JP2013175307A - Solid oxide fuel cell and method of manufacturing solid oxide fuel cell - Google Patents

Solid oxide fuel cell and method of manufacturing solid oxide fuel cell Download PDF

Info

Publication number
JP2013175307A
JP2013175307A JP2012037918A JP2012037918A JP2013175307A JP 2013175307 A JP2013175307 A JP 2013175307A JP 2012037918 A JP2012037918 A JP 2012037918A JP 2012037918 A JP2012037918 A JP 2012037918A JP 2013175307 A JP2013175307 A JP 2013175307A
Authority
JP
Japan
Prior art keywords
cell
cells
base tube
interconnector
solid oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
JP2012037918A
Other languages
Japanese (ja)
Inventor
Shin Yoshida
慎 吉田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Heavy Industries Ltd
Original Assignee
Mitsubishi Heavy Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Heavy Industries Ltd filed Critical Mitsubishi Heavy Industries Ltd
Priority to JP2012037918A priority Critical patent/JP2013175307A/en
Publication of JP2013175307A publication Critical patent/JP2013175307A/en
Ceased legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Fuel Cell (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a solid oxide fuel cell in which output per unit volume is improved by increasing the number of cells connected in series while insulation properties between cells are maintained.SOLUTION: Provided is a solid oxide fuel cell having a cell group 13 in which a plurality of cells 12, each of which is equipped with a fuel electrode, a solid electrolyte membrane and an air electrode, is arrayed on a substrate tube 11 in a circumferential direction of the substrate tube 11. A plurality of the cell groups 13 is arrayed along the axial direction of the substrate tube 11, the plurality of cells 12 is electrically connected in series in the circumferential direction of the substrate tube 11 via an interconnector in one of the cell groups 13, one cell 12 out of the one cell group 13 is electrically connected in series with one cell 12 out of another cell group 13 next to the one cell group 13 via the interconnector.

Description

本発明は、基体管上に複数のセルが形成された円筒型の固体酸化物形燃料電池及びその製造方法に関する。   The present invention relates to a cylindrical solid oxide fuel cell in which a plurality of cells are formed on a base tube and a method for manufacturing the same.

円筒型の固体酸化物形燃料電池（ＳＯＦＣ）は、発電室の内部に複数のセルスタックを収容する。図４に示すように、セルスタック１００は、基体管１０１の円周方向に、燃料極１０３、固体電解質膜１０４、空気極１０５を積層させたセル１０２が複数形成される。複数のセル１０２は、基体管１０１の軸方向に配列され、隣り合うセル１０２同士がインターコネクタ１０６で電気的に直列に接続される。   A cylindrical solid oxide fuel cell (SOFC) accommodates a plurality of cell stacks inside a power generation chamber. As shown in FIG. 4, the cell stack 100 includes a plurality of cells 102 in which a fuel electrode 103, a solid electrolyte membrane 104, and an air electrode 105 are stacked in the circumferential direction of the base tube 101. The plurality of cells 102 are arranged in the axial direction of the base tube 101, and adjacent cells 102 are electrically connected in series by an interconnector 106.

上記の固体酸化物形燃料電池において１つの基体管（セルスタック）での発電量を増大させるためには、基体管の軸方向でセル数を増加させる。このとき、セル数の増加に伴って基体管を長くすると、固体酸化物形燃料電池の発電室を大きくする必要が生じ、装置容積が増大してしまう。基体管の長さを変えずにセル数を増大させるためには、セル間を短縮して発電に寄与しない領域の面積をできる限り小さくする必要がある。しかし、セル間の距離が小さくなりすぎると、セル間での絶縁性が低下して性能が低下する。これらの理由で、増加可能なセル数には限界があった。   In the above solid oxide fuel cell, in order to increase the amount of power generation in one base tube (cell stack), the number of cells is increased in the axial direction of the base tube. At this time, if the base tube is lengthened with an increase in the number of cells, it is necessary to enlarge the power generation chamber of the solid oxide fuel cell, and the apparatus volume increases. In order to increase the number of cells without changing the length of the base tube, it is necessary to shorten the area between the cells so as not to contribute to power generation as much as possible. However, if the distance between the cells becomes too small, the insulation between the cells decreases and the performance deteriorates. For these reasons, there is a limit to the number of cells that can be increased.

特許文献１は、基体管の円周方向で複数の単電池素子を設けた固体電解質型燃料電池を開示している。単電池素子は、基体管の上部側から下部側に向かって電気的に直列に接続され、さらに下部側から上流側に向かって電気的に直列接続されるリターン型の構造とされている。   Patent Document 1 discloses a solid oxide fuel cell in which a plurality of single cell elements are provided in the circumferential direction of a base tube. The unit cell elements are electrically connected in series from the upper side to the lower side of the base tube, and further have a return type structure that is electrically connected in series from the lower side to the upstream side.

特開２００２−６３９１６号公報（特許請求の範囲、段落［００１９］、図１〜図３）JP 2002-63916 A (claim, paragraph [0019], FIGS. 1 to 3)

本発明は、セルを微細化することで、セルを基体管の周方向と軸方向に配列し、直列接続されるセル数を増加させることにより、単位体積当たりの出力を向上させた固体酸化物形燃料電池及び固体酸化物形燃料電池の製造方法を提供することを目的とする。   The present invention provides a solid oxide in which the output per unit volume is improved by miniaturizing the cells, arranging the cells in the circumferential direction and the axial direction of the base tube, and increasing the number of cells connected in series. An object of the present invention is to provide a fuel cell and a method for producing a solid oxide fuel cell.

上記課題を解決するために、本発明は、基体管上に燃料極と固体電解質膜と空気極とを備えるセルが前記基体管の円周方向に複数配列されたセル群を有し、前記セル群が前記基体管の軸方向に沿って複数配列され、１つの前記セル群内で、前記基体管の円周方向に前記複数のセルがインターコネクタを介して電気的に直列接続され、前記１つのセル群内の一のセルが、前記１つのセル群の隣の別のセル群内の一のセルと前記インターコネクタを介して電気的に直列接続される固体酸化物形燃料電池を提供する。
上記発明において、前記基体管の軸方向に沿って、前記セルが整列されている。 In order to solve the above problems, the present invention has a cell group in which a plurality of cells each including a fuel electrode, a solid electrolyte membrane, and an air electrode are arranged on a base tube in the circumferential direction of the base tube, A plurality of groups are arranged along the axial direction of the base tube, and within the one cell group, the plurality of cells are electrically connected in series in the circumferential direction of the base tube via an interconnector. Provided is a solid oxide fuel cell in which one cell in one cell group is electrically connected in series with one cell in another cell group adjacent to the one cell group via the interconnector. .
In the above invention, the cells are aligned along the axial direction of the base tube.

また本発明は、基体管の外周面上に、前記基体管の円周方向及び軸方向の各々に、複数の燃料極及び固体電解質膜の積層膜を形成する積層膜形成工程と、前記基体管の円周方向に形成された前記複数の積層膜のうち一の積層膜と、該一の積層膜と前記基体管の軸方向で隣接する前記積層膜との間に、前記基体管の軸方向に電気的に直列接続するためのインターコネクタを形成する第１のインターコネクタ形成工程と、前記基体管の円周方向で隣接する前記積層膜の間に、前記基体管の円周方向に電気的に直列接続するためのインターコネクタを形成する第２のインターコネクタ形成工程と、前記第１のインターコネクタ形成工程及び前記第２のインターコネクタ形成工程の後に、前記積層体上に空気極を形成する工程とを有する固体酸化物形燃料電池の製造方法を提供する。   The present invention also provides a laminated film forming step of forming a laminated film of a plurality of fuel electrodes and solid electrolyte membranes on the outer peripheral surface of the substrate pipe in each of the circumferential direction and the axial direction of the substrate pipe; An axial direction of the substrate tube between one of the plurality of stacked films formed in the circumferential direction of the substrate and the stacked film adjacent to the one stacked film in the axial direction of the substrate tube Between the first interconnector forming step of forming an interconnector for electrical connection in series with the laminated film adjacent in the circumferential direction of the base tube, and in the circumferential direction of the base tube An air electrode is formed on the laminate after the second interconnector forming step for forming an interconnector for serial connection to the first interconnector, the first interconnector forming step, and the second interconnector forming step. Solid oxide form having a process To provide a method of manufacturing a charge battery.

本発明の固体酸化物形燃料電池では、基体管の軸方向だけでなく円周方向にもセルが形成されるように分離しているので、セル素子数が増加して単位体積当たりの出力を増大する。更に、基体管軸方向のみにセルを直列接続させる場合と比較して、基体管軸方向のセルの寸法を広く確保することができる。このため、固体酸化物形燃料電池の作製が容易となる。   In the solid oxide fuel cell of the present invention, since the cells are separated not only in the axial direction of the base tube but also in the circumferential direction, the number of cell elements increases and the output per unit volume is increased. Increase. Furthermore, compared with the case where the cells are connected in series only in the base tube axis direction, the size of the cells in the base tube axis direction can be secured widely. This facilitates the production of a solid oxide fuel cell.

また上記発明において、前記１つのセル群内の前記セルが、前記別のセル群内の前記セルと前記基体管の円周方向に位置がずれて配置され、複数の前記セルが、前記基体管の軸方向に対してらせん状になるように電気的に直列に接続されることが好ましい。   Further, in the above invention, the cells in the one cell group are arranged at positions shifted in a circumferential direction of the base tube with respect to the cells in the another cell group, and a plurality of the cells are arranged in the base tube. It is preferable to be electrically connected in series so as to be spiral with respect to the axial direction.

基体管の軸方向に隣り合うセル間の電位差を小さくすることができる。隣り合うセル間の電位差が小さいほど、絶縁破壊が発生するセル間の距離が短くなる。このため、発電に寄与しない接続部分の面積を小さくすることができる。従って、上記構成の固体酸化物形燃料電池では、セル数を更に増加させて高集積化することができ、出力を更に増大させることができる。   The potential difference between cells adjacent in the axial direction of the base tube can be reduced. The smaller the potential difference between adjacent cells, the shorter the distance between cells where dielectric breakdown occurs. For this reason, the area of the connection part which does not contribute to electric power generation can be made small. Therefore, in the solid oxide fuel cell having the above configuration, the number of cells can be further increased to achieve high integration, and the output can be further increased.

上記発明において、隣り合う前記セルの前記燃料極の間に、絶縁性材料からなる絶縁膜が形成されていることが好ましい。   In the above invention, it is preferable that an insulating film made of an insulating material is formed between the fuel electrodes of adjacent cells.

上記絶縁膜を設けることにより、セル間の距離を縮めた場合でもセル間の絶縁性を保持させて短絡を防止することができる。また、緻密な絶縁膜を設ければ、気密性が保たれるので性能が向上する。   By providing the insulating film, even when the distance between the cells is shortened, the insulation between the cells can be maintained and the short circuit can be prevented. In addition, when a dense insulating film is provided, airtightness is maintained, so that performance is improved.

本発明の固体酸化物形燃料電池は、セル数が増加しているため、高い出力で発電することができる。
また、隣り合うセル群でセルの位置を円周方向にずらし、基体管軸方向にらせん状になるようにセル同士を直列接続することで、基体管軸方向に隣り合うセル間の電位差を小さくすることができる。この結果、絶縁破壊を抑制しつつ高集積化された固体酸化物形燃料電池とすることができる。 Since the solid oxide fuel cell of the present invention has an increased number of cells, it can generate electric power with high output.
In addition, by shifting the cell position in the circumferential direction in adjacent cell groups and connecting the cells in series so as to be spiral in the base tube axis direction, the potential difference between the cells adjacent in the base tube axis direction is reduced. can do. As a result, it is possible to obtain a highly integrated solid oxide fuel cell while suppressing dielectric breakdown.

第１実施形態におけるセルの位置とセル間の電気的接続を表す概略図である。It is the schematic showing the position of the cell in 1st Embodiment, and the electrical connection between cells. 第２実施形態におけるセルの位置とセル間の電気的接続を表す概略図である。It is the schematic showing the position of the cell in 2nd Embodiment, and the electrical connection between cells. 第３実施形態におけるセルの位置とセル間の電気的接続を表す概略図である。It is the schematic showing the position of the cell in 3rd Embodiment, and the electrical connection between cells. 円筒型の固体酸化物形燃料電池におけるセルスタックの発電部の断面概略図である。It is the cross-sectional schematic of the electric power generation part of the cell stack in a cylindrical solid oxide fuel cell.

円筒型の固体酸化物形燃料電池は、発電室内に複数のセルスタックを収容する。セルスタックは、中央部に発電部が設けられ、両端部は非発電部となっている。セルスタックの発電部において、基体管の外周面上に、基体管側から順に燃料極、固体電解質膜、空気極を積層されたセルが形成されている。セルスタックは、基体管の内側に燃料（水素ガス等）が流通し、基体管の外側に空気が流通するものである。   A cylindrical solid oxide fuel cell accommodates a plurality of cell stacks in a power generation chamber. The cell stack is provided with a power generation unit in the center, and both ends are non-power generation units. In the power generation section of the cell stack, a cell in which a fuel electrode, a solid electrolyte membrane, and an air electrode are stacked in this order from the substrate tube side is formed on the outer peripheral surface of the substrate tube. In the cell stack, fuel (hydrogen gas or the like) flows inside the base tube, and air flows outside the base tube.

固体電解質膜の一部は、セルの基体管軸方向の一端部で基体管と接触する。但し、一つのセルの固体電解質膜は、隣のセルの燃料極とは接触していない。
隣り合うセル同士を連結するインターコネクタが形成されている。インターコネクタは、一つのセルの固体電解質膜と、このセルと接続されるセルの燃料極との間で、基体管と接触している。空気極は、固体電解質膜及びインターコネクタに接触して設けられる。 A part of the solid electrolyte membrane is in contact with the substrate tube at one end of the cell in the axial direction of the substrate tube. However, the solid electrolyte membrane of one cell is not in contact with the fuel electrode of the adjacent cell.
An interconnector that connects adjacent cells is formed. The interconnector is in contact with the base tube between the solid electrolyte membrane of one cell and the fuel electrode of the cell connected to the cell. The air electrode is provided in contact with the solid electrolyte membrane and the interconnector.

基体管はカルシア安定化ジルコニア（ＣＳＺ）、または、ＣＳＺと酸化ニッケル（ＮｉＯ）との混合物などを主とする多孔質材料からなる。基体管は多孔質であり、燃料とされる水素ガスが基体管内側から外側（燃料極側）に向かって流通可能となっている。
燃料極は酸化ニッケル（ＮｉＯ）とジルコニア系電解質材料との複合材で構成されている。複合材としては、例えば、ＮｉＯとイットリア安定化ジルコニア（ＹＳＺ）の混合物とされる。
固体電解質膜は電子絶縁性であり、ガスを通さない気密性と高温での高いイオン透過性とを有することが求められる。固体電解質膜は、主としてＹ２Ｏ３安定化ＺｒＯ２（ＹＳＺ）などからなる。
インターコネクタは燃料ガスと空気とが混合しないように緻密な膜となっている。インターコネクタは、例えばＬａＣｒＯ３、（Ｌａ，Ｓｒ）ＣｒＯ３、Ｌａ（Ｃｒ，Ｍｇ）Ｏ３、（Ｌａ，Ｃａ）ＣｒＯ３、（Ｓｒ，Ｌａ）ＴｉＯ３などで構成される。
空気極は、例えば（Ｌａ，Ｓｒ，Ｃａ）ＭｎＯ３で表されるペロブスカイト型酸化物を主成分とする。
セルスタックでの気密性を確保するために、固体電解質膜及びインターコネクタは、相対密度９０％以上の緻密膜とされる。 The base tube is made of a porous material mainly composed of calcia-stabilized zirconia (CSZ) or a mixture of CSZ and nickel oxide (NiO). The base tube is porous, and hydrogen gas used as fuel can flow from the inside of the base tube toward the outside (fuel electrode side).
The fuel electrode is composed of a composite material of nickel oxide (NiO) and a zirconia-based electrolyte material. As the composite material, for example, a mixture of NiO and yttria stabilized zirconia (YSZ) is used.
The solid electrolyte membrane is electronically insulating, and is required to have gas tightness that prevents gas from passing and high ion permeability at high temperatures. The solid electrolyte membrane is mainly made of Y 2 O 3 stabilized ZrO 2 (YSZ) or the like.
The interconnector is a dense membrane so that fuel gas and air are not mixed. The interconnector is composed of, for example, LaCrO 3 , (La, Sr) CrO 3 , La (Cr, Mg) O 3 , (La, Ca) CrO 3 , (Sr, La) TiO 3, and the like.
The air electrode contains, for example, a perovskite oxide represented by (La, Sr, Ca) MnO 3 as a main component.
In order to ensure airtightness in the cell stack, the solid electrolyte membrane and the interconnector are dense membranes having a relative density of 90% or more.

図１は、第１実施形態のセルスタックの発電部について、外周面を平面に展開した概略図である。なお、図１ではインターコネクタを省略している。
第１実施形態のセルスタック１０では、基体管１１の円周方向に複数のセル１２が配列されたセル群１３が形成されている。セル群１３は、基体管１１の軸方向に複数配列されている。基体管１１の軸方向で、複数のセル１２が整列して配置されている。すなわち、隣り合うセル群１３間では、セル１２は基体管１１軸方向の同位置に設けられている。 FIG. 1 is a schematic view of the power generation unit of the cell stack of the first embodiment developed on a flat outer peripheral surface. In FIG. 1, the interconnector is omitted.
In the cell stack 10 of the first embodiment, a cell group 13 in which a plurality of cells 12 are arranged in the circumferential direction of the base tube 11 is formed. A plurality of cell groups 13 are arranged in the axial direction of the base tube 11. A plurality of cells 12 are aligned in the axial direction of the base tube 11. That is, between the adjacent cell groups 13, the cells 12 are provided at the same position in the axial direction of the base tube 11.

１つのセル１２は、基体管１１の軸方向に電池が構成されている。従って、１つのセル１２内で電流が流れる方向は、基体管１１の軸方向と同じとなっている。   One cell 12 includes a battery in the axial direction of the base tube 11. Therefore, the direction of current flow in one cell 12 is the same as the axial direction of the base tube 11.

図１内の矢印は、セル間の電気的な接続方向（電流が流れる方向）を表している。基体管１１の両端部には集電部（不図示）が設けられる。一方の端部の集電部は、基体管１１端部側に設けられるセル群１３Ａ内のセル１２ａの負極（燃料極）と直列接続する。セル１２ａの正極（空気極）は、基体管１１の円周方向で隣り合うセル１２ｂの負極と直列接続する。このように、セル群１３内でセル１２同士は直列接続する。しかし、既に集電部と接続されているセル１２ａの負極と、隣のセル１２ｂの正極とは接続されない。   The arrows in FIG. 1 represent the electrical connection direction between cells (the direction in which current flows). Current collectors (not shown) are provided at both ends of the base tube 11. The current collector at one end is connected in series with the negative electrode (fuel electrode) of the cell 12a in the cell group 13A provided on the end of the base tube 11. The positive electrode (air electrode) of the cell 12 a is connected in series with the negative electrode of the cell 12 b adjacent in the circumferential direction of the base tube 11. Thus, the cells 12 are connected in series within the cell group 13. However, the negative electrode of the cell 12a already connected to the current collector and the positive electrode of the adjacent cell 12b are not connected.

セル１２ｂの正極は、セル群１３Ａの隣のセル群１３Ｂ内のセル１２ｃの負極と直列接続する。セル１２ｃは、基体管１１の軸方向でセル１２ｂと対角に位置している。セル１２ｃは、同じセル群１３Ｂ内で隣り合うセル１２ｄと直列接続する。上記の接続は、基体管１１の他方の端部に設けられるセル１２まで繰り返される。基体管１１の他方の端部に設けられるセル１２ｅの正極は、基体管１１の一方の端部の集電部と接続する。   The positive electrode of the cell 12b is connected in series with the negative electrode of the cell 12c in the cell group 13B adjacent to the cell group 13A. The cell 12 c is located diagonally to the cell 12 b in the axial direction of the base tube 11. The cell 12c is connected in series with the adjacent cell 12d in the same cell group 13B. The above connection is repeated up to the cell 12 provided at the other end of the base tube 11. The positive electrode of the cell 12 e provided at the other end of the base tube 11 is connected to the current collector at one end of the base tube 11.

図１ではセル１２ｂとセル１２ｃとを接続しているが、セル１２ｂと基体管１１軸方向に隣り合うセル１２ｄとを接続しても良い。こうすることで、セル間の接続距離を更に短くすることができる。   Although the cell 12b and the cell 12c are connected in FIG. 1, the cell 12b and the cell 12d adjacent in the axial direction of the base tube 11 may be connected. By doing so, the connection distance between the cells can be further shortened.

図１では、円周方向に２つのセル、軸方向に９つのセルを設けた場合が例示されているが、本実施形態はこれに限定されない。円周方向のセル数（１つのセル群内のセル数）及び軸方向のセル数（セル群の数）は、基体管の寸法、セルの単位長さあたりの出力等を考慮して決定される。セルの単位長さあたりの出力は、セル数と相関がある。すなわち、１つのセルスタック上に設けられるセル数が少ない場合には、集積されるセル数が少ない上に空気極の抵抗が大きいため、セルの単位長さあたりの出力が低い。一方、セル数を多くすると、発電に寄与しないセル間の面積（無効面積）が増大するので、単位長さあたりの出力が低くなる。   Although FIG. 1 illustrates the case where two cells are provided in the circumferential direction and nine cells are provided in the axial direction, the present embodiment is not limited to this. The number of cells in the circumferential direction (number of cells in one cell group) and the number of cells in the axial direction (number of cells) are determined in consideration of the dimensions of the base tube, the output per unit length of the cell, etc. The The output per unit length of the cell is correlated with the number of cells. That is, when the number of cells provided on one cell stack is small, the number of cells to be integrated is small and the resistance of the air electrode is large, so the output per unit length of the cell is low. On the other hand, if the number of cells is increased, the area between cells that does not contribute to power generation (ineffective area) increases, so the output per unit length decreases.

第１実施形態において、隣り合うセル１２の燃料極の間に、絶縁膜が設けられても良い。絶縁膜を設ける場合は、絶縁膜上に固体電解質膜が形成される。絶縁膜は、例えばＳｒＴｉＯ３系ペロブスカイト型酸化物、ＳｒＬａＴｉＯ３＋Ａｌ２Ｏ３、ＳｒＺｒＯ３＋Ａｌ２Ｏ３、ＭｇＡｌ２Ｏ４＋ＭｇＯなどとされる。絶縁膜は、相対密度９０％以上の緻密膜とされる。こうすることで、セルスタック１０の気密性が確保され、出力を増大させることができる。 In the first embodiment, an insulating film may be provided between the fuel electrodes of adjacent cells 12. When an insulating film is provided, a solid electrolyte film is formed on the insulating film. The insulating film is, for example, SrTiO 3 -based perovskite oxide, SrLaTiO 3 + Al 2 O 3 , SrZrO 3 + Al 2 O 3 , MgAl 2 O 4 + MgO, or the like. The insulating film is a dense film having a relative density of 90% or more. By doing so, the airtightness of the cell stack 10 is ensured, and the output can be increased.

第１実施形態のセルスタックの形成工程を以下で説明する。
基体管１１上に、燃料極を形成する。燃料極の形成方法として、スクリーン印刷、ジェットディスペンサによる製膜、ＣＶＤ法、転写法などが採用できる。円周方向及び軸方向に配置するセルの数、及び、セル間の距離に応じて、燃料極をパターニングして形成する。スクリーン印刷及びＣＶＤ法では、設けるセルの数及び位置に対応させたマスクを用いて、燃料極を成膜する。ジェットディスペンサを用いた製膜では、設けるセルの数及び位置に対応する部分にのみ、燃料極を形成する。 A process of forming the cell stack according to the first embodiment will be described below.
A fuel electrode is formed on the base tube 11. As a method for forming the fuel electrode, screen printing, film formation with a jet dispenser, CVD method, transfer method, or the like can be employed. The fuel electrode is formed by patterning according to the number of cells arranged in the circumferential direction and the axial direction and the distance between the cells. In the screen printing and the CVD method, the fuel electrode is formed using a mask corresponding to the number and position of cells to be provided. In film formation using a jet dispenser, a fuel electrode is formed only in a portion corresponding to the number and position of cells to be provided.

絶縁膜が設けられる場合は、燃料極が形成された後で固体電解質膜の形成前に絶縁膜の形成工程が実施される。燃料極のパターニングに対応させて、燃料極の間の基体管１１上に絶縁膜が形成される。絶縁膜の形成方法は、燃料極の形成方法と同様の方法が採用可能である。   When an insulating film is provided, an insulating film forming step is performed after the fuel electrode is formed and before the formation of the solid electrolyte film. Corresponding to the patterning of the fuel electrode, an insulating film is formed on the base tube 11 between the fuel electrodes. As a method for forming the insulating film, a method similar to the method for forming the fuel electrode can be employed.

燃料極及び基体管１１（あるいは絶縁膜）上に固体電解質膜を形成して、燃料極及び固体電解質膜の積層膜を作製する。固体電解質膜の形成方法は、燃料極の場合と同様の方法が採用可能である。１つのセル内で電流が流れる方向を考慮して、固体電解質膜の形成位置が決定される。図１では、１つのセル内で基体管の軸方向に紙面左から右に向かって電流が流れるので、固体電解質膜は燃料極に対して右側にずらして形成され、燃料極の紙面右側端部で基体管１１または絶縁膜と接触する。   A solid electrolyte film is formed on the fuel electrode and the base tube 11 (or insulating film) to produce a laminated film of the fuel electrode and the solid electrolyte film. As a method for forming the solid electrolyte membrane, the same method as that for the fuel electrode can be employed. The formation position of the solid electrolyte membrane is determined in consideration of the direction in which the current flows in one cell. In FIG. 1, since a current flows from left to right in the axial direction of the base tube in one cell, the solid electrolyte membrane is formed to be shifted to the right side with respect to the fuel electrode. In contact with the base tube 11 or the insulating film.

セル間を接続するインターコネクタを形成する。インターコネクタの形成方法は、燃料極の場合と同様の方法が採用可能である。第１実施形態では、図１で示した経路で直列接続するように、インターコネクタがパターニングされて形成される。具体的に、セル（１２ａ，１２ｃ）の正極側に位置する積層膜と、そのセル（１２ａ，１２ｃ）と基体管１１円周方向に隣接するセル（１２ｂ，１２ｄ）の負極側に位置する積層膜とを接続するようにインターコネクタが形成される。また、セル（１２ｂ）の正極側に位置する積層膜と、そのセル（１２ｂ）の隣のセル群内のセル（１２ｃ）の負極側に位置する積層膜とを接続するようにインターコネクタが形成される。   An interconnector for connecting cells is formed. As a method for forming the interconnector, the same method as that for the fuel electrode can be employed. In the first embodiment, the interconnector is formed by patterning so as to be connected in series along the path shown in FIG. Specifically, the laminated film located on the positive electrode side of the cell (12a, 12c) and the laminated film located on the negative electrode side of the cell (12a, 12d) adjacent to the cell (12a, 12c) in the circumferential direction of the substrate tube 11 An interconnector is formed to connect the membrane. An interconnector is formed so as to connect the laminated film located on the positive electrode side of the cell (12b) and the laminated film located on the negative electrode side of the cell (12c) in the cell group adjacent to the cell (12b). Is done.

基体管１１上に積層膜（燃料極、固体電解質膜）及びインターコネクタが形成された後に、基体管１１が大気中で共焼結される。焼結温度は、具体的に１３５０℃〜１４５０℃とされる。   After the laminated film (fuel electrode, solid electrolyte membrane) and the interconnector are formed on the base tube 11, the base tube 11 is co-sintered in the atmosphere. The sintering temperature is specifically 1350 ° C. to 1450 ° C.

共焼結後の基体管１１上に、空気極が形成される。空気極の形成方法は、燃料極の場合と同様の方法が採用可能である。セル形成部分に段差がある場合、均一に空気極を形成するためには、ジェットディスペンサによる製膜やＣＶＤ法など、製膜装置が基体管と接触しない製膜方法を採用することが好ましい。   An air electrode is formed on the base tube 11 after co-sintering. As a method for forming the air electrode, a method similar to that for the fuel electrode can be employed. In the case where there is a step in the cell forming portion, it is preferable to employ a film forming method in which the film forming apparatus does not contact the base tube, such as film formation by a jet dispenser or CVD method, in order to form the air electrode uniformly.

空気極が形成された基体管１１が、大気中にて焼結される。焼結温度は、具体的に１１００℃〜１２５０℃とされる。ここでの焼結温度は、基体管〜インターコネクタを形成した後の共焼結温度よりも低温とされる。   The base tube 11 on which the air electrode is formed is sintered in the atmosphere. The sintering temperature is specifically 1100 ° C. to 1250 ° C. The sintering temperature here is lower than the co-sintering temperature after forming the base tube to the interconnector.

本実施形態のセルスタックは、従来の基体管軸方向にのみセルを直列接続させる場合と比較して、基体管１１の軸方向でのセルの１２の寸法を大きくすることができる。
基体管軸方向のみにセルを配列した場合、基体管半径をｒ、基体管軸方向のセル（有効発電部）の長さをｌ１とすると、セルの面積Ｓは２πｒ×ｌ１となる。
一方、本実施形態のセルスタックでは、図１のように基体管円周方向に２つのセルを配列した場合、基体管軸方向のセルの長さは２πｒ×（１／２）である。基体管軸方向のセル（有効発電部）の長さをｌ２とすると、上記と同面積のセルとするためには、ｌ２＝Ｓ／（２πｒ×（１／２））＝２ｌ１となる。
このように、本実施形態のセルスタックでは、セルの基体管軸方向の寸法を広く確保することができるので、スクリーン印刷等による施工が容易になる。 The cell stack of this embodiment can increase the size of the cells 12 in the axial direction of the base tube 11 as compared with the case where the cells are connected in series only in the base tube axial direction.
When the cells are arranged only in the base tube axis direction, assuming that the base tube radius is r and the length of the cell (effective power generation unit) in the base tube axis direction is l 1 , the cell area S is 2πr × l 1 .
On the other hand, in the cell stack of this embodiment, when two cells are arranged in the circumferential direction of the base tube as shown in FIG. 1, the length of the cell in the base tube axis direction is 2πr × (½). When the length of the substrate tube axis direction of the cell (effective power generation unit) and l 2, in order to cells of the same area, l 2 = S / (2πr × (1/2)) = 2l 1 and Become.
Thus, in the cell stack of this embodiment, since the dimension of the cell in the base tube axis direction can be secured widely, the construction by screen printing or the like is facilitated.

図２は、第２実施形態のセルスタックの発電部について、外周面を平面に展開した概略図である。図２においてもインターコネクタは省略されている。
第２実施形態のセルスタック２０は、１つのセル２２内で電流が流れる方向は、基体管２１の円周方向である。隣り合うセル群２３Ａ，２３Ｂでは、１つのセル内で電流が流れる方向が反対となっている。第２実施形態においても、隣り合うセル群２３間では、セル２２は基体管２１軸方向の同位置に設けられている。 FIG. 2 is a schematic diagram in which the outer peripheral surface of the power generation unit of the cell stack of the second embodiment is developed in a plane. The interconnector is also omitted in FIG.
In the cell stack 20 of the second embodiment, the direction of current flow in one cell 22 is the circumferential direction of the base tube 21. In the adjacent cell groups 23A and 23B, the direction of current flow in one cell is opposite. Also in the second embodiment, between adjacent cell groups 23, the cells 22 are provided at the same position in the axial direction of the base tube 21.

図２内の矢印は、セル間の電気的な接続方向（電流が流れる方向）を表している。第１実施形態と同様に、基体管２１の両端部に集電部が設けられている。一方の端部の集電部は、基体管２１端部側に設けられるセル群２３Ａ内のセル２２ａの負極と直列接続する。セル群２３Ａ内で、セル２２ａ，ｂは直列接続する。セル２２ｂの正極は、セル群２３Ａに隣り合うセル群２３Ｂ内のセル２２ｃの負極と直列接続する。セル２２ｃは、基体管２１軸方向でセル２２ｂと隣り合っている。セル２２ｃは、同じセル群２３Ｂ内のセル２２ｄと直列接続する。基体管２１の他方の端部に設けられるセルまで、上記の接続が繰り返される。基体管２１の他方の端部に設けられるセル２２ｅの正極は、基体管２１の一方の端部の集電部と接続する。   The arrows in FIG. 2 represent the electrical connection direction between cells (the direction in which current flows). As in the first embodiment, current collectors are provided at both ends of the base tube 21. The current collector at one end is connected in series with the negative electrode of the cell 22a in the cell group 23A provided on the end of the base tube 21. In the cell group 23A, the cells 22a and 22b are connected in series. The positive electrode of the cell 22b is connected in series with the negative electrode of the cell 22c in the cell group 23B adjacent to the cell group 23A. The cell 22c is adjacent to the cell 22b in the axial direction of the base tube 21. The cell 22c is connected in series with the cell 22d in the same cell group 23B. The above connection is repeated up to the cell provided at the other end of the base tube 21. The positive electrode of the cell 22 e provided at the other end of the base tube 21 is connected to the current collector at one end of the base tube 21.

第２実施形態は、第１実施形態と比較してセル間の接続距離を更に短くすることができる。   In the second embodiment, the connection distance between cells can be further shortened as compared with the first embodiment.

第２実施形態のセルスタック２０は、第１実施形態と同様の工程にて作製される。第２実施形態では、セル内で電流が流れる方向と、セル間の接続経路とを考慮して、固体電解質膜、インターコネクタ及び空気極の形成位置が設定される。   The cell stack 20 of the second embodiment is manufactured by the same process as that of the first embodiment. In the second embodiment, the formation positions of the solid electrolyte membrane, the interconnector, and the air electrode are set in consideration of the direction in which the current flows in the cell and the connection path between the cells.

第２実施形態のセルスタック２０においても、隣り合うセルの燃料極の間に絶縁膜が設けられていても良い。   Also in the cell stack 20 of the second embodiment, an insulating film may be provided between the fuel electrodes of adjacent cells.

図３は、第３実施形態のセルスタックの発電部について、外周面を平面に展開した概略図である。図３においてもインターコネクタは省略されている。
第３実施形態のセルスタック３０において、１つのセル３２内で電流が流れる方向は基体管３１の円周方向である。隣り合うセル群３３間で、１つのセル３２内で電流が流れる方向は同じである。第３実施形態では、基体管３１の軸方向では、隣り合うセル群内のセルは位置をずらして配置されている。セル群３３Ａ内のセル３２ａ，ｂの位置は、隣のセル群３３Ｂ内のセル３２ｃ，ｄの位置と基体管３１の円周方向にずれている。有効発電部（燃料極と電解質と空気極との３層が重なる部分）の円周方向の長さをＬ１、インターコネクタの円周方向の長さをＬ２、セル間の円周方向の長さをＬ３とした場合に、セル３２ｃに対するセルａの円周方向へのずれ量Ｘ、及び、セル３２ｄに対するセル３２ｂの円周方向のずれ量Ｘは、Ｌ２＋Ｌ３≦Ｘ≦Ｌ１とする。 FIG. 3 is a schematic view in which the outer peripheral surface of the power generation unit of the cell stack of the third embodiment is developed in a plane. Also in FIG. 3, the interconnector is omitted.
In the cell stack 30 of the third embodiment, the direction of current flow in one cell 32 is the circumferential direction of the base tube 31. The direction in which current flows in one cell 32 between the adjacent cell groups 33 is the same. In the third embodiment, in the axial direction of the base tube 31, the cells in the adjacent cell group are arranged at different positions. The positions of the cells 32a, b in the cell group 33A are shifted from the positions of the cells 32c, d in the adjacent cell group 33B in the circumferential direction of the base tube 31. The circumferential length of the effective power generation unit (the portion where the three layers of the fuel electrode, electrolyte, and air electrode overlap) is L 1 , the length of the interconnector in the circumferential direction is L 2 , and the circumferential length between the cells When the length is L 3 , the amount X of displacement of the cell a in the circumferential direction with respect to the cell 32c and the amount of displacement X of the cell 32b in the circumferential direction with respect to the cell 32d are L 2 + L 3 ≦ X ≦ L Set to 1 .

図３内の矢印は、セル間の電気的な接続方向（電流が流れる方向）を表している。第１実施形態と同様に、基体管３１の一方の端部の集電部は、基体管３１端部側のセル群３３Ａ内のセル３２ａの負極と直列接続する。セル群３３Ａ内でセル３２ａ，３２ｂは直列接続する。セル３２ｂの正極は、セル群Ａの隣のセル群３３Ｂ内で最も近いセル３２ｃの負極と直列接続する。セル群３３Ｂ内で、セル３２ｃ，ｄは直列接続する。上記の接続は、基体管３１の他方の端部に設けられるセルまで繰り返される。基体管３１の他方の端部に設けられるセル３２ｅの正極は、基体管３１の一方の端部の集電部と接続する。   The arrows in FIG. 3 represent the electrical connection direction between cells (the direction in which current flows). As in the first embodiment, the current collector at one end of the base tube 31 is connected in series with the negative electrode of the cell 32a in the cell group 33A on the base tube 31 end side. The cells 32a and 32b are connected in series in the cell group 33A. The positive electrode of the cell 32b is connected in series with the negative electrode of the closest cell 32c in the cell group 33B adjacent to the cell group A. In the cell group 33B, the cells 32c and d are connected in series. The above connection is repeated up to the cell provided at the other end of the base tube 31. The positive electrode of the cell 32 e provided at the other end of the base tube 31 is connected to the current collector at one end of the base tube 31.

第３実施形態のセルスタック３０は、第１実施形態と同様の工程にて作製される。第３実施形態では、セルの配置、セル内で電流が流れる方向、及び、セル間の接続経路を考慮して、各層の形成位置が設定される。   The cell stack 30 of the third embodiment is manufactured by the same process as that of the first embodiment. In the third embodiment, the formation position of each layer is set in consideration of the arrangement of the cells, the direction in which the current flows in the cells, and the connection path between the cells.

なお、第３実施形態のセルスタック３０においても、隣り合うセルの燃料極の間に絶縁膜が設けられていても良い。   In the cell stack 30 of the third embodiment, an insulating film may be provided between the fuel electrodes of adjacent cells.

上述のようにセル３２を配置して接続することにより、各セル３２はらせん状に接続されることになる。こうすることで、セル間の接続距離を短くすることができる。更に、らせん状にセルを接続することによって、基体管軸方向に隣り合うセル間の電位差が小さくなる。   By arranging and connecting the cells 32 as described above, the cells 32 are spirally connected. By doing so, the connection distance between the cells can be shortened. Furthermore, by connecting the cells in a spiral shape, the potential difference between cells adjacent in the base tube axis direction is reduced.

例えば１つのセルで正極と負極との電位差が１Ｖであるとする。第２実施形態（図２）の接続では、基体管２１軸方向で隣り合うセル２２ａの負極とセル２２ｄの正極との電位差は、４Ｖになる。一方、第３実施形態（図３）のらせん状の接続では、基体管３１軸方向で隣り合うセル３２ｂの負極とセル３２ｄの正極との電位差は３Ｖとなる。   For example, it is assumed that the potential difference between the positive electrode and the negative electrode is 1 V in one cell. In the connection of the second embodiment (FIG. 2), the potential difference between the negative electrode of the cell 22a adjacent to the base tube 21 in the axial direction and the positive electrode of the cell 22d is 4V. On the other hand, in the spiral connection of the third embodiment (FIG. 3), the potential difference between the negative electrode of the cell 32b and the positive electrode of the cell 32d adjacent in the axial direction of the base tube 31 is 3V.

１つのセルスタック内でセル数を増やすにはセル間の距離を小さくする必要があるが、セル間の距離が小さく電位差が大きい場合には絶縁破壊が発生する恐れがある。このため、第２実施形態のように基体管軸方向に隣り合うセルの電位差が大きい場合には、絶縁破壊が発生しない程度にセル同士を離間させなくてはならない。第３実施形態は第２実施形態と比較して基体管軸方向に隣り合うセルの電位差が小さいために、セル間の距離をより縮めることが可能である。このため、第３実施形態のようにらせん状に電気的に接続すると、セル数を増加させることができ、高集積化が実現できる。   In order to increase the number of cells in one cell stack, it is necessary to reduce the distance between cells. However, when the distance between cells is small and the potential difference is large, there is a possibility that dielectric breakdown may occur. For this reason, when the potential difference between adjacent cells in the base tube axis direction is large as in the second embodiment, the cells must be separated from each other to such an extent that dielectric breakdown does not occur. Since the third embodiment has a smaller potential difference between cells adjacent in the base tube axis direction than the second embodiment, the distance between the cells can be further reduced. For this reason, when electrically connected in a spiral shape as in the third embodiment, the number of cells can be increased, and high integration can be realized.

１０，２０，３０ セルスタック
１１，２１，３１ 基体管
１２，１２ａ，１２ｂ，１２ｃ，１２ｄ，１２ｅ セル
２２，２２ａ，２２ｂ、２２ｃ，２２ｄ，２２ｅ セル
３２，３２ａ，３２ｂ、３２ｃ，３２ｄ，３２ｅ セル
１３，１３Ａ，１３Ｂ，２３，２３Ａ，２３Ｂ，３３，３３Ａ，３３Ｂ セル群 10, 20, 30 Cell stack 11, 21, 31 Base tube 12, 12a, 12b, 12c, 12d, 12e Cell 22, 22a, 22b, 22c, 22d, 22e Cell 32, 32a, 32b, 32c, 32d, 32e Cell 13, 13A, 13B, 23, 23A, 23B, 33, 33A, 33B cell group

Claims (5)

基体管上に燃料極と固体電解質膜と空気極とを備えるセルが前記基体管の円周方向に複数配列されたセル群を有し、前記セル群が前記基体管の軸方向に沿って複数配列され、
１つの前記セル群内で、前記基体管の円周方向に前記複数のセルがインターコネクタを介して電気的に直列接続され、
前記１つのセル群内の一のセルが、前記１つのセル群の隣の別のセル群内の一のセルと前記インターコネクタを介して電気的に直列接続される固体酸化物形燃料電池。 A cell having a fuel electrode, a solid electrolyte membrane, and an air electrode on a substrate tube has a cell group arranged in the circumferential direction of the substrate tube, and the cell group includes a plurality of cells along the axial direction of the substrate tube. Arranged,
Within one cell group, the plurality of cells are electrically connected in series via an interconnector in the circumferential direction of the base tube,
A solid oxide fuel cell in which one cell in the one cell group is electrically connected in series with one cell in another cell group adjacent to the one cell group via the interconnector. 前記基体管の軸方向に沿って、前記セルが整列されている請求項１に記載の固体酸化物形燃料電池。   The solid oxide fuel cell according to claim 1, wherein the cells are aligned along the axial direction of the base tube. 前記１つのセル群内の前記セルが、前記別のセル群内の前記セルと前記基体管の円周方向に位置がずれて配置され、
複数の前記セルが、前記基体管の軸方向に対してらせん状になるように電気的に直列に接続される請求項１に記載の固体酸化物形燃料電池。 The cells in the one cell group are arranged at positions shifted in the circumferential direction of the base tube and the cells in the other cell group,
The solid oxide fuel cell according to claim 1, wherein the plurality of cells are electrically connected in series so as to be spiral with respect to the axial direction of the base tube. 隣り合う前記セルの前記燃料極の間に、絶縁性材料からなる絶縁膜が形成されている請求項１乃至請求項３のいずれかに記載の固体酸化物形燃料電池。   The solid oxide fuel cell according to any one of claims 1 to 3, wherein an insulating film made of an insulating material is formed between the fuel electrodes of adjacent cells. 基体管の外周面上に、前記基体管の円周方向及び軸方向の各々に、複数の燃料極及び固体電解質膜の積層膜を形成する積層膜形成工程と、
前記基体管の円周方向に形成された前記複数の積層膜のうち一の積層膜と、該一の積層膜と前記基体管の軸方向で隣接する前記積層膜との間に、前記基体管の軸方向に電気的に直列接続するためのインターコネクタを形成する第１のインターコネクタ形成工程と、
前記基体管の円周方向で隣接する前記積層膜の間に、前記基体管の円周方向に電気的に直列接続するためのインターコネクタを形成する第２のインターコネクタ形成工程と、
前記第１のインターコネクタ形成工程及び前記第２のインターコネクタ形成工程の後に、前記積層体上に空気極を形成する工程とを有する固体酸化物形燃料電池の製造方法。 A laminated film forming step of forming a laminated film of a plurality of fuel electrodes and solid electrolyte membranes on the outer peripheral surface of the base tube in each of the circumferential direction and the axial direction of the base tube;
The substrate tube between one of the plurality of stacked films formed in the circumferential direction of the substrate tube and the stacked film adjacent to the one stacked film in the axial direction of the substrate tube A first interconnector forming step of forming an interconnector for electrical series connection in the axial direction of
A second interconnector forming step of forming an interconnector for electrically connecting in series in the circumferential direction of the base tube between the laminated films adjacent in the circumferential direction of the base tube;
A method of manufacturing a solid oxide fuel cell, comprising: forming an air electrode on the stacked body after the first interconnector forming step and the second interconnector forming step.
JP2012037918A 2012-02-23 2012-02-23 Solid oxide fuel cell and method of manufacturing solid oxide fuel cell Ceased JP2013175307A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012037918A JP2013175307A (en) 2012-02-23 2012-02-23 Solid oxide fuel cell and method of manufacturing solid oxide fuel cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012037918A JP2013175307A (en) 2012-02-23 2012-02-23 Solid oxide fuel cell and method of manufacturing solid oxide fuel cell

Publications (1)

Publication Number Publication Date
JP2013175307A true JP2013175307A (en) 2013-09-05

Family

ID=49268055

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2012037918A Ceased JP2013175307A (en) 2012-02-23 2012-02-23 Solid oxide fuel cell and method of manufacturing solid oxide fuel cell

Country Status (1)

Country Link
JP (1) JP2013175307A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016072215A (en) * 2014-09-30 2016-05-09 Toto株式会社 Solid oxide fuel cell stack
JP2016072216A (en) * 2014-09-30 2016-05-09 Toto株式会社 Solid oxide fuel cell stack

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003187828A (en) * 2001-12-20 2003-07-04 Nisshin Steel Co Ltd Ferritic stainless steel for solid oxide type fuel cell member
JP2005235658A (en) * 2004-02-20 2005-09-02 Dainippon Printing Co Ltd Solid-oxide fuel cell and board using the same
JP2005353571A (en) * 2004-05-10 2005-12-22 Shinko Electric Ind Co Ltd Solid electrolyte fuel cell
JP2006179291A (en) * 2004-12-22 2006-07-06 Shinko Electric Ind Co Ltd Fuel cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003187828A (en) * 2001-12-20 2003-07-04 Nisshin Steel Co Ltd Ferritic stainless steel for solid oxide type fuel cell member
JP2005235658A (en) * 2004-02-20 2005-09-02 Dainippon Printing Co Ltd Solid-oxide fuel cell and board using the same
JP2005353571A (en) * 2004-05-10 2005-12-22 Shinko Electric Ind Co Ltd Solid electrolyte fuel cell
JP2006179291A (en) * 2004-12-22 2006-07-06 Shinko Electric Ind Co Ltd Fuel cell

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016072215A (en) * 2014-09-30 2016-05-09 Toto株式会社 Solid oxide fuel cell stack
JP2016072216A (en) * 2014-09-30 2016-05-09 Toto株式会社 Solid oxide fuel cell stack

Similar Documents

Publication Publication Date Title
JP4828664B1 (en) Fuel cell structure
JP5117600B2 (en) Fuel cell structure
KR101869305B1 (en) Cell, cell stacker, module, and module storage device
JP2013175306A (en) Solid oxide fuel battery
JP2013110092A (en) Fuel cell structure
US9761895B2 (en) Cell stack device, fuel cell module, fuel cell device, and method of fabricating cell stack device
JP4883733B1 (en) Fuel cell structure
JP5116182B1 (en) Fuel cell structure
JP2013175307A (en) Solid oxide fuel cell and method of manufacturing solid oxide fuel cell
JP2012181927A (en) Solid oxide fuel cell and fuel cell module
JP5717559B2 (en) Covered film member, current collecting member, and fuel cell apparatus
JP5501882B2 (en) Solid oxide fuel cell and method for producing the same
JPWO2018199095A1 (en) Solid oxide fuel cell
JP6898188B2 (en) Fuel cell stack
JP5417548B2 (en) Fuel cell structure
JP5062786B1 (en) Fuel cell structure
JP5959404B2 (en) Fuel cell stack unit
JP2013093177A (en) Fuel cell structure
KR20110056574A (en) Flat tubular solid oxide fuel cell and method of manufacturing the same
JP6983017B2 (en) Fuel cell stack
WO2020022489A1 (en) Fuel battery cell and cell stack device
WO2019208187A1 (en) Solid oxide fuel battery cell
JP6039461B2 (en) Solid oxide fuel cell
JP2014191992A (en) Method for manufacturing solid oxide fuel battery
JP5717573B2 (en) Cell stack and fuel cell module

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20141226

A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A712

Effective date: 20150119

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20150911

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20150929

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20151016

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20160209

A045 Written measure of dismissal of application

Free format text: JAPANESE INTERMEDIATE CODE: A045

Effective date: 20160628