JPH0831446A - Solid electrolyte fuel cell - Google Patents
Solid electrolyte fuel cellInfo
- Publication number
- JPH0831446A JPH0831446A JP6169666A JP16966694A JPH0831446A JP H0831446 A JPH0831446 A JP H0831446A JP 6169666 A JP6169666 A JP 6169666A JP 16966694 A JP16966694 A JP 16966694A JP H0831446 A JPH0831446 A JP H0831446A
- Authority
- JP
- Japan
- Prior art keywords
- fuel electrode
- layer
- nio
- electrolyte
- layers
- 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.)
- Withdrawn
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 56
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 11
- 230000007423 decrease Effects 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 230000008646 thermal stress Effects 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
- H01M4/8642—Gradient in composition
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、固体電解質燃料電池
（以下ＳＯＦＣという）の燃料極に適用される皮膜の構
成に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the constitution of a coating applied to the fuel electrode of a solid oxide fuel cell (hereinafter referred to as SOFC).
【０００２】[0002]
【従来の技術】ＳＯＦＣは、ポーラスなセラミックチュ
ーブ（以下基体管という）の上に、燃料極、電解質、空
気極を前記順に積層したものからなり、作動温度約１０
００℃で酸素イオンと水素イオンを反応させて発電する
電池である。そして基体管には、ＺｒＯ2 −ＣａＯ、燃
料極には、ＮｉＯ、電解質にはＺｒＯ2 −Ｙ2 Ｏ3 、空
気極には、ＬａＣｏＯ3の材料などが使用される。2. Description of the Related Art An SOFC comprises a porous ceramic tube (hereinafter referred to as a substrate tube) on which a fuel electrode, an electrolyte, and an air electrode are laminated in the stated order.
It is a battery that generates electric power by reacting oxygen ions and hydrogen ions at 00 ° C. Then, ZrO2-CaO is used for the base tube, NiO is used for the fuel electrode, ZrO2-Y2O3 is used for the electrolyte, and LaCoO3 is used for the air electrode.
【０００３】[0003]
【発明が解決しようとする課題】従来のＳＯＦＣを約１
０００℃で発電させると、燃料極に割れや剥離などが生
じ、大幅な出力低下が生じることがある。燃料極に損傷
が生じる原因は、燃料極（主成分ＮｉＯ）と基体管（主
成分ＺｒＯ2 −ＣａＯ）の線膨脹係数αの差（基体管Ｚ
ｒＯ2 −ＣａＯの線膨脹係数：１０×１０-6／℃、燃料
極ＮｉＯの線膨脹係数：１４×１０-6／℃）が考えられ
る。燃料極の線膨脹係数α2 を基体管の線膨脹係数α1
に近づける方法として、燃料極のＮｉＯにＹＳＺ（Ｚｒ
Ｏ2 −Ｙ2 Ｏ3 ）を混合する方法があるが、ＮｉＯ・Ｙ
ＳＺ複合材は導電率が低く、性能（出力密度）に優れた
ＳＯＦＣを製作するのは困難である。The conventional SOFC has about 1
When power is generated at 000 ° C., the fuel electrode may be cracked or peeled off, resulting in a large reduction in output. The cause of the damage to the fuel electrode is the difference in the linear expansion coefficient α between the fuel electrode (main component NiO) and the base pipe (main component ZrO 2 -CaO) (base pipe Z
A linear expansion coefficient of rO 2 -CaO: 10 × 10 −6 / ° C. and a linear expansion coefficient of fuel electrode NiO: 14 × 10 −6 / ° C.) are considered. The linear expansion coefficient α2 of the fuel electrode is the linear expansion coefficient α1 of the base tube.
As a method of approaching YSZ (Zr
There is a method of mixing O2-Y2O3), but NiO.Y
Since the SZ composite material has a low conductivity, it is difficult to manufacture an SOFC excellent in performance (power density).
【０００４】本発明は、前記問題点を解決することがで
きるＳＯＦＣすなわち、燃料極の導電率を確保しつつ、
燃料極の割れや剥離を防止することができる固体電解質
燃料電池（ＳＯＦＣ）を提供することを目的とする。The present invention secures the SOFC capable of solving the above problems, that is, the conductivity of the fuel electrode,
It is an object of the present invention to provide a solid oxide fuel cell (SOFC) capable of preventing the fuel electrode from cracking or peeling.
【０００５】[0005]
【課題を解決するための手段】本発明に係る固体電解質
燃料電池は、ポーラスなセラミックチューブの基体管の
上に燃料極と電解質と空気極を前記順に積層した固体電
解質燃料電池において、（Ａ）前記燃料極は、Ａ層とＢ
層とＣ層を前記順に積層した３層からなり、（Ｂ）前記
燃料極のＢ層はＮｉＯで構成し、（Ｃ）前記Ｂ層と、基
体管の間に設けたＡ層は、ＮｉＯ・ＹＳＺ複合傾斜材で
構成するとともに、ＮｉＯの含有率をＢ層側では高く基
体管に向かって徐々に低下させ、（Ｄ）前記Ｂ層と電解
質の間に設けたＣ層はＮｉＯ・ＹＳＺ複合傾斜材で構成
するとともに、ＮｉＯ含有率をＢ層側では高く、電解質
に向かって徐々に低下させることを特徴とする。The solid electrolyte fuel cell according to the present invention is a solid electrolyte fuel cell in which a fuel electrode, an electrolyte and an air electrode are laminated in the above-mentioned order on a substrate tube of a porous ceramic tube (A). The fuel electrode consists of layers A and B
(B) The B layer of the fuel electrode is made of NiO, and (C) the B layer and the A layer provided between the base tube are made of NiO. In addition to being composed of a YSZ composite gradient material, the NiO content is high on the B layer side and gradually decreases toward the substrate tube, and (D) the C layer provided between the B layer and the electrolyte is a NiO.YSZ composite gradient material. In addition to being made of a material, the NiO content is high on the B layer side and gradually decreases toward the electrolyte.
【０００６】[0006]
【作用】図１及び図２に示すように、燃料極のＢ層をＮ
ｉＯ１００％の層とし、燃料極のＡ層のＮｉＯ・ＹＳＺ
複合材におけるＮｉＯ含有率を基体管側に徐々に低下さ
せるとともに、Ｃ層におけるＮｉＯ・ＹＳＺ複合材にお
けるＮｉＯ含有率を電解質側に徐々に低下させることに
より、ＮｉＯ１００％１層の場合よりも、燃料極に生じ
る熱応力を緩和することができる。また、ＮｉＯ・ＹＳ
Ｚ複合材は、導電率が低いので、Ａ層とＣ層の複合材の
間にＮｉＯ１００％のＢ層を形成し、この膜に導電膜と
しての機能をもたせる。As shown in FIG. 1 and FIG. 2, the B layer of the fuel electrode is
NiO / YSZ of A layer of fuel electrode as a layer of 100% io
By gradually decreasing the NiO content in the composite material toward the base tube side and gradually decreasing the NiO content in the NiO.YSZ composite material in the C layer toward the electrolyte side, the NiO content is lower than that in the case of one layer of 100% NiO. The thermal stress generated in the pole can be relieved. Also, NiO / YS
Since the Z composite material has a low electric conductivity, a B layer of 100% NiO is formed between the composite material of the A layer and the C layer, and this film has a function as a conductive film.
【０００７】また、電解質（ＺｒＯ2 −Ｙ2 Ｏ3 ）、及
び基体管（ＺｒＯ2 −ＣａＯ）側にＹＳＺの含有率が高
い複合膜を配置し（電解質、基体管に近い成分を配置
し）、電解質と燃料極間、及び基体管と燃料極間の密着
性を向上させる。Further, an electrolyte (ZrO2-Y2O3) and a composite film having a high YSZ content are arranged on the side of the base tube (ZrO2-CaO) (an electrolyte and a component close to the base tube are arranged), and an electrolyte and a fuel are provided. Improves the adhesion between the electrodes and between the base tube and the fuel electrode.
【０００８】[0008]
【実施例】本発明の第１実施例を図１及び図２に示す。
図１に示すように、基体管１の上に、燃料極２、電解質
３、空気極４を上記順に溶射法により成膜する点は、従
来のＳＯＦＣと同じである。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of the present invention is shown in FIGS.
As shown in FIG. 1, the fuel electrode 2, the electrolyte 3, and the air electrode 4 are formed on the substrate tube 1 in this order by a thermal spraying method in the same manner as in the conventional SOFC.
【０００９】ここで本発明の特徴とするＳＯＦＣは、燃
料極２を図２に示すように、Ａ層、Ｂ層、Ｃ層の３層で
構成し、Ａ層はＮｉＯ・ＹＳＺ複合傾斜材（基体管側へ
徐々にＮｉＯの含有率を低下させる）で構成し、Ｂ層は
ＮｉＯ１００％で構成し、Ｃ層はＮｉＯ・ＹＳＺ複合傾
斜材（電解質側へ徐々にＮｉＯの含有率を低下させる）
で構成する。In the SOFC, which is a feature of the present invention, the fuel electrode 2 is composed of three layers of A layer, B layer and C layer as shown in FIG. 2, and the A layer is a NiO / YSZ composite gradient material ( The B layer is made of 100% NiO, and the C layer is made of a NiO / YSZ composite gradient material (the NiO content is gradually reduced toward the electrolyte side).
It consists of.
【００１０】このように燃料極のＡ層とＣ層はＮｉＯ・
ＹＳＺ複合傾斜材を用いることによって、燃料極２に生
じる熱応力を緩和させ、他方、燃料極の導電機能は、Ｎ
ｉＯ１００％で構成するＢ層にもたせる。また、電解質
及び基体管側にＹＳＺの含有率が高い複合膜を配置し
（電解質、基体管に近い成分を配置し）、電解質３と燃
料極２の間、及び基体管１燃料極２間の密着性を向上さ
せる。そのため、本発明により、燃料極の導電性を確保
しつつ、燃料極に生じる割れや剥離を防止することがで
きるＳＯＦＣを実現することができる。Thus, the A and C layers of the fuel electrode are made of NiO.
By using the YSZ composite gradient material, the thermal stress generated in the fuel electrode 2 is relaxed, while the conductive function of the fuel electrode is N
It is also applied to the layer B composed of 100% of iO. In addition, a composite film having a high YSZ content is arranged on the electrolyte and the base tube side (the electrolyte and components close to the base tube are arranged), and between the electrolyte 3 and the fuel electrode 2 and between the base tube 1 and the fuel electrode 2. Improves adhesion. Therefore, according to the present invention, it is possible to realize an SOFC that can prevent cracks and peeling that occur in the fuel electrode while ensuring the conductivity of the fuel electrode.
【００１１】[0011]
【発明の効果】本発明は前述のように構成されているの
で、以下に記載するような効果を奏する。 （１）燃料極２を図２に示すように、Ａ層、Ｂ層、Ｃ層
の３層で構成することにより、燃料極の導電性を確保し
つつ、燃料極に生じる熱応力を緩和することにより、燃
料極に生じる割れや剥離を防止することができる。 （２）そのため高性能で耐久性に優れたＳＯＦＣを実現
することができる。Since the present invention is constructed as described above, it has the following effects. (1) As shown in FIG. 2, the fuel electrode 2 is composed of three layers, that is, an A layer, a B layer, and a C layer, so that the conductivity of the fuel electrode is secured and the thermal stress generated in the fuel electrode is relaxed. As a result, it is possible to prevent the fuel electrode from cracking or peeling. (2) Therefore, an SOFC having high performance and excellent durability can be realized.
【図１】本発明の第１実施例に係るＳＯＦＣの構成図。FIG. 1 is a configuration diagram of an SOFC according to a first embodiment of the present invention.
【図２】第１実施例の燃料極の構成図。FIG. 2 is a configuration diagram of a fuel electrode according to the first embodiment.
【符号の説明】 １…基体管、 ２…燃料極、 ３…電解質、 ４…空気極、 α…線膨脹係数、 α1 …線膨脹係数（基体管）、 α2 …線膨脹係数（燃料極）。[Explanation of Codes] 1 ... Substrate tube, 2 ... Fuel electrode, 3 ... Electrolyte, 4 ... Air electrode, α ... Linear expansion coefficient, α1 ... Linear expansion coefficient (base tube), α2 ... Linear expansion coefficient (fuel electrode).
Claims (1)
（１）の上に燃料極（２）と電解質（３）と空気極
（４）を前記順に積層した固体電解質燃料電池におい
て、（Ａ）前記燃料極（２）は、Ａ層とＢ層とＣ層を前
記順に積層した３層からなり、（Ｂ）前記燃料極のＢ層
はＮｉＯで構成し、（Ｃ）前記Ｂ層と、基体管（１）の
間に設けたＡ層は、ＮｉＯ・ＹＳＺ複合傾斜材で構成す
るとともに、ＮｉＯの含有率をＢ層側では高く基体管に
向かって徐々に低下させ、（Ｄ）前記Ｂ層と電解質
（３）の間に設けたＣ層はＮｉＯ・ＹＳＺ複合傾斜材で
構成するとともに、ＮｉＯ含有率をＢ層側では高く、電
解質に向かって徐々に低下させることを特徴とする固体
電解質燃料電池。1. A solid electrolyte fuel cell in which a fuel electrode (2), an electrolyte (3) and an air electrode (4) are laminated in this order on a base tube (1) of a porous ceramic tube, wherein (A) the fuel The electrode (2) is composed of three layers in which an A layer, a B layer and a C layer are laminated in this order, (B) the B layer of the fuel electrode is composed of NiO, (C) the B layer and a base tube ( The layer A provided between 1) is composed of a NiO / YSZ composite gradient material, and the content of NiO is high on the layer B side, and gradually decreases toward the base tube, and (D) the layer B and the electrolyte. A solid electrolyte fuel cell characterized in that the C layer provided between (3) is composed of a NiO / YSZ composite gradient material, and the NiO content is high on the B layer side and gradually decreases toward the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6169666A JPH0831446A (en) | 1994-07-21 | 1994-07-21 | Solid electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6169666A JPH0831446A (en) | 1994-07-21 | 1994-07-21 | Solid electrolyte fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0831446A true JPH0831446A (en) | 1996-02-02 |
Family
ID=15890674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6169666A Withdrawn JPH0831446A (en) | 1994-07-21 | 1994-07-21 | Solid electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0831446A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1016458C2 (en) * | 2000-10-23 | 2002-05-01 | Stichting En Onderzoek Ct Nede | Anode assembly. |
| EP1284519A2 (en) | 2001-08-14 | 2003-02-19 | Nissan Motor Co., Ltd. | Solid electrolyte fuel cell and related manufacturing method |
-
1994
- 1994-07-21 JP JP6169666A patent/JPH0831446A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1016458C2 (en) * | 2000-10-23 | 2002-05-01 | Stichting En Onderzoek Ct Nede | Anode assembly. |
| WO2002035634A1 (en) * | 2000-10-23 | 2002-05-02 | Stichting Energieonderzoek Centrum Nederland | Anode assembly for an electrochemical cell |
| EP1284519A2 (en) | 2001-08-14 | 2003-02-19 | Nissan Motor Co., Ltd. | Solid electrolyte fuel cell and related manufacturing method |
| EP1284519A3 (en) * | 2001-08-14 | 2008-07-16 | Nissan Motor Co., Ltd. | Solid electrolyte fuel cell and related manufacturing method |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20011002 |