The present invention relates to a flat plate type fuel cell (hereinafter referred to as a “planar fuel cell apparatus”) which includes a single fuel cell having an anode layer, a cathode layer, and a solid electrolyte layer sandwiched therebetween.
A conventionally known fuel cell apparatus is, for example, a solid oxide fuel cell (hereinafter, may be referred to as SOFC) apparatus which uses solid electrolyte (solid oxide).
The SOFC apparatus uses, for example, a planar single fuel cell having an anode layer provided on one side of a solid electrolyte layer and in contact with fuel gas, and a cathode layer provided on the other side of the solid electrolyte layer and in contact with oxidizer gas (e.g., air).
A fuel gas chamber into which fuel gas is introduced is provided on an anode layer side of the single fuel cell, and an oxidizer gas chamber into which oxidizer gas is introduced is provided on a cathode layer side of the single fuel cell. The single fuel cell, the fuel gas chamber, the oxidizer gas chamber, etc., constitute an electricity generation unit, which is a unit of electricity generation.
Further, in order to obtain an intended voltage, there has been developed a fuel cell stack in which a plurality of single fuel cells (accordingly, electricity generation units) are stacked with interconnectors intervening therebetween (i.e., a fuel cell stack composed of a plurality of tiers).
Also, in recent years, in order to improve the output voltage of the fuel cell apparatus, there has been disclosed a fuel cell stack which combines tiers (electricity generation units) different in terms of fuel gas flow channels for uniformizing the in-plane temperature distribution of the single fuel cells (cell in-plane temperature distribution) (see Patent Document 1).
Further, there has been disclosed a technique for improving (uniformizing) the cell in-plane temperature distribution by alternating, tier by tier, flow directions of fuel gas and oxidizer gas flowing through respective flow channels (see Patent Document 2).
The techniques described in Patent Documents 1 and 2 attempt to uniformize cell in-plane temperature distribution by changing gas flow directions tier by tier (electricity generation unit by electricity generation unit) in the fuel cell stacks; however, their attempts have not always resulted in sufficient achievement.
For example, as exemplified in
Specifically, the technique of merely reversing the direction of fuel gas in different tiers as described in Patent Document 1 and the technique of alternating the directions of fuel gas and oxidizer gas tier by tier as described in Patent Document 2 have encountered difficulty in sufficiently uniformizing cell in-plane temperature distribution.
In the case of a failure to sufficiently uniformize cell in-plane temperature, even though the output voltage is high in an early stage of use after manufacture, performance has been apt to deteriorate as a result of use over a long period of time. This is for the following reason: thermal stress causes the occurrence of cracking or deformation in the single fuel cell and its peripheral components, etc., and a high-temperature region or a low-temperature region may fall outside optimum temperature ranges for the single fuel cell and components.
Also, in the case where cell in-plane temperature is not sufficiently uniformized, a high output voltage has not been obtained in some cases.
The present invention has been conceived in view of the above problem, and an object of the invention is to provide a planar fuel cell apparatus capable of uniformizing the planar temperature of the single fuel cell (i.e., cell in-plane temperature).
(1) A planar fuel cell apparatus of a first mode of the present invention comprises a single fuel cell having an anode layer, a cathode layer, and a solid electrolyte layer sandwiched therebetween; a fuel gas chamber disposed on an anode layer side; an oxidizer gas chamber disposed on a cathode layer side; one or a plurality of fuel gas inlets through which fuel gas flows into the fuel gas chamber, and one or a plurality of fuel gas outlets through which the fuel gas flows out from the fuel gas chamber; and one or a plurality of oxidizer gas inlets through which oxidizer gas flows into the oxidizer gas chamber, and one or a plurality of oxidizer gas outlets through which the oxidizer gas flows out from the oxidizer gas chamber. The planar fuel cell apparatus is characterized in that, as viewed in a stacking direction, a first rectilinear line which connects a centroid Cfi of the fuel gas inlet(s) and a centroid Cfo of the fuel gas outlet(s), and a second rectilinear line which connects a centroid Cai of the oxidizer gas inlet(s) and a centroid Cao of the oxidizer gas outlet(s) cross each other, and the centroid Cfo of the fuel gas outlet(s) is located closer to the centroid Cai of the oxidizer gas inlet(s) than to the centroid Cao of the oxidizer gas outlet(s).
The planar fuel cell apparatus of the first mode is such that, as viewed in the stacking direction, the first rectilinear line which connects the centroid Cfi of the fuel gas inlet(s) and the centroid Cfo of the fuel gas outlet(s), and the second rectilinear line which connects the centroid Cai of the oxidizer gas inlet(s) and the centroid Cao of the oxidizer gas outlet(s) cross each other. That is, the planar fuel cell apparatus employs so-called cross-flow design in which a fuel gas flow channel and an oxidizer gas flow channel cross each other.
In the planar fuel cell apparatus of cross-flow design, for example, as exemplified in
By virtue of such disposition of the centroid Cfo of the fuel gas outlet(s), as viewed in the stacking direction, a region to which fuel gas having high temperature as a result of reaction (electricity generation) is supplied, and a region to which low-temperature oxidizer gas introduced into the oxidizer gas chamber from outside is supplied become close to each other (e.g., overlap each other); therefore, temperature over the surface of the single fuel cell (in-plane temperature, or cell in-plane temperature) is uniformized.
Thus, there is yielded a marked effect that durability of the fuel cell apparatus is improved without involvement of a great deterioration in electricity generation capability (e.g., output voltage) in contrast to conventional practice. That is, since uniformity of cell in-plane temperature distribution is improved, the fuel cell apparatus can attain compatibility between high electricity generation capability (electricity generation capability of such a high level as not to damage electricity generation capability) and high durability.
Also, according to the first mode, since uniformity of temperature distribution can be improved on the single fuel cell basis, the present invention can be applied to not only a fuel cell stack in which a plurality of single fuel cells are stacked but also a single-tier fuel cell apparatus which uses one single fuel cell.
Further, in a fuel cell stack in which the single fuel cells (accordingly, electricity generation units) are stacked, even when thermal conduction is poor between the adjacent single fuel cells (e.g., adjacent upper and lower tiers), high durability can be provided without involvement of the above-mentioned deterioration in electricity generation capability.
Further, since temperature distribution is directly uniformized within a single tier, a greater effect is yielded than in the case of a method of utilizing thermal conduction between adjacent single fuel cells.
The expression “as viewed in the stacking direction” indicates a view in a direction (stacking direction) in which the anode layer, the solid electrolyte layer, and the cathode layer are laminated together. The term “centroid” indicates the center of gravity on a plane. The centroid of a gas inlet or outlet indicates the center of gravity of an opening of the gas inlet or outlet as viewed in a direction in which the planar fuel cell apparatus extends (a planar direction, or a direction perpendicular to the stacking direction). In the case where a plurality of gas inlets (outlets) exist, the center of gravity is of a set of all the gas inlets (or all the gas outlets) on a plane.
(2) In a planar fuel cell apparatus of a second mode of the present invention, as viewed in the stacking direction, the centroid Cfo of the fuel gas outlet(s) is disposed at a position offset from a reference line Lf toward a boundary line Lfp by a distance of 0.3 Xp to Xp; the centroid Cai of the oxidizer gas inlet(s) is disposed at a position located a distance of 0.1 Yp or less from a reference line La toward a boundary line Lap or a distance of 0.1 Ym or less from the reference line La toward a boundary line Lam; and the centroid Cao of the oxidizer gas outlet(s) is disposed at a position located a distance of 0.1 Yp or less from the reference line La toward the boundary line Lap or a distance of 0.1 Ym or less from the reference line La toward the boundary line Lam.
Meanings of Lf, La, Lfp, Lfm, Lap, Lam, Xp, Xm, Yp, and Ym are as follows (the same also applies in the following other modes).
Lf: a rectilinear reference line on the single fuel cell which passes through the centroid Cfi of the fuel gas inlet(s) and through a centroid g of the single fuel cell;
La: a rectilinear reference line on the single fuel cell which is orthogonal to the reference line Lf and passes through the centroid g;
Lfp: a rectilinear boundary line which extends on the single fuel cell, is located closer to the centroid Cai of the oxidizer gas inlet(s) than to the reference line Lf, and is in parallel with and most distant from the reference line Lf;
Lfm: a rectilinear boundary line which extends on the single fuel cell, is located closer to the centroid Cao of the oxidizer gas outlet(s) than to the reference line Lf, and is in parallel with and most distant from the reference line Lf;
Lap: a rectilinear boundary line which extends on the single fuel cell, is located closer to the centroid Cfi of the fuel gas inlet(s) than to the reference line La, and is in parallel with and most distant from the reference line La;
Lam: a rectilinear boundary line which extends on the single fuel cell, is located closer to the centroid Cfo of the fuel gas outlet(s) than to the reference line La, and is in parallel with and most distant from the reference line La;
Xp: the shortest distance between the reference line Lf and the boundary line Lfp;
Xm: the shortest distance between the reference line Lf and the boundary line Lfm;
Yp: the shortest distance between the reference line La and the boundary line Lap; and
Ym: the shortest distance between the reference line La and the boundary line Lam.
In the second mode, the centroid Cfo of the fuel gas outlet(s), the centroid Cai of the oxidizer gas inlet(s), and the centroid Cao of the oxidizer gas outlet(s) are disposed as mentioned above (see, for example,
(3) In a planar fuel cell apparatus of a third mode of the present invention, as viewed in the stacking direction, the centroid Cfo of the fuel gas outlet(s) is disposed at a position located a distance of 0.1 Xp or less from the reference line Lf toward the boundary line Lfp or a distance of 0.1 Xm or less from the reference line Lf toward the boundary line Lfm; the centroid Cai of the oxidizer gas inlet(s) is disposed at a position offset from the reference line La toward the boundary line Lam by a distance of 0.6 Ym to Ym; and the centroid Cao of the oxidizer gas outlet(s) is disposed at a position located a distance of 0.1 Yp or less from the reference line La toward the boundary line Lap or a distance of 0.1 Ym or less from the reference line La toward the boundary line Lam.
In the third mode, the centroid Cfo of the fuel gas outlet(s), the centroid Cai of the oxidizer gas inlet(s), and the centroid Cao of the oxidizer gas outlet(s) are disposed as mentioned above (see, for example,
By virtue of such feature, uniformity of cell in-plane temperature distribution is improved. Thus, the third mode can yield an effect similar to that of the first mode and can attain compatibility between high electricity generation capability (output voltage) and high durability, as is apparent from experimental examples to be described later.
(4) In a planar fuel cell apparatus of a fourth mode of the present invention, as viewed in the stacking direction, the centroid Cfo of the fuel gas outlet(s) is disposed at a position offset from the reference line Lf toward the boundary line Lfp by a distance of 0.3 Xp to Xp; the centroid Cai of the oxidizer gas inlet(s) is disposed at a position offset from the reference line La toward the boundary line Lam by a distance of 0.6 Ym to Ym; and the centroid Cao of the oxidizer gas outlet(s) is disposed at a position located a distance of 0.1 Yp or less from the reference line La toward the boundary line Lap or a distance of 0.1 Ym or less from the reference line La toward the boundary line Lam.
In the fourth mode, the centroid Cfo of the fuel gas outlet(s), the centroid Cai of the oxidizer gas inlet(s), and the centroid Cao of the oxidizer gas outlet(s) are disposed as mentioned above (see, for example,
(5) In a planar fuel cell apparatus of a fifth mode, as viewed in the stacking direction, the centroid Cfo of the fuel gas outlet(s) is disposed at a position offset from the reference line Lf toward the boundary line Lfp by a distance of 0.3 Xp to Xp; the centroid Cai of the oxidizer gas inlet(s) is disposed at a position offset from the reference line La toward the boundary line Lam by a distance of 0.6 Ym to Ym; and the centroid Cao of the oxidizer gas outlet(s) is disposed at a position offset from the reference line La toward the boundary line Lap by a distance of 0.4 Yp to 0.9 Yp.
In the fifth mode, the centroid Cfo of the fuel gas outlet(s), the centroid Cai of the oxidizer gas inlet(s), and the centroid Cao of the oxidizer gas outlet(s) are disposed as mentioned above (see, for example,
By virtue of such feature, uniformity of cell in-plane temperature distribution is more improved. Thus, the fifth mode can yield an effect similar to that of the first mode and can attain compatibility between high electricity generation capability (output voltage) and high durability, as is apparent from experimental examples to be described later.
(6) In a planar fuel cell apparatus of a sixth mode, as viewed in the stacking direction, the centroid Cao of the oxidizer gas outlet(s) is disposed at a position offset from the reference line La toward the boundary line Lap by a distance of 0.4 Yp to 0.6 Yp.
In the sixth mode, the centroid Cao of the oxidizer gas outlet(s) is disposed as mentioned above (see, for example,
(7) A planar fuel cell apparatus of a seventh mode of the present invention comprises a plurality of stacked planar fuel cell units each comprising a single fuel cell having an anode layer, a cathode layer, and a solid electrolyte layer sandwiched therebetween; a fuel gas chamber disposed on an anode layer side; an oxidizer gas chamber disposed on a cathode layer side; one or a plurality of fuel gas inlets through which fuel gas flows into the fuel gas chamber, and one or a plurality of fuel gas outlets through which the fuel gas flows out from the fuel gas chamber; and one or a plurality of oxidizer gas inlets through which oxidizer gas flows into the oxidizer gas chamber, and one or a plurality of oxidizer gas outlets through which the oxidizer gas flows out from the oxidizer gas chamber. At least any one of the planar fuel cell units is the planar fuel cell apparatus according to any one of the first to sixth modes.
The planar fuel cell apparatus of the seventh mode is a planar fuel cell apparatus (e.g., a fuel cell stack) in which a plurality of planar fuel cell units (e.g., electricity generation units) are stacked, and includes any one of the planar fuel cell apparatus of the first to sixth modes; therefore, the planar fuel cell apparatus of the seventh mode can provide high output voltage.
In the case where the planar shape (a shape viewed from the stacking direction) of the fuel cell apparatus is quadrangular, the following configuration can be employed.
A planar fuel cell apparatus comprises a single fuel cell having a planar quadrangular shape and having a first main surface and a second main surface to which sides fuel gas and oxidizer gas are supplied respectively; a fuel gas chamber disposed on a first main surface side; an oxidizer gas chamber disposed on a second main surface side; in plan view (as viewed in a direction perpendicular to the main surfaces), one or a plurality of fuel gas inlets disposed at a position(s) corresponding to one of two mutually facing first sides (e.g., first side H1 and second side H2 in
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A planar fuel cell apparatus to which the present invention is applied will next be described while referring to a solid oxide fuel cell apparatus.
a) First, the schematic structure of a planar fuel cell apparatus of the first embodiment will be described.
As shown in
In the drawings, oxidizer gas is denoted by “A,” and fuel gas is denoted by “F.” Also, “IN” indicates that gas is introduced, and “OUT” indicates that gas is discharged. Further, for convenience of description, directions such as “upper” and “lower” are mentioned on the basis of directions in the drawings, but are not intended to specify the directivity of an actual fuel cell apparatus.
The fuel cell apparatus 1 of the first embodiment is a planar (rectangular parallelepiped) solid oxide fuel cell apparatus and is a fuel cell stack configured such that a plurality of (e.g., 20) tiered (planar) electricity generation units 7 are disposed between end plates 3 and 5 disposed at vertically opposite ends in
The end plates 3 and 5 and the electricity generation units 7 have a plurality of (e.g., eight) bolt insertion holes 9 extending therethrough in a stacking direction (vertical direction in
The end plates 3 and 5 and the electricity generation units 7 are unitarily fixed by bolts 11a, 11b, 11c, 11d, 11e, 11f, 11g, and 11h (collectively referred to as bolts 11) disposed in the bolt insertion holes 9 and nuts 13 threadingly engaged with the respective bolts 11.
Of the bolts 11, the particular (four) bolts 11b, 11d, 11f, and 11h have an inner flow channel 15 formed therein along the axial direction (the vertical direction in
b) Next, the structure of the electricity generation unit 7 will be described in detail.
As shown in
More specifically, the electricity generation unit 7 is configured such that the metal interconnector 21a, a cathode insulating frame 23, a metal separator 25, a metal anode frame 27, an anode insulating frame 29, the metal interconnector 21b, etc., are stacked. The stacked members 21, 23, 24, 27, and 29 have the bolt insertion holes 9 formed therein and allowing insertion of the respective bolts 11.
The single cell 17 is joined to the separator 25; a cathode current collector 33 is disposed in a flow channel (a flow channel in which oxidizer gas flows; i.e., an oxidizer gas chamber) 31 within the cathode insulating frame 23; and an anode current collector 37 is disposed in a flow channel (a flow channel in which fuel gas flows; i.e., fuel gas chamber) 35 within the anode frame 27 and the anode insulating frame 29.
The components will next be described in detail.
<Interconnector 21>
As shown in
A single interconnector 21 suffices for disposition between the adjacent electricity generation units 7. Also, the interconnectors 21 at the upper and lower ends of the fuel cell apparatus 1 are used as the end plates 3 and 5 (see
<Cathode Insulating Frame 23>
The cathode insulating frame 23 is an electrically insulative frame plate having a quadrangular (rectangular) shape as viewed in the stacking direction (as viewed in the vertical direction in
The cathode insulating frame 23 has two hole portions 41d and 41h, or a pair of elongated holes, formed at mutually facing frame portions (portions corresponding to opposite sides of a rectangle) and serving as oxidizer gas flow channels. As will be described in detail later, one hole portion 41d is accompanied by a plurality of (e.g., six) grooves (grooves for oxidizer gas inlets Ain) 43d, which are flow channels communicating with the opening portion 23a, and the other hole portion 41h is accompanied by a plurality of (e.g., six) grooves (grooves for oxidizer gas outlets Aout) 43h, which are flow channels communicating with the opening portion 23a.
<Cathode Current Collector 33>
The cathode current collector 33 is an elongated electrically conductive member (e.g., a column member of stainless steel such as SUS430). A plurality of the cathode current collectors 33 are disposed in the opening portion 23 a of the cathode insulating frame 23 along the direction of disposition of a pair of the bolt insertion holes 9 (9d, 9h); i.e., along a flow channel of oxidizer gas. The cathode current collectors 33 may be embodied in the form of latticed rectangular parallelepiped protrusions formed on the interconnector 21 on a side toward the oxidizer gas chamber 31.
<Separator 25>
The separator 25 is an electrically conductive frame plate (e.g., a plate of stainless steel such as SUS430) having a quadrangular (rectangular) shape as viewed in the stacking direction. The separator 25 has a rectangular opening portion 25a formed at a central portion as viewed in the stacking direction. An outer peripheral portion (its upper surface side) of the single cell 17 is joined by brazing to an edge portion (its lower surface side) of the separator 25 extending along the opening portion 25a. That is, the single cell 17 is joined in such a manner as to close the opening portion 25a of the separator 25.
<Anode Frame 27>
The anode frame 27 is an electrically conductive frame plate (e.g., a plate of stainless steel such as SUS430) having a quadrangular (rectangular) shape as viewed in the stacking direction. The anode frame 27 has a rectangular opening portion 27a formed at a central portion as viewed in the stacking direction and partially constituting the fuel gas chamber 35.
<Anode Insulating Frame 29>
Similar to the cathode insulating frame 23, the anode insulating frame 29 is an electrically insulative frame plate having a quadrangular (rectangular) shape as viewed in the stacking direction and is a mica frame formed of soft mica. The anode insulating frame 29 has a rectangular opening portion 29a formed at a central portion as viewed in the stacking direction and partially constituting the fuel gas chamber 35.
The anode insulating frame 29 has two hole portions 45b and 45f, or a pair of elongated holes, formed at mutually facing frame portions (portions corresponding to opposite sides of a rectangle) and serving as fuel gas flow channels. As will be described in detail later, one hole portion 45b is accompanied by a plurality of (e.g., four) grooves (grooves for fuel gas inlets Fin) 47b, which are flow channels communicating with the opening portion 29a, and the other hole portion 45f is accompanied by a plurality of (e.g., four) grooves (grooves for fuel gas outlets Fout) 47f, which are flow channels communicating with the opening portion 29a.
<Anode Current Collector 37>
As shown in
<Single Fuel Cell 17>
The single cell 17 is a so-called anode support type and is configured such that a cathode layer 57 and an anode layer 59 are laminated together with a solid electrolyte layer 55 sandwiched therebetween. The single cell 17 has a quadrangular (rectangular) shape as viewed in the stacking direction and is supplied with fuel gas on its first main surface side (on the anode layer 59 side) and with oxidizer gas on its second main surface side (on the cathode layer 57 side).
Materials used to form the solid electrolyte layer 55 include, for example, zirconia-based, ceria-based, and perovskite-type electrolyte materials. Zirconia-based materials include yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), and calcia-stabilized zirconia (CaSZ). Generally, yttria-stabilized zirconia (YSZ) is used in many cases. A ceria-based material to be used is so-called rare earth element-added ceria. A perovskite-type material to be used is a lanthanum element-containing perovskite-type compound oxide.
Materials used to form the cathode layer 57 include perovskite-type oxides, noble metals, and cermets of noble metals and ceramic.
Materials used to form the anode layer 59 include, for example, mixtures of metals such as Ni and Fe and ceramics such as ZrO2 ceramics, such as zirconia stabilized by at least one of rare earth elements such as Sc and Y, and CeO ceramics. Also, metals such as Ni, cermets of Ni and the ceramics, and Ni-based alloys can be used.
c) Next, fuel gas and oxidizer gas flow channels, which are essential members of the first embodiment, will be described in detail.
As shown in
Meanwhile, as shown in
As shown in
Further, as viewed in the stacking direction, the centroid Cfo of the fuel gas outlets Fout is located closer to the centroid Cai of the oxidizer gas inlets Ain than to the centroid Cao of the oxidizer gas outlets Aout. This condition is hereinafter called “flow channel disposition condition 1.”
In
The centroid will next be described with reference to
The centroid is the center of gravity of a plane figure of the flow inlet Fin or Ain or the flow outlet Fout or Aout as viewed in a direction perpendicular to the stacking direction (the vertical direction in
Specifically, when, of the inner peripheral surfaces of the anode insulating frame 29, an inner peripheral surface on the side where the fuel gas inlet Fin is provided is viewed in a direction perpendicular to the inner peripheral surface, as shown in
Here, for example, the centroid Cfi of a set of the fuel gas inlets Fin is disposed at the horizontal center of the first surface M1. Accordingly, as viewed in the stacking direction, the centroid Cfi of a set of the fuel gas inlets Fin is located at the midpoint of a first side H1 of the first frame W1 (see
Similarly, when, of the inner peripheral surfaces of the anode insulating frame 29, an inner peripheral surface on the side where the fuel gas outlet Fout is provided is viewed in a direction perpendicular to the inner peripheral surface, as shown in
Here, for example, since the fuel gas outlets Fout are disposed leftward in
Meanwhile, when, of the inner peripheral surfaces of the cathode insulating frame 23, an inner peripheral surface on the side where the the oxidizer gas inlet Ain is provided is viewed in a direction perpendicular to the inner peripheral surface, as shown in
Here, for example, the centroid Cai of a set of the oxidizer gas inlets Ain is the horizontal center of the third surface M3. Accordingly, as viewed in the stacking direction, the centroid Cai of a set of the oxidizer gas inlets Ain is located at the midpoint of a third side H3 of the first frame W1 (see
Similarly, when, of the inner peripheral surfaces of the cathode insulating frame 23, an inner peripheral surface on the side where the the oxidizer gas outlet Aout is provided is viewed in a direction perpendicular to the inner peripheral surface, as shown in
Here, for example, the centroid Cao of a set of the oxidizer gas outlets Aout is located at the horizontal center of the fourth surface M4. Accordingly, as viewed in the stacking direction, the centroid Cao of a set of the oxidizer gas outlets Aout is located at the midpoint of a fourth side H4 of the first frame W1 (see
Notably, the positions of the flow inlets Fin and Ain and the flow outlets Fout and Aout shown in
d) Next, a method of manufacturing the fuel cell apparatus 1 will be described briefly.
[Manufacturing Process For Members]
First, the interconnectors 21, the anode frames 27, the separators 25, and the end plates 3 and 5 were punched out from plate materials of, for example, SUS430.
The cathode insulating frames 23 and the anode insulating frames 29 shown in
[Manufacturing Process For Single Fuel Cell 17]
The single cells 17 were manufactured according to the usual method.
Specifically, first, in order to form the anode layers 59, anode paste was prepared by use of, for example, 40 to 70 parts by mass yttria-stabilized zirconia (YSZ) powder, 40 to 70 parts by mass nickel oxide powder, and binder solution. By use of the anode paste, an anode green sheet was manufactured.
In order to manufacture the solid electrolyte layers 55, solid electrolyte paste was prepared by use of, for example, YSZ powder and binder solution. By use of the solid electrolyte paste, a solid electrolyte green sheet was manufactured.
Next, the solid electrolyte green sheet was laminated on the anode green sheet. The resultant laminate was heated at 1,200° C.-1,500° C. for 1-10 hours, thereby yielding a sintered laminate.
In order to form the cathode layers 57, cathode paste was prepared by use of, for example, La1-xSrxCo1-yFeyO3 powder and binder solution.
Next, the cathode paste was applied by printing to the surface of the solid electrolyte layer 55 of the sintered laminate. Then, the printed cathode paste was fired in such a manner as to avoid becoming dense; specifically, at 900° C.-1,200° C. for 1-5 hours, thereby forming the cathode layers 57.
Thus, the single cells 17 were completed. The separators 25 were fixed by brazing to the single cells 17, respectively.
[Manufacturing Process For Fuel Cell Apparatus 1]
Next, the above-mentioned members were stacked in a desired number of tiers as shown in
The bolts 11 were inserted through the respective bolt insertion holes 9 of the stacked body. The nuts 13 were screwed to the bolts 11 and tightened, thereby unitarily fixing the stacked body through tightening.
Thus, the fuel cell apparatus 1 of the first embodiment was completed.
e) Next, the effect of the first embodiment will be described.
The fuel cell apparatus 1 of the first embodiment employs so-called cross-flow design in which a fuel gas flow channel and an oxidizer gas flow channel cross each other. In the fuel cell apparatus 1 of cross-flow design, as viewed in the stacking direction, the centroid Cfo of the fuel gas outlets Fout is disposed closer to the centroid Cai of the oxidizer gas inlets Ain than to the centroid Cao of the oxidizer gas outlets Aout. That is, the fuel gas flow channel and the oxidizer gas flow channel are disposed in such a manner as to meet the above-mentioned “flow channel disposition condition 1.”
By virtue of such disposition of the centroid Cfo of the fuel gas outlets Fout, as shown in
Thus, there is yielded the following marked effect: as a result of noninvolvement of a great deterioration in output voltage, high output voltage can be secured, and durability of the fuel cell apparatus 1 is improved. That is, since uniformity of temperature distribution can be improved, the fuel cell apparatus 1 can attain compatibility between high output voltage and high durability.
Also, according to the first embodiment, since uniformity of temperature distribution can be improved on the single fuel cell 17 basis, the present invention can be applied to not only a fuel cell stack in which a plurality of the single fuel cells 17 (accordingly, the electricity generation units 7) are stacked but also a single-tier fuel cell apparatus 1 which uses one single fuel cell 17.
Further, in the fuel cell apparatus 1 in which the single fuel cells 17 are stacked (i.e., a fuel cell stack), even when thermal conduction is poor between the adjacent single fuel cells 17 (i.e., the adjacent upper and lower electricity generation units 7), the above-mentioned compatibility between high output voltage and high durability can be attained.
Further, since temperature distribution is directly uniformized within a single tier, a greater effect is yielded than in the case of a method of utilizing thermal conduction between the adjacent single cells 17.
Next, a second embodiment will be described; however, the description of contents similar to those of the first embodiment is omitted. In the following description, structural members similar to those of the first embodiment are denoted by the same reference numerals as those of the first embodiment.
The fuel cell apparatus 1 of the second embodiment meets the following “flow channel disposition condition 2” as well as “flow channel disposition condition 1” of the first embodiment with respect to the oxidizer gas flow channel and the fuel gas flow channel.
Specifically, in the fuel cell apparatus 1 of the second embodiment, as shown in
In the first frame W1 of
By virtue of such a configuration, the second embodiment yields an effect similar to that of the first embodiment. As shown in experimental example 1 to be described later, since the second embodiment meets “flow channel disposition condition 2” to thereby improve uniformity of temperature distribution, the second embodiment can attain compatibility between high electricity generation capability and high durability.
Next, a third embodiment will be described; however, the description of contents similar to those of the first embodiment is omitted. In the following description, structural members similar to those of the first embodiment are denoted by the same reference numerals as those of the first embodiment.
The fuel cell apparatus 1 of the third embodiment meets the following “flow channel disposition condition 3” as well as “flow channel disposition condition 1” of the first embodiment with respect to the oxidizer gas flow channel and the fuel gas flow channel.
Specifically, in the fuel cell apparatus 1 of the third embodiment, as shown in
In the first frame W1 of
By virtue of such a configuration, the third embodiment yields an effect similar to that of the first embodiment. Also, as shown in
Specifically, the oxidizer gas inlets Ain are disposed away from a low-temperature region (e.g., an Xp-Yp region at the upper right of
By virtue of such feature, uniformity of cell in-plane temperature distribution is improved. Thus, as is apparent from experimental example 1 to be described later, the third embodiment can attain compatibility between high electricity generation capability (output voltage) and high durability.
Next, a fourth embodiment will be described; however, the description of contents similar to those of the first embodiment is omitted. In the following description, structural members similar to those of the first embodiment are denoted by the same reference numerals as those of the first embodiment.
The fuel cell apparatus 1 of the fourth embodiment meets the following “flow channel disposition condition 4” as well as “flow channel disposition condition 1” of the first embodiment with respect to the oxidizer gas flow channel and the fuel gas flow channel.
Specifically, in the fuel cell apparatus 1 of the fourth embodiment, as shown in
In the first frame W1 of
By virtue of such a configuration, the fourth embodiment yields an effect similar to that of the first embodiment. Also, as shown in
Next, a fifth embodiment will be described; however, the description of contents similar to those of the first embodiment is omitted. In the following description, structural members similar to those of the first embodiment are denoted by the same reference numerals as those of the first embodiment.
The fuel cell apparatus 1 of the fifth embodiment meets the following “flow channel disposition condition 5” as well as “flow channel disposition condition 1” of the first embodiment with respect to the oxidizer gas flow channel and the fuel gas flow channel.
Specifically, in the fuel cell apparatus 1 of the fifth embodiment, as shown in
In the first frame W1 of
By virtue of such a configuration, the fifth embodiment yields an effect similar to that of the first embodiment. Also, as shown in
Next, a sixth embodiment will be described; however, the description of contents similar to those of the fifth embodiment is omitted. In the following description, structural members similar to those of the fifth embodiment are denoted by the same reference numerals as those of the fifth embodiment.
The fuel cell apparatus 1 of the sixth embodiment meets the following “flow channel disposition condition 6” as well as “flow channel disposition condition 1” of the first embodiment with respect to the oxidizer gas flow channel and the fuel gas flow channel.
Specifically, in the fuel cell apparatus 1 of the sixth embodiment, as shown in
In the first frame W1 of
By virtue of such a configuration, the sixth embodiment yields an effect similar to that of the fifth embodiment, and, as is apparent from experimental example 1 to be described later, the cell in-plane temperature distribution can be uniformized to a higher extent than in the fifth embodiment. Thus, the sixth embodiment can attain compatibility between higher electricity generation capability and higher durability.
Next, a seventh embodiment will be described; however, the description of contents similar to those of the first embodiment is omitted. In the following description, structural members similar to those of the first embodiment are denoted by the same reference numerals as those of the first embodiment.
As shown in
Here, for example, the centroid Cfi of the fuel gas inlets Fin is greatly offset rightward from the midpoint of the first side H1, and the centroid Cfo of the fuel gas outlets Fout is slightly offset rightward from the midpoint of the second side H2. That is, in
Also, the centroid Cai of the oxidizer gas inlets Ain is greatly offset downward (i.e., to a position near an end portion of the single cell 17) from the midpoint of the third side H3, and the centroid Cfo of the oxidizer gas outlets Aout is greatly offset upward (i.e., to a position near an another end portion of the single cell 17) from the midpoint of the fourth side H4.
Even the seventh embodiment having such a configuration yields effects similar to those of the above embodiments by means of meeting “flow channel disposition condition 1” or meeting any one of “flow channel disposition condition 2” to “flow channel disposition condition 6,” in addition to “flow channel disposition condition 1.”
Next, experiments conducted to verify the effects of the present invention will be described.
In experimental example 1, computer simulation was performed on an object model of experiment (experimental model 1) and a model of reference (reference model or reference cell) with respect to a planar solid oxide fuel cell apparatus of a one-tier electricity generation unit type using one single cell.
The operation of experimental model 1 was simulated such that while the position of the centroid Cfi of the fuel gas inlets was fixed, the positions of the centroid Cfo of the fuel gas outlets, the centroid Cai of the oxidizer gas inlets, and the centroid Cao of the oxidizer gas outlets were varied to obtain an output voltage and the temperature distribution (the difference between a maximum temperature (max) and a minimum temperature (min)) of the single cell surface with respect to the individual cases of the positions. Also, the output voltage and the temperature distribution of the reference model were obtained. A change of the output voltage and a change of the temperature distribution of experimental model 1 in relation to the reference model were examined.
As will be described in detail below, experimental example 1 verified effects of the flow channel positions of the second embodiment (see Table 1 and
a) Structure of Experimental Model 1
The basic structure of experimental model 1 is similar to that of the electricity generation unit in each of the above embodiments.
More specifically, in experimental model 1, the planar shapes (as viewed in the stacking direction) of members, such as the electricity generation unit, the single cell, the fuel gas chamber, and the oxidizer gas chamber, were square, and the members had the following sizes. Materials of the members were similar to those of the above embodiments.
Sizes in Plan View
Fuel gas chamber and oxidizer gas chamber: 12 cm×12 cm, single cell: 9 cm×9 cm
Also, in experimental model 1, as shown in the following Tables 1 to 4, the positions of the centroid Cfo of the fuel gas outlets, the centroid Cai of the oxidizer gas inlets, and the centroid Cao of the oxidizer gas outlets were varied. Meanwhile, the position of the centroid Cfi of the fuel gas inlets was the midpoint of the first side H1 of the first frame W1 of experimental model 1 as shown in, for example,
b) Structure of Reference Model
In the reference model, as shown in
c) Operating Conditions of Experimental Model 1 and Reference Model
Experiment model 1 and the reference model were operated as follows: fuel gas (e.g., a mixed gas of hydrogen, nitrogen, and water (water vapor)) and oxidizer gas (e.g., air (a mixed gas of oxygen and nitrogen)) were supplied at a fixed flow rate for a predetermined time at a predetermined electricity generation temperature of the fuel cell apparatus.
d) Contents of Experiments
In experimental example 1, simulation was performed under the above-mentioned operating conditions while the positions of the centroid Cfo of the fuel gas outlets, the centroid Cai of the oxidizer gas inlets, and the centroid Cao of the oxidizer gas outlets were varied as shown in the following Tables 1 to 4, thereby obtaining the output voltage of experimental model 1. Similarly, the reference model underwent simulation under the same experimental conditions to obtain the output voltage thereof.
Then, the amount dVolt [%] of change of output voltage of experimental model 1 in relation to the reference model was calculated. The results of the calculation are shown in the following Tables 1 to 4. In the tables, the sign − (minus) of the amount dVolt of change of output voltage indicates that the output voltage is lower than that of the reference model.
Also, experimental model 1 underwent simulation under operating conditions similar to those of the above case of obtaining the output voltage while the centroid positions were varied similarly to the case, whereby the maximum cell in-plane temperature (max) and the minimum cell in-plane temperature (min) of the single cell were obtained, and temperature difference ΔT (max−min) was calculated. Similarly, the temperature difference ΔT was calculated for the reference model.
Then, the amount dT [° C.] of change of temperature difference ΔT of experimental model 1 in relation to the reference model was calculated. The results of the calculation are shown in the following Tables 1 to 4. In the tables, the sign − (minus) of the amount dT of change of the temperature difference ΔT indicates that the temperature difference ΔT becomes small.
In the following Tables 1 to 4, in the case of use of Xp for expression of the position of the centroid Cfo of the fuel gas outlets, the centroid Cfo is offset from Lf toward Lfp, and, in the case of use of Xm, the centroid Cfo is offset from Lf toward Lfm. In the case of use of 0, the centroid Cfo is positioned on Lf.
In the case of use of Yp for expression of the positions of the centroid Cai of the oxidizer gas inlets and the centroid Cao of the oxidizer gas outlets, the centroid Cai and the centroid Cao are offset from La toward Lap, and, in the case of use of Ym, the centroid Cai and the centroid Cao are offset from La toward Lam. In the case of use of 0, the centroid Cai and the centroid Cao are positioned on La.
e) Results of Experiments
The contents and results of experiments will next be described in detail with reference to the tables.
Table 1 shows the results of an experiment conducted for verifying the flow channel condition of the second embodiment (flow channel condition 2: see
In view of manufacturing variations, the centroid Cai of the oxidizer gas inlets and the centroid Cao of the oxidizer gas outlets were considered to be disposed at any position within a range of 10% of Yp to 10% of Ym from the midpoint of the third side H3 and a range of 10% of YP to 10% of Ym from the midpoint of the fourth side H4, respectively.
The criteria employed in Table 1 are as follows.
<Criteria>
A: A drop in output voltage is 3.5% or less, and a reduction in temperature difference ΔT is 0.5° C. or more.
B: The conditions of the above judgment A are not met.
As is apparent from Table 1, when the position of the centroid Cfo of the fuel gas outlets falls within a range of 0.3 Xp to Xp (see the hatched portion of Table 1), the amount dVolt of change of output voltage of experimental model 1 is small (i.e., a drop in output voltage is 2.05% or less), and the amount dT of change of temperature difference ΔT of experimental model 1 is large (i.e., the temperature difference is improved by 0.5° C. or more to thereby become small). That is, output voltage does not deteriorate much, and the uniformity of temperature distribution is improved.
Table 2 shows the results of an experiment conducted for verifying the flow channel condition of the third embodiment (flow channel disposition condition 3: see
In view of manufacturing variations, the centroid Cfo of the fuel gas outlets and the centroid Cao of the oxidizer gas outlets were considered to be disposed at any position within a range of 10% of Xm to 10% of Xp from the midpoint of the second side H2 and a range of 10% of Yp to 10% of Ym from the midpoint of the fourth side H4, respectively. The criteria employed in Table 2 are as follows.
<Criteria>
A: A drop in output voltage is 3.5% or less, and a reduction in temperature difference ΔT is 0.5° C. or more.
B: The conditions of the above judgment A are not met.
As is apparent from Table 2, when the position of the centroid Cai of the oxidizer gas inlets falls within a range of 0.6 Ym to Ym (see the hatched portion of Table 2), the amount dVolt of change of output voltage of experimental model 1 is small (i.e., a drop in output voltage is 2.41% or less), and the amount dT of change of temperature difference ΔT of experimental model 1 is large (i.e., the temperature difference is improved by 0.6° C. or more to thereby become small). That is, output voltage does not deteriorate much, and the uniformity of temperature distribution is improved.
Table 3 shows the results of an experiment conducted for verifying the flow channel condition of the fourth embodiment (flow channel disposition condition 4: see
In view of manufacturing variations, the centroid Cao of the oxidizer gas outlets was considered to be disposed at any position within a range of 10% of Yp to 10% of Ym from the midpoint of the fourth side H4.
The criteria employed in Table 3 are as follows.
<Criteria>
A: A drop in output voltage is 3.5% or less, and a reduction in temperature difference ΔT is 0.5° C. or more. AA: A drop in output voltage is 3.5% or less, and a reduction in temperature difference ΔT is 2.0° C. or more. As is apparent from Table 3, when the position of the centroid Cfo of the fuel gas outlets falls within a range of 0.3 Xp to Xp (the condition of the centroid Cfo of the fuel gas outlets in flow channel disposition condition 2), and the position of the centroid Cai of the oxidizer gas inlets falls within a range of 0.6 Ym to Ym (the condition of the centroid Cai of the oxidizer gas inlets in flow channel disposition condition 3) (see the hatched portion of Table 3), the amount dVolt of change of output voltage of experimental model 1 is small (i.e., a drop in output voltage is 3.20% or less), and the amount dT of change of temperature difference ΔT of experimental model 1 is larger (i.e., the temperature difference is improved by 2.0° C. or more to thereby become small). That is, output voltage does not deteriorate much, and the uniformity of temperature distribution is improved further.
Table 4 shows the results of an experiment conducted for verifying the flow channel condition of the fifth embodiment (flow channel disposition condition 5: see
The criteria employed in Table 4 are as follows.
<Criteria>
AA: A drop in output voltage is 3.5% or less, and a reduction in temperature difference ΔT is 2.0° C. or more.
AAA: A drop in output voltage is 1.0% or less, and a reduction in temperature difference ΔT is 2.0° C. or more.
AAAA: A drop in output voltage is 1.0% or less, and a reduction in temperature difference ΔT is 5.0° C. or more.
As is apparent from Table 4, when the position of the centroid Cfo of the fuel gas outlets falls within a range of 0.3 Xp to Xp, the position of the centroid Cai of the oxidizer gas inlets falls within a range of 0.6 Ym to Ym, and the position of the centroid Cao of the oxidizer gas outlets falls within a range of 0.4 Yp to 0.9 Yp (see the hatched and shaded portions in Table 4), the amount dVolt of change of output voltage of experimental model 1 is smaller (i.e., a drop in output voltage is 0.85% or less), and the amount dT of change of temperature difference ΔT of experimental model 1 is larger (i.e., the temperature difference is improved by 3.8° C. or more to thereby become small). That is, output voltage does not deteriorate to a greater degree, and the uniformity of temperature distribution is further improved.
Also, as is apparent from Table 4, when the position of the centroid Cfo of the fuel gas outlets falls within a range of 0.3 Xp to Xp, the position of the centroid Cai of the oxidizer gas inlets falls within a range of 0.6 Ym to Ym, and the position of the centroid Cao of the oxidizer gas outlets falls within a range of 0.4 Yp to 0.6 Yp (see the hatched portion in Table 4), the amount dVolt of change of output voltage of experimental model 1 is far smaller (i.e., a drop in output voltage is 0.62% or less), and the amount dT of change of temperature difference ΔT of experimental model 1 is far larger (i.e., the temperature difference is improved by 5.0° C. or more to thereby become small). That is, output voltage does not deteriorate to a far greater degree, and the uniformity of temperature distribution is improved to a far greater degree.
In experimental example 2, an experiment (simulation) was performed on experimental model 2 and the reference model (reference cell) to verify the basis which experimental example 1 has in setting the positions of the centroid Cfo of the fuel gas outlets, the centroid Cai of the oxidizer gas inlets, and the centroid Cao of the oxidizer gas outlets with the position of the centroid Cfi of the fuel gas inlets employed as a reference position.
Experimental example 2 used the reference model, and experimental model 2 in which, as shown in the following Table 5 and
Output voltages of the reference model and experimental model 2 were obtained for the case of generating electricity under the operating conditions of experimental example 1, and the obtained output voltages were compared between the reference model and experimental model 2. Specifically, there was obtained the amount of change of output voltage of experimental model 2 in relation to the reference model. The obtained results are shown in Table 5 and
The horizontal axis of
As is apparent from Table 5 and
The present invention has been described with reference to the embodiments. However, the present invention is not limited thereto, but may be embodied in various other forms.
(1) For example, the present invention can be applied to a solid oxide fuel cell (SOFC) apparatus which uses ZrO2 ceramic or the like as electrolyte, a polymer electrolyte fuel cell (PEFC) apparatus which uses a polymer electrolyte membrane as electrolyte, a molten carbonate fuel cell (MCFC) apparatus which uses Li—Na/K carbonate as electrolyte, a phosphoric-acid fuel cell (PAFC) apparatus which uses phosphoric acid as electrolyte, etc.
(2) In the present invention, the planar shapes of the single cell, the electricity generation unit, the fuel cell stack, etc., are not limited to quadrangular shapes (e.g., a rectangular shape, a square shape, a diamond shape, and a trapezoidal shape), but can employ various other shapes such as polygons (e.g., hexagon and octagon) and curved shapes (e.g., a circular shape and an elliptic shape).
(3) Further, the fuel cell apparatus of the present invention can employ the form of a single-tier fuel cell apparatus which uses one planar single cell (electricity generation unit) in addition to the form of a fuel cell stack in which a plurality of planar single cells (electricity generation units) are stacked. Also, of all the electricity generation units of the fuel cell stack, only one or a plurality of electricity generation units may have the structure of the present invention.
1: planar fuel cell apparatus (fuel cell stack)
7: electricity generation unit
17: single fuel cell
31: oxidizer gas chamber (air flow channel)
35: fuel gas chamber (fuel flow channel)
55: solid electrolyte layer
59: anode layer
57: cathode layer
Fin: fuel gas inlet
Fout: fuel gas outlet
Ain: oxidizer gas inlet
Aout: oxidizer gas outlet
Number | Date | Country | Kind |
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2015-073680 | Mar 2015 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2016/001779 | 3/28/2016 | WO | 00 |