifold 50. The fuel gas manifold 50 is provided with a fuel gas supply pipe 51 for supplying fuel gas into the fuel cell 33. The top plate 50a of the fuel gas manifold 50 is provided with cell insertion holes arranged in a line at a predetermined interval, and the fuel cell 33 is inserted and fixed in the cell insertion hole. Between the inner surface of the cell insertion hole of the top plate 50a and the outer surface of the fuel cell 33, a sealing agent such as glass is interposed and joined.

  The fuel gas supply pipe 51 passes through the inside of the housing and is connected to a side surface of the fuel gas manifold 50 via a fuel reformer 55 disposed above the cell stack 35. A gas to be reformed such as city gas or propane gas is supplied to the fuel gas supply pipe 51 at 2 kPa or less. Therefore, the gas to be reformed is also supplied into the fuel gas manifold 50 and the gas flow path 34 of the fuel cell 33. The reformed fuel gas is supplied at a pressure of 2 kPa or less.

  The oxygen-containing gas supply pipe 39 extends between the cell stacks 35 to the vicinity of the top plate 50a, and supplies an oxygen-containing gas, for example, air from the tip thereof. Excess oxygen-containing gas that has not been used in power generation flows between the cells 33 and flows upward, and is mixed and burned in the vicinity of the cell tip with fuel gas that has passed through the inside of the cells and was not used for power generation. The fuel reformer 55 is exposed to fuel gas.

  The heat exchanging section 41 includes a discharge path 41a through which combustion gas is discharged and an oxygen-containing gas chamber 41b disposed inside the discharge path 41a. In other words, the oxygen-containing gas chamber 41b. A discharge passage 41a is disposed around the gas passage, and heat exchange is possible between the combustion gas in the discharge passage 41a and the oxygen-containing gas introduced from the outside.

In the fuel cell of the present invention, in order to uniformly supply the fuel gas to the fuel cell 33 standing on the fuel gas manifold 50, the flow length L of each gas flow channel 34 in each fuel cell 33 . are the same, the length L of each gas flow passage 34, with the ratio of the cross-sectional area D in the direction orthogonal to the Re gas flow direction (L / D) is 20 to 300, a plurality of fuel cells 33 The variation in the cross-sectional area D of all the gas flow paths 34 in FIG. By having such a relationship, the fuel gas supplied to the gas chamber in the fuel gas manifold 50 at a constant pressure sufficiently and evenly flows in the gas flow path 34 of the fuel cell 33, and the power generation performance is sufficiently increased. Can demonstrate.

On the other hand, when L / D is less than 20, the fuel gas supplied into the gas manifold 50 easily passes through, and the pressure in the fuel gas manifold 50 cannot be obtained sufficiently, so that some fuel cells. In the cell 33, the gas supply amount is insufficient, and the gas cannot be supplied uniformly to each fuel cell 33. Further, when L / D exceeds 300, the influence of the variation in the cross-sectional area D of the gas flow path 34 becomes relatively large, and fuel gas is not sufficiently supplied in part, so that fuel withering easily occurs.

The ratio (L / D) between the channel length L and the cross-sectional area D of each gas channel 34 of the fuel battery cell 33 is 40 or more, particularly 60 or more, from the viewpoint of ensuring the distribution pressure of the fuel gas. In view of uniform distribution of the fuel gas, it is desirable that it is 200 or less, particularly 150 or less. A fuel battery cell having such an L / D ratio can be achieved, for example, by controlling the dimensions of the through holes and the length of the support substrate molded body when the support substrate 33a is produced by extrusion molding.

In the fuel cell of the present invention, the cross-sectional area D of each gas flow path 34 of the support substrate 33a is in the range of 0.5 to 7.5 mm ² , and the flow path length L of the gas flow path 34 is 100. It is set within a range of ˜300 mm. By setting it within this range, gas can pass through the gas flow path 34 of the fuel battery cell 33 without being pressurized even when a city gas having a low pressure is used as the reformed gas. In particular , the sectional area D is preferably 1.5 to 3.5 mm ² and the flow path length L is preferably 120 to 250 mm from the viewpoint of uniform distribution of fuel gas.

In the fuel battery cell of the present invention, the variation in the cross-sectional area D of the gas flow paths 34 formed in the fuel battery cells 33 and the gas flow paths 34 of each fuel battery cell 33 is set to be within 20%. In other words, the variation in the cross-sectional area D of all the gas flow paths 34 in the plurality of fuel cells 33 constituting the cell stack of the present invention is set to be within 20%. Since the length L of the gas flow path 34 of each fuel cell is regulated by the length of the support substrate 33, the length L of the gas flow path 34 can be controlled to be substantially constant, but the cross-sectional area D of the gas flow path 34 is extruded as described above. Although it is sometimes determined and variation is likely to occur, by making this variation within 20%, the amount of gas passing through each gas flow path 34 of the fuel cell 33 can be made uniform, and each fuel cell The amount of gas flowing through 33 can be made uniform. The variation in the cross-sectional area D of the gas flow path 34 is particularly preferably 10% or less, and more preferably 5% or less.

  The manufacturing method of the fuel cell 33 as described above will be described. First, a rare earth element oxide powder excluding La, Ce, Pr, and Nd elements and Ni and / or NiO powder are mixed, and a support substrate material in which an organic binder and a solvent are mixed is extruded into the mixed powder. Then, a plate-like support substrate molded body is prepared, and this is dried and degreased. As for the drying conditions, it is desirable that the drying is performed at room temperature for 3 days and then in the temperature range of 80 ° C to 150 ° C for 2 hours or more. Furthermore, after drying, calcination is performed in a temperature range of 800 to 1100 ° C.

In the support substrate molded body, the cross-sectional area of the through holes and the length of the support substrate molded body are set so that the dimensional ratio L / D of each gas flow path of the manufactured fuel battery cell satisfies a predetermined value.

Next, a slurry to be a fuel-side electrode molded body prepared by mixing Ni and / or NiO powder, a ZrO ₂ powder in which a rare earth element is dissolved, an organic binder, and a solvent is prepared.

  Next, the slurry used as a fuel side electrode is apply | coated to the one side main surface of the said support substrate molded object using a mesh platemaking, and it dries at the temperature of 80-150 degreeC.

Next, a sheet-like solid electrolyte molded body is prepared using a solid electrolyte material in which a rare earth element is solid-solved ZrO ₂ powder, an organic binder, and a solvent. Next, a slurry to be the fuel side electrode is applied to one side of the solid electrolyte molded body, and the solid electrolyte molded body is applied to the coating film to be the fuel side electrode formed on the one main surface of the support substrate molded body. Wrapped so that the coating film serving as the fuel-side electrode contacts and the both end surfaces of the solid electrolyte molded body are spaced apart from each other at a predetermined interval on the other main surface, and dried at a temperature of 80 to 150 ° C. To do.

  Next, a sheet-like interconnector molded body is prepared using an interconnector material in which a lanthanum-chromium oxide powder, an organic binder, and a solvent are mixed.

Next, a slurry to be an intermediate film molded body in which Ni and / or NiO powder, ZrO ₂ powder in which a rare earth element is solid-solved, an organic binder, and a solvent is mixed is prepared and applied to one surface of the interconnector molded body. .

  Next, the sheet-like interconnector molded body is laminated so that the surface on which the slurry is applied comes into contact with the exposed support substrate molded body.

  Thereby, while laminating the fuel side electrode molded body and the solid electrolyte molded body sequentially on the one side main surface of the support substrate molded body, the intermediate film molded body and the interconnector molded body are laminated on the other side main surface. Create a body. In addition, each molded object can be produced by sheet | seat shaping | molding by a doctor blade, printing, slurry dip, spraying by spraying, etc., or may be produced by a combination thereof.

  Next, the multilayer molded body is degreased and cofired at 1300 to 1600 ° C. in an oxygen-containing atmosphere.

  Next, a transition metal perovskite oxide powder, which is a P-type semiconductor, and a solvent are mixed to prepare a paste. The laminate is immersed in the paste, and oxygen is deposited on the surfaces of the solid electrolyte 33b and the interconnector 33f. The fuel cell 33 of the present invention can be produced by forming the side electrode molded body and the current collector film molded body by dipping, or by direct spray coating and baking at 1000 to 1300 ° C.

  In addition, since the Ni component in the support substrate 33a, the fuel-side electrode 33b, and the intermediate film 33e is NiO by firing in the oxygen-containing atmosphere, the fuel battery cell 33 is subsequently reduced from the support substrate 33a side. Then, NiO is reduced at 800 to 1000 ° C. Further, this reduction process may be performed during power generation.

  In the fuel cell of the present invention, an oxygen-containing gas composed of air is temporarily stored in the oxygen-containing gas chamber 41b and supplied between the fuel cells 33 from the oxygen-containing gas chamber 41b via the oxygen-containing gas supply pipe 39. The reformed gas such as city gas is supplied to the fuel gas supply pipe 51 and the reformer 55, flows through the gas flow path 34 of the fuel battery cell 33 via the fuel gas manifold 50, and is led out from the cell tip. Combustion with external oxygen-containing gas is performed, and the combustion gas is discharged to the outside through the discharge path 41a.

  In addition, this invention is not limited to the said form, A various change is possible in the range which does not change the summary of invention. For example, the inner electrode may be formed from an oxygen side electrode.

First, NiO powder is mixed to 48 volume% in terms of Ni metal, and Y ₂ O ₃ powder is mixed to 52 volume%, and this mixture is mixed with a pore agent, an organic binder composed of a cellulose-based binder, and a solvent composed of water. Then, the mixed support substrate material was extrusion-molded to produce 50 support substrate molded bodies (6 through-holes) having different cross-sectional areas and lengths of circular through-holes under each condition. These support substrate molded bodies were dried and calcined at 1000 ° C.

Next, an acrylic binder and toluene are added to 8YSZ powder (ZrO ₂ containing 8 mol of Y ₂ O ₃ ) to produce a slurry that becomes a solid electrolyte molded body, and a sheet-shaped solid electrolyte molded body is obtained by a doctor blade method. Was made.

Next, 48% by volume of NiO powder in terms of metallic Ni and 8YSZ powder (ZrO ₂ containing 8 mol of Y ₂ O ₃ ) are mixed to 52% by volume, an acrylic binder and toluene are added, and fuel is added. The slurry used as the side electrode molded object was produced.

  The slurry to be the fuel-side electrode molded body was applied to the surface of one side main surface of the support substrate molded body using a mesh plate and dried at a temperature of 130 ° C.

  Moreover, the slurry used as the said fuel side electrode molded object was screen-printed on the said solid electrolyte molded object, and it dried at the temperature of 130 degreeC.

  Next, the coating film to be the fuel-side electrode of the solid electrolyte molded body comes into contact with the coating film of the fuel-side electrode molded body formed on the support substrate molded body, and a gap between both ends of the coating film on the other side main surface is a predetermined interval. Then, it was wound so as to be separated and dried.

  Next, a sheet-like interconnector molded body was prepared using an interconnector material in which a lanthanum-chromium oxide powder, an organic binder, and a solvent were mixed.

Next, a slurry to be an intermediate film molded body in which Ni and / or NiO powder, ZrO ₂ powder in which a rare earth element is solid-solved, an organic binder, and a solvent was mixed was prepared and applied to one surface of the interconnector molded body. .

  Next, the sheet-like interconnector molded body is laminated so that the surface on which the slurry is applied is in contact with the exposed support substrate molded body, and this laminated body is debindered and co-fired at 1500 ° C. in the atmosphere. did.

Next, an oxygen-side electrode slurry is prepared from La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O ₃ powder and a solvent composed of normal paraffin, and this slurry is sprayed on the solid electrolyte, An electrode molded body was formed, and the slurry was applied to the outer surface of the interconnector 33f and baked at 1150 ° C. to form a current collecting film 33g. Thus, the fuel battery cell 33 of the present invention as shown in FIG. 1 was produced. .

 The thickness of the support substrate 33a is 3.2 mm, the width is 26 mm, the thickness of the solid electrolyte 33c is 40 μm, the thickness of the oxygen side electrode 33d is 50 μm, the thickness of the fuel side electrode 33b is 10 μm, the thickness of the interconnector 33f is 50 μm, and the current collecting film The thickness of 33 g was 50 μm. Further, 15 mm non-power generation portions were formed at both ends of each fuel cell 33.

  Eleven types of cell stacks were prepared by sealing and fixing 50 fuel cells prepared under each condition to a fuel gas manifold using glass as a sealant.

Further, the length (gas flow path length) L of 50 fuel cells in each stack and the diameter of the gas flow path having a circular cross section are measured in advance, and the cross sectional area D is obtained from the average value of the diameters. The / D ratio was calculated and listed in Table 1. Further, the variation of the cross-sectional area D is obtained from a calculation formula of (D2-D1) / D1 × 100, where D1 is the minimum value of the cross-sectional area of all the gas flow paths of 50 cells, and D2 is the maximum value. It was described in.

  Next, hydrogen gas was allowed to flow inside the fuel battery cell 33, and reduction treatment of the support substrate 33a and the fuel side electrode 33b was performed at 850 ° C.

Hydrogen was circulated through the gas flow path 34 of the obtained fuel battery cell 33, air was circulated outside the fuel battery cell 33, heated to 850 ° C., power generation characteristics were obtained, and listed in Table 1.

  From Table 1, the sample No. of the comparative example having an L / D ratio of less than 20 is shown. In 1, the power generation performance of the cell was deteriorated compared to other samples. When the stack after the power generation test was observed, current flow occurred in a state where the fuel gas was insufficient, so that many cells with fuel depletion that oxidized the cells occurred mainly on the gas supply port side of the gas manifold. . It is considered that the power generation performance deteriorates due to the support substrate becoming an insulator due to the oxidation of the cell. This sample No. As in 1, when the L / D ratio is too small, the pressure loss of the cell becomes small and the cell loses the function of distributing the gas uniformly. For this reason, the amount of gas distributed to the cells greatly depends on the gas flow velocity distribution flowing in the manifold and the resulting gas pressure distribution in the manifold. It is thought that it occurred.

 On the other hand, the comparative sample No. 11, the pressure path loss in the cell becomes large, and the gas flow rate is largely governed by the variation in the cross-sectional area D of the gas flow path, so that gas is not supplied to some cells, and there is a sign of fuel deficiency. It was.

 On the other hand, the sample of the present invention having an L / D ratio of 20 to 300 was able to generate power without abnormality and had good power generation performance.

It is explanatory drawing which shows the fuel cell of this invention. It is a cross-sectional view showing the cell stack of FIG. It is a cross-sectional perspective view of a fuel battery cell. It is a longitudinal cross-sectional view of a fuel cell. It is a longitudinal cross-sectional view of the conventional fuel cell.

Explanation of symbols

31 ... Housing 33 ... Fuel cell 33a ... Support substrate 33b ... Fuel side electrode (inner electrode)
33c: Solid electrolyte 33d: Oxygen side electrode (outer electrode)
34 ... gas passages 35 ... cell stack 50 ... manifold L ... length of the gas flow path

Claims (8)

The fuel cell that having a plurality of gas passages inside a cell stack formed by arranging a plurality at a predetermined interval, the length of each said gas passage at a plurality of the fuel cells L ( mm) are identical, with the ratio of the length of each said gas passage at a plurality of the fuel cells L and (mm) and the cross-sectional area ^{D (mm 2) (L /} D) is 2 from 0 to 300 The cell stack is characterized in that variation in the cross-sectional area D of all the gas flow paths in the plurality of fuel cells is within 20% . Claim 1 Symbol placement cell stack, wherein the cross-sectional area D of the gas flow path of the fuel cell is in the range of 0.5~7.5mm ^2. Cell stack according to claim 1 or 2 length L of the gas flow path of the fuel cell is being in the range of 100 to 300 mm. Cell stack according to any one of claims 1 to 3 gas at a pressure of less than 2kPa to the gas flow path of the fuel cell is characterized in that it is supplied. Fuel cell characterized by being accommodated in a housing of the cell stack according to any one of claims 1 to 4. The fuel cell according to claim 5, wherein the gas chamber provided in the housing, the gas is supplied to the gas channel of the fuel cell. Has a manifold in said housing, said cell stack provided in said manifold, according to claim 5 or 6, wherein the gas in said manifold, characterized in that it is derived through the gas flow path of the fuel cell Fuel cell. The fuel cell according to any one of claims 5 to 7, characterized in that used for the distributed generation.

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