JP2013033621A - Fuel battery unit and fuel battery stack - Google Patents

Fuel battery unit and fuel battery stack Download PDF

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JP2013033621A
JP2013033621A JP2011168852A JP2011168852A JP2013033621A JP 2013033621 A JP2013033621 A JP 2013033621A JP 2011168852 A JP2011168852 A JP 2011168852A JP 2011168852 A JP2011168852 A JP 2011168852A JP 2013033621 A JP2013033621 A JP 2013033621A
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fuel cell
separator
bent
fuel battery
electrode
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JP5751978B2 (en
Inventor
Nobuyuki Hotta
信行 堀田
Takeshi Ono
大野  猛
Akikazu Taido
明和 泰道
Hiroaki Yagi
宏明 八木
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Ngk Spark Plug Co Ltd
日本特殊陶業株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

PROBLEM TO BE SOLVED: To provide a fuel battery cell capable of preventing a crack in the vicinity of a lamination edge between the fuel battery cell and a collector.SOLUTION: A fuel battery unit 11 comprises a fuel battery cell 9 in which a flat plate type solid electrolyte body 1 is sandwiched between a fuel electrode 3 and an air electrode 2, a joining part 5 provided on the top surface of the fuel battery cell 9, and a plate type metallic separator 44, and the fuel battery cell 9 and the rear surface of the separator 44 are joined through the joining part 5. In the fuel battery unit 11, the separator 44 has a bent part 6 formed by being folded such that the principal planes of the separator face each other and that a virtual line A running axially in the out-of-plane direction of the solid electrolyte body 1 intersects the facing principal planes. A structure having the bent part 6 like this prevents a crack from occurring by reducing stress that occurs in the vicinity of a lamination edge between the fuel battery cell 9 and the collector.

Description

  The present invention relates to a fuel cell unit having a solid electrolyte body having a fuel electrode and an air electrode, a fuel cell unit in which a separator is joined, and a fuel cell stack in which the fuel cell units are stacked. In particular, the present invention provides a fuel cell unit and a fuel cell stack in which cracks are unlikely to occur in the vicinity of the stacked end portion of the fuel cell and the current collector even when the operation and stop are repeated.

  A conventionally known solid oxide fuel cell unit has, for example, a metal separator bonded to the periphery of a fuel cell having a fuel electrode and an air electrode on each surface of a plate-shaped solid electrolyte body. As a separator to be used, a separator provided with an L-shaped bending structure to suppress stress deformation at the joint, or a separator provided with a wave-like flexure to relieve stress applied to the joint It has been known. (For example, see Patent Documents 1 and 2)

JP 2010-21038 A JP 2008-293741 A

  The fuel cell unit described above includes a separator having a wavy or L-shaped bending structure, so that it can follow the deformation of the solid electrolyte body in the in-plane direction, but is sufficient for following the deformation in the out-of-plane direction. Because it is not possible to cope with this, the fuel cell stack and the fuel cell stack are collected by the difference in contraction due to the fluctuation of heat caused by repeated operation and stop of the fuel cell stack, and the stress applied when stacking the fuel cell unit via the interconnector or current collector. There has been a problem that a crack is generated in an electrode in the vicinity of an end portion of the laminate with the electric body.

  Further, when the metal separator is thin, the oxidation resistance is not sufficiently secured, and the separator itself may be damaged.

  In that case, it was considered to increase the thickness of the separator in order to ensure the oxidation resistance of the separator. However, if the thickness of the separator is increased too much, the deformation of the separator itself is hindered, thereby collecting the fuel cell. There was also a problem that cracks were induced in the electrode near the end of the laminate with the electric body.

  The present invention has been made to solve the above-described problems, and its purpose is to suppress cracks generated in the electrode near the stacking end portion of the fuel cell and the current collector, and furthermore, the oxidation resistance of the separator. This is to compensate for the long-term reliability of the fuel cell unit by preventing damage due to lack of performance.

  A fuel cell unit according to the present invention is a plate-shaped fuel cell comprising a flat type fuel cell sandwiched between a fuel electrode and an air electrode, a joint provided on the surface of the fuel cell, and a metal material. A separator comprising: a separator comprising: a separator comprising: a separator, wherein the fuel cell and the separator are joined via a joint provided on a surface of the fuel cell; The imaginary line which opposes and is axially penetrated in the out-of-plane direction of the fuel cell has a bent portion formed so that the opposing main surfaces intersect each other.

In the present invention, since the separator has the above-described bent portion, when the stress is applied to the fuel cell unit from the outside, the contraction difference due to the fluctuation of heat due to repeated operation / stop of the fuel cell stack, The separator follows the stress generated by warping in the out-of-plane direction of the fuel cell, and the force applied to the joint is reduced, which occurs at the electrode near the stack end of the fuel cell and the current collector. Cracks can be prevented.
In the present invention, the continuous surface on the side to be joined to the joining portion in the continuous surface from one side surface of the separator to the other side surface is defined as the “back surface” of the separator, and the main surface is the other side. The continuous surface is defined as the “main surface”. Therefore, when the separator is bent, the main surfaces can face each other.
In addition, when a plurality of separators are joined and apparently one separator is formed, the above definition is applied to the joined separators.

  Further, the separator is formed so that angles formed by the opposing main surface and the imaginary line are right angles.

In the present invention, the angle formed between the opposing main surface and the imaginary line is almost a right angle, and the separator follows the warp in the in-plane direction in addition to the out-of-plane direction of the fuel cell, and the force applied to the joint portion By reducing it, it is possible to further prevent cracks generated in the electrode near the end of the stack of the fuel cell and the current collector. The angle is preferable in that the force applied to the joint portion can be reduced against the deformation in the out-of-plane direction as the angle approaches 90 degrees. In particular, when the angle is 90 degrees, the angle is a right angle, which is more preferable in that the force applied to the joint can be reduced to the maximum.
In the present invention, that the angle formed between the opposing main surface and the imaginary line is a right angle indicates that the angle formed is in the range of 85 to 95 °. Each angle formed by the opposing main surface and the imaginary line may be different as long as it is within the above range.

  Further, the separator is made of a plurality of plate materials, and the bent portion is characterized in that the plate materials face each other and end portions of the plate materials are joined to each other.

  In the present invention, by forming the separator having the bent portion by joining the end portions of the plurality of plate members, it is possible to form the separator having the bent portion more easily than folding one separator. it can.

  The separator is made of a single plate material, and the bent portion is formed by bending the single plate material.

  In this invention, the separator which has a bending part can be formed at low cost by forming the separator which has a bending part by bending back one board | plate material.

  Further, the bent portion and the joint portion are separated from each other, and the bent portion is arranged closer to the center of the fuel cell than the joint portion.

  In the present invention, by separating the bent portion of the separator and the joint portion on the surface of the fuel cell, and further disposing the bent portion closer to the center of the fuel cell than the joint portion, The separator length to the frame portion can be made longer than the separator of the fuel cell unit described above. Therefore, it becomes easier to follow and deform the stress generated by the separator, and it is possible to suppress the generation of cracks in the electrode near the stacked end portion of the fuel cell and the current collector.

  In the fuel cell unit, the separator has a thickness of 0.04 mm or more and 0.3 mm or less.

  In the present invention, the separator has a follow-up deformability in the out-of-plane direction of the fuel cell in terms of the structure, and the electrode in the vicinity of the stacking end portion of the fuel cell and the current collector caused by increasing the thickness of the separator. It is possible to prevent the occurrence of cracks. Further, the thickness of the separator can be ensured more than before, and thus the oxidation resistance of the separator can be improved.

  The fuel cell stack according to the present invention is characterized in that the fuel cell units are stacked.

  In the present invention, a fuel cell stack is formed by stacking a plurality of fuel cell units, and in such a fuel cell stack, there is a particular concern about the generation of stress generated when the fuel cell units are stacked. The present invention is particularly effective for a fuel cell stack in which a plurality of fuel cell units are stacked.

According to the present invention, the separator has the above-described bent portion, and the shrinkage difference due to the stress generated when stacking the fuel cell units, the fluctuation of heat due to the repeated operation / stopping of the fuel cell stack, In addition, the separator is deformed following the stress generated by the warpage in the out-of-plane direction of the fuel cell, and cracks occurring in the electrode near the stacked end portion of the fuel cell and the current collector can be prevented.
In addition, since the separator has the ability to follow and deform in the out-of-plane direction of the fuel cell in terms of structure, the thickness of the separator itself can be ensured more than before, thereby improving the oxidation resistance of the separator. Can do.

1 is a cross-sectional view showing a solid oxide fuel cell of Example 1. FIG. 2 is a cross-sectional view showing a solid oxide fuel cell of Example 2. FIG. 3 is a cross-sectional view showing a solid electrolyte fuel cell of Example 3. FIG. 4 is a cross-sectional view showing a solid oxide fuel cell of Example 4. FIG. FIG. 5 is a cross-sectional view showing a solid oxide fuel cell of Example 5. 6 is a cross-sectional view showing a solid oxide fuel cell of Example 6. FIG. 7 is a cross-sectional view showing a solid oxide fuel cell of Comparative Example 1. FIG. FIG. 8 is a perspective view showing a fuel cell stack according to the present invention. FIG. 9 is a cutaway view showing a fuel cell stack according to the present invention. 10 is a perspective view showing a solid oxide fuel cell of Example 1. FIG.

Hereinafter, an embodiment and a manufacturing method of the present invention are described based on a drawing.
Example 1
FIG. 1 is a cross-sectional view showing a fuel cell unit 10 of the first embodiment. The fuel cell unit 10 includes a flat solid electrolyte body 1 made of YSZ (stabilized zirconia), an air electrode 2 made of La0.6Sr0.4Co0.2Fe0.8Ox (LSCF), and a fuel electrode 3 made of Ni-YSZ. A plate-shaped fuel cell 9 that is sandwiched and a separator (SUS) made of a metal material that is joined to the fuel cell unit 10 via the joint 5 on the surface of the solid electrolyte 1 of the fuel cell unit 9. Has been.

  As shown in FIG. 10, the separator 4 is composed of two plate members 41 and 42 made of SUS430 having an opening at the center, and one of the two plate members has a thickness of 0.15 mm and a vertical length. The first separator 41 has a length L1 of 180 mm and a horizontal length L2 of 180 mm, and the other is a second separator 42 having a vertical length L3 of 130 mm and a horizontal length L4 of 130 mm. The first separator 41 and the second separator 42 are both frame-shaped and have openings, and the sizes of the openings are 120 mm in length and 120 mm in width for both the opening of the first separator and the opening of the second separator. Are the same size. Further, a through-hole through which a fixing bolt penetrates when a plurality of fuel cell units are stacked to form a fuel cell stack is formed in the peripheral portion of the first separator 41.

  The second separator 42 is provided on the upper surface of the solid electrolyte body 1 on the back surface thereof, with the joining portion 5 made of brazing material containing Ag as a main component and further adding about 1 wt% of TiAl alloy and Cr, respectively, The solid electrolyte body 1 was brazed to the solid electrolyte body 1 over a length of 5 mm from the end of the solid electrolyte body 1 (in the atmosphere, 1020 ° C., 2 hours).

  At that time, the air electrode 2 and a part of the solid electrolyte body 1 are exposed from the opening of the second separator 42. The first separator 41 is overlapped so that the main surface thereof faces the main surface of the second separator 42 so that the air electrode 2 and a part of the solid electrolyte body 1 are exposed from the first opening. Yes.

  The end portions on the opening side of the first separator 41 and the second separator 42 that were overlapped were joined to each other by laser welding to form a welded portion 7. Therefore, in the separator 4, the main surfaces of the first separator 41 and the second separator 42 are opposed to each other, and the imaginary line A that passes through the out-of-plane direction of the fuel cell 9 and the opposed main surfaces intersect each other. It has the bent part 6 formed.

  Since the separator 4 has the bent portion 6 described above, even if the fuel cell 9 is warped or undulated in the axial direction of the imaginary line A, causing thermal deformation, the first separator 41 and the second separator 42 Since the gap between the main surfaces can be deformed so as to open widely from the bent portion 6 toward the outside (through hole side), a crack is generated at the electrode near the stacked end portion of the fuel cell and the current collector. Hard to do.

  Of the separator 4 joined to the fuel cell 9, the length t1 of the movable part is the length from the joining end of the separator 4 to the frame part f composed of an air electrode frame 57 and a fuel electrode frame 61, which will be described later. In this embodiment, it is 10 mm.

Further, as shown in FIG. 8, a fuel cell stack 100 formed by stacking a plurality of fuel cell units 10 was prepared as follows.
An interconnector / air electrode current collector 45 made of Crofer 22H, an air electrode frame 57, a fuel electrode frame 65, insulating frames 55 and 63 made of mica, the fuel cell unit 10, and a fuel electrode side current collector made of a nickel porous body. 9 are stacked as shown in FIG. 9, and fixing bolts 71, 73 are inserted into through holes 67, 69 formed in the outer periphery of the separator 4 and each member of the fuel cell unit 10, and the tip thereof Are integrally formed by screwing and tightening nuts N corresponding to the respective bolts.
The upper interconnector 45 is formed with first and second grooves 75 and 77 serving as air flow paths so as to communicate with the through holes 67 and 69. Accordingly, air is introduced from one through hole 67 into the air flow path 43 in the fuel cell through the first groove 75, and after the air comes into contact with the air electrode 2, the other passes through the second groove 77. Is discharged into the through hole 69.

  In addition, the fuel cell unit constituting the fuel cell stack 100 is not limited to the fuel cell unit 10, and the fuel cell units 11 to 15 of different embodiments may be adopted, or the fuel cell units may be mixed.

(Example 2)
Next, the second embodiment will be described, but the same contents as the first embodiment will be omitted.
In the fuel cell unit 11 of FIG. 2, a separator 44 having a bent portion 6 in which the main surface of the plate-like separator 44 faces is used by bending a metal plate material having one opening. .
That is, the plate-type separator 44 is mainly formed by gradually bending a portion of the separator 44 made of ZMG232L having a thickness of 0.15 mm, a length of 180 mm, and a width of 180 mm from the end on the opening side. A U-shaped bent portion 6 is formed so that the surfaces face each other. The main surfaces are in a positional relationship parallel to each other, and a gap is formed between the main surfaces.

  Similar to the first embodiment, the back surface of the separator 44 and the solid electrolyte body 1 are brazed and joined to each other through the joint portion 5 over a length of 5 mm from the end of the solid electrolyte body 1, and the air electrode is opened from the opening portion. 2 and a part of the solid electrolyte body 1 are exposed.

  Since the separator 44 has the U-shaped bent portion 6, it is formed between the main surfaces of the separator even when the fuel cell warps or undulates in the axial direction of the imaginary line A and is deformed by thermal deformation. Since the formed gap can be deformed so as to widen from the bent portion 6 toward the outside (through hole side), cracks are hardly generated at the electrode near the stack end portion of the fuel cell and the current collector. .

The angle formed between the opposing separator main surface and the imaginary line A is substantially a right angle.
Moreover, the length t2 of the movable part of this embodiment is 10 mm.

Next, a method for manufacturing the fuel cell units 10 and 11 will be described.
60 parts by weight of nickel oxide (NiO) powder and 40 parts by weight of zirconia (8YSZ) powder in which 8 mol% of yttria is solid-mixed are used as a component raw material. In addition, a predetermined amount of a dispersant, an organic solvent (toluene and methyl ethyl ketone (MEK)), a plasticizer, and a binder are further added to form a slurry, and the slurry is used to form a green sheet having a thickness of 200 μm by a doctor blade method. did.

  Then, the seven green sheets were laminated and pressure-bonded and cut into 130 mm × 130 mm to obtain a fuel electrode laminated green sheet having a thickness of 1300 μm.

  As a raw material of the solid electrolyte body, 8YSZ powder was used. A solid electrolyte slurry was prepared by mixing 100 parts by weight of this 8YSZ powder with 13 parts by weight of polyvinyl alcohol and 35 parts by weight of butyl carbitol as a binder.

  This solid electrolyte slurry was screen-printed to a thickness of 25 μm so as to cover the entire surface of the fuel electrode laminated green sheet to form an unfired solid electrolyte.

  The green body of the unfired laminate was fired simultaneously at 1400 ° C. for 1 hour to obtain a sintered body of the laminate composed of the fuel electrode 3 and the solid electrolyte body 1.

  As a raw material for the air electrode 2, a commercially available LSCF powder having an average particle diameter of 2 μm was used.

  Then, a predetermined amount of binder was mixed with 100 parts by weight of the LSCF powder to prepare an air electrode slurry, and screen printing was performed on the fixed electrolyte body 1 of the sintered body of the laminate. Then, it dried and baked on 1200 degreeC 1 hour keeping conditions.

  As a result, a fuel cell 9 in which the solid electrolyte body 1 was sandwiched between the fuel electrode 3 and the air electrode 2 was obtained.

  Thereafter, the separators 4 and 44 having the bent portions 6 were applied to the solid electrolyte body 1 by bending, and were joined and integrated at the joint portions 5 formed of a brazing material, thereby producing fuel cell units 10 and 11.

(Example 3)
Next, the third embodiment will be described, but the same contents as those of the previous embodiment will be omitted.
In the second embodiment, the separator 44 of the fuel cell unit 11 is provided with only one bent portion 6. However, in the fuel cell unit 12 of the third embodiment, as shown in FIG. 3, the bent portion 61 and the bent portion 62 are provided. And a separator 444 having two bent portions.

That is, instead of the separator 44, a U-shaped separator 44 made of ZMG232L having a thickness of 0.15 mm, a length of 180 mm, and a width of 180 mm is bent at two positions on the opening side. A bent portion 61 and a U-shaped bent portion 62 are formed, and the junction 5 is connected to the main surface of the separator 444 and the solid electrolyte body 1 over a length of 5 mm from the end of the solid electrolyte body 1 in the same manner as described above. And brazed.
In the present embodiment, the bent portion 61 and the bent portion 62 are bent in opposite directions to form a Z-shaped bent portion as a whole, and the bent portion 61 and the bent portion 62 are joined. The fuel cell 9 is disposed on the outer side of the part 5.
Moreover, the length t3 of the movable part of this embodiment is 10 mm.

Example 4
Next, although Example 4 will be described, the same contents as those in the above example are omitted.
Example 4 is a modified example of Example 3. In the fuel cell unit 13 of FIG. 4, the back surface of the separator 444 was brazed and joined to the solid electrolyte body 1 via the joint 5.
In this embodiment, the U-shaped bent portion 61 and the U-shaped bent portion 62 are bent in opposite directions, and the bent portion 61 and the bent portion 62 are located above the joint portion 5. Is arranged.
Moreover, the length t4 of the movable part of this embodiment is 10 mm.

(Example 5)
Next, although Example 5 will be described, the same contents as in the above example are omitted.
Example 5 is a modification of Example 2, and in the fuel cell unit 14 of FIG. 5, the bent part 6 and the joint part 5 of the separator 44 are separated from each other by 2.5 mm, so that the bent part 6 is joined to the joint part. It joined so that it might be located in the center part side of a fuel cell rather than 5. FIG.

That is, a separator 44 made of ZMG232L having a thickness of 0.15 mm, a length of 180 mm, and a width of 180 mm is gradually bent at a portion of 7.5 mm from the end on the opening side, thereby folding the U-shape. The curved portion 6 was formed, and the main surface of the separator 44 and the solid electrolyte body 1 were brazed and joined via the joint portion 5 over a length of 5 mm from the end portion of the solid electrolyte body 1 in the same manner as described above.
Therefore, in the present embodiment, since the bent portion 6 is arranged 2.5 mm away from the joint portion 5 on the center side of the fuel cell 9, the length t5 of the movable portion is 15 mm.

(Example 6)
Next, the sixth embodiment will be described, but the same contents as those of the previous embodiment will be omitted.
The sixth embodiment is a modification of the fourth embodiment. As shown in FIG. 6, the separator 444 has an angle formed between each principal surface facing in parallel with the virtual line A that passes through the out-of-plane direction of the fuel cell 9. It is folded so that θ1 and θ2 are 45 degrees.
In the present embodiment, since the principal surfaces are parallel to each other, the angle formed between each principal surface and the virtual line A is 45 degrees, but θ1 and / or θ2 is 0 ° <θ ≦ 90 °. And θ1 and θ2 may be different.
Moreover, the length t6 of the movable part of this embodiment is 10 mm.

Next, experimental examples conducted for confirming the effects of the present invention will be described.
(Test sample)
Test samples 1 to 6 corresponding to Examples 1 to 6 described above were prepared. Moreover, the test sample 7-the test sample 12 corresponding to what changed the thickness of the separator in Example 2 with 0.03 mm-0.32 mm, respectively was prepared.
In Comparative Example 1, as shown in FIG. 7, a test sample 13 was prepared in which the separator 444 was folded so that the main surface facing only the imaginary line B that passed through the in-plane direction of the fuel cell 9 intersected.
Test samples corresponding to the above-described Examples and Comparative Examples were prepared, and a load test was performed using them. In the load test, a portion corresponding to the frame portion was fixed with a jig, and the entire surface of the air electrode 2 was pressed by a predetermined amount with a compression tester. The load (N) at the time when the displacement stroke of each test sample became 0.25 mm was compared with the case where the load of the test sample 13 which is Comparative Example 1 was set to 100, and the degree of change was evaluated. .
In addition, it shows that it is a structure where a stroke is displaced greatly with a small load, so that the value of the measured load is small. That is, it means that the stress generated in the fuel cell when the given displacement is given is small.

Moreover, the thermal endurance test was done using the said test sample.
In the thermal endurance test, the fuel cell stack 100 is used, and the fuel cell stack 100 is installed in an electric furnace. Thereafter, the temperature in the electric furnace is increased to 850 ° C. over 3 hours and held for 18 hours. Next, the temperature is lowered to room temperature in 3 hours. This cycle was repeated 30 times.
The results of the load test and thermal endurance test are shown in Table 1.

  As shown in Table 1, in the separator thickness of 0.15 mm of Test Sample 1 to Test Sample 6 and Test Sample 13, the load was smaller than that of Test Sample 13, and the result exceeded that of Comparative Example 1. In particular, the test sample 5 corresponding to Example 5 gave the best results. This is presumed to be due to the fact that the length t5 of the movable part of the separator is longer than that of the other examples.

On the other hand, regarding the durability, the test sample 7 having a separator thickness of 0.03 mm could not withstand oxidation, and cracks occurred in the separator itself. In the test sample 8 having a separator thickness of 0.05 mm, cracks in the separator itself due to oxidation were not confirmed in this test. Moreover, in the test samples 12 and 13, since the crack generate | occur | produced in the electrode near the lamination | stacking edge part of a fuel cell and a collector, it was judged that it was defect. Since the test sample 12 is thick with a separator thickness of 0.32 mm, the load value (Table 1) is high, and the stress generated in the fuel cell is large, so that the electrode near the stack end of the fuel cell and the current collector is used. It is thought that a crack occurred.
Since Comparative Example 1 of the test sample 13 cannot sufficiently cope with the deformation follow-up in the out-of-plane direction, the stress generated in the fuel cell is large, and the electrode in the vicinity of the stacked end portion of the fuel cell and the current collector is cracked. It is thought that it occurred.

  In addition, this invention is not limited to the said Example at all, and it cannot be overemphasized that it can implement with a various aspect in the range which does not deviate from this invention.

  For example, in the embodiment of the present application, two separators are joined to produce a separator having a bent portion, but it may be produced using a larger number. Also, a plurality of bent portions may be formed.

  Further, in the embodiment of the present invention, various modified examples have been described based on a separator made of a single plate material, but the same modified example can be achieved even with a separator made of a plurality of plate materials.

  Further, the same effect can be obtained even if the material is formed using the materials described below.

Examples of the material for the solid electrolyte body include ZrO 2 ceramics, LaGaO 3 ceramics, BaCeO 3 ceramics, SrCeO 3 ceramics, SrZrO 3 ceramics, and CaZrO 3 ceramics in addition to the materials described above.

Examples of the material for the fuel electrode include ceramics such as ZrO 2 ceramics such as zirconia and CeO 2 ceramics stabilized by at least one of metals such as Ni and Fe and rare earth elements such as Sc and Y. And a mixture with at least one of them. Moreover, metals, such as Pt, Au, Ag, Pd, Ir, Ru, Rh, Ni, and Fe, are mentioned. These metals may be used alone or in an alloy of two or more metals. Further, a mixture (including cermet) of these metals and / or alloys and at least one of each of the above ceramics may be mentioned. Moreover, the mixture of metal oxides, such as Ni and Fe, and at least 1 type of each of the said ceramic etc. are mentioned.

As a material for the air electrode, for example, various metals, metal oxides, metal double oxides, and the like can be used. Examples of the metal include metals such as Pt, Au, Ag, Pd, Ir, Ru, and Rh, or alloys containing two or more metals. Furthermore, examples of the metal oxide include oxides such as La, Sr, Ce, Co, Mn and Fe (La 2 O 3 , SrO, Ce 2 O 3 , Co 2 O 3 , MnO 2 and FeO). It is done. In addition, as the double oxide, a double oxide containing at least La, Pr, Sm, Sr, Ba, Co, Fe, Mn, etc. (La 1-X Sr X CoO 3 -based double oxide, La 1-X Sr X FeO 3 -based double oxide, La 1-X Sr X Co 1-Y Fe Y O 3 -based double oxide, La 1-X Sr X MnO 3 -based double oxide, Pr 1-X Ba X CoO 3 -based double oxide Oxides and Sm 1-X Sr X CoO 3 -based double oxides).

  As materials for separators, interconnectors, air electrode frames and fuel electrode frames, materials having excellent heat resistance, chemical stability, strength, etc. can be used. For example, heat-resistant alloys such as stainless steel, nickel-base alloys, and chromium-base alloys And metal materials such as

Specifically, examples of stainless steel include ferritic stainless steel, martensitic stainless steel, and austenitic stainless steel. Examples of the ferritic stainless steel include Crofer 22H, Crofer 22APU, ZMG232L, SUS430, SUS434, SUS405, and SUS444. Examples of martensitic stainless steel include SUS403, SUS410, and SUS431. Examples of austenitic stainless steel include SUS201, SUS301, and SUS305. Further, examples of the nickel-based alloy include Inconel 600, Inconel 718, Incoloy 802, and the like. As a chromium-based alloy, Ducrloy
CRF (94Cr5Fe1Y 2 O 3), and the like.

Various materials such as metal brazing material and glass can be used as materials for joining the separator (materials constituting the joining portion), and various materials can be selected in consideration of the operating temperature and life characteristics of the fuel cell. For example, as brazing material, Ni brazing material,
A small amount (several mass%) of a metal oxide selected from SiO 2 , Al 2 O 3 , Cr 2 O 3 , CuO and the like is added to Ag, an alloy containing Ag as a main component, and an alloy containing Ag or Ag as a main component. As the glass, crystallized glass mainly composed of CaO—Al 2 O 3 —SiO 2 can be used.

DESCRIPTION OF SYMBOLS 1 Solid electrolyte body 2 Air electrode 3 Fuel electrode 4,44,444, Separator 41 1st separator 42 2nd separator 43 Air flow path 45 Interconnector and air electrode side current collector 51 Fuel electrode side current collector 55,63 Insulation Frame 57 Air electrode frame 5 Junction part 6, 61, 62 Bending part 65 Fuel electrode frame 67, 69 Through hole 7 Welding part 71, 73 Bolt 75 First groove 77 Second groove 9 Fuel cell 10, 11, 12, 13, 14, 15, 16 Fuel cell unit f Frame portion N Nut

Claims (7)

  1. It is composed of a flat plate type fuel cell sandwiching a solid electrolyte body between a fuel electrode and an air electrode, a joint provided on the surface of the fuel cell, and a plate-like separator made of a metal material, In the fuel cell unit in which the fuel cell and the separator are joined via a joint provided on the surface of the fuel cell,
    The separator has a bent portion formed so that the principal surfaces thereof are opposed to each other, and the imaginary line passing through the out-of-plane direction of the fuel cell and the opposed principal surfaces intersect with each other.
    A fuel cell unit.
  2.   2. The fuel cell unit according to claim 1, wherein the separator is formed such that an angle formed between the opposing main surface and the imaginary line is a right angle.
  3.   3. The separator according to claim 1, wherein the separator is formed of a plurality of plate materials, and the bent portions are formed by facing the plate materials and joining end portions of the plate materials. Fuel cell unit.
  4.   3. The fuel cell unit according to claim 1, wherein the separator is made of a single plate material, and the bent portion is formed by bending the single plate material. 4.
  5.   The said bent part and the said junction part are spaced apart, and the said bent part is arrange | positioned rather than the said junction part to the center part side of a fuel cell, The Claim 1 thru | or 4 characterized by the above-mentioned. Fuel cell unit.
  6.   6. The fuel cell unit according to claim 1, wherein the separator has a thickness of 0.04 mm to 0.3 mm.
  7.   The fuel cell stack according to claim 1, wherein a plurality of the fuel cell units are stacked.
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JP2015022891A (en) * 2013-07-18 2015-02-02 日本特殊陶業株式会社 Fuel cell with separator and fuel cell stack
JP2015088265A (en) * 2013-10-29 2015-05-07 日本特殊陶業株式会社 Fuel battery unit cell with separator, fuel battery stack, and method for manufacturing the same
WO2015108012A1 (en) * 2014-01-15 2015-07-23 日本特殊陶業株式会社 Fuel cell cassette and fuel cell stack
CN108288543A (en) * 2014-02-27 2018-07-17 三星电机株式会社 Multilayer ceramic capacitor and plate with the multilayer ceramic capacitor
US10164286B2 (en) * 2013-10-29 2018-12-25 Ngk Spark Plug Co., Ltd. Separator-fitted single fuel cell inducing joint portion with protruding portion and sealing portion, and fuel cell stack
WO2019026168A1 (en) 2017-08-01 2019-02-07 日産自動車株式会社 Cell unit

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Publication number Priority date Publication date Assignee Title
JP2015022891A (en) * 2013-07-18 2015-02-02 日本特殊陶業株式会社 Fuel cell with separator and fuel cell stack
JP2015088265A (en) * 2013-10-29 2015-05-07 日本特殊陶業株式会社 Fuel battery unit cell with separator, fuel battery stack, and method for manufacturing the same
US10164286B2 (en) * 2013-10-29 2018-12-25 Ngk Spark Plug Co., Ltd. Separator-fitted single fuel cell inducing joint portion with protruding portion and sealing portion, and fuel cell stack
WO2015108012A1 (en) * 2014-01-15 2015-07-23 日本特殊陶業株式会社 Fuel cell cassette and fuel cell stack
CN105917507A (en) * 2014-01-15 2016-08-31 日本特殊陶业株式会社 Fuel cell cassette and fuel cell stack
JP6039110B2 (en) * 2014-01-15 2016-12-07 日本特殊陶業株式会社 Fuel cell cassette and fuel cell stack for solid oxide fuel cell
US10707499B2 (en) 2014-01-15 2020-07-07 Morimura Sofc Technology Co., Ltd. Fuel cell cassette and fuel cell stack
CN108288543A (en) * 2014-02-27 2018-07-17 三星电机株式会社 Multilayer ceramic capacitor and plate with the multilayer ceramic capacitor
CN108288543B (en) * 2014-02-27 2020-06-16 三星电机株式会社 Multilayer ceramic capacitor and board having the same
WO2019026168A1 (en) 2017-08-01 2019-02-07 日産自動車株式会社 Cell unit

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