JPH0237669A - Fuel cell of solid electrolyte type - Google Patents
Fuel cell of solid electrolyte typeInfo
- Publication number
- JPH0237669A JPH0237669A JP63329105A JP32910588A JPH0237669A JP H0237669 A JPH0237669 A JP H0237669A JP 63329105 A JP63329105 A JP 63329105A JP 32910588 A JP32910588 A JP 32910588A JP H0237669 A JPH0237669 A JP H0237669A
- Authority
- JP
- Japan
- Prior art keywords
- anode
- interconnector
- cathode
- grooves
- solid electrolyte
- 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.)
- Pending
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 27
- 239000000446 fuel Substances 0.000 title claims description 26
- 239000007789 gas Substances 0.000 claims abstract description 31
- 239000002737 fuel gas Substances 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000010354 integration Effects 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000956 alloy Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は固定電解質型燃料電池に係り、より詳しくはプ
ラナ−型構造を有する固体電解質型燃料電池に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fixed electrolyte fuel cell, and more particularly to a solid electrolyte fuel cell having a planar structure.
固体電解質型燃料電池は酸素イオン導電性を有する固体
を電解質とし、燃料ガスとして水素、酸化炭素、ナフサ
ガス、ナフサ改質ガス、液化天然ガス（ＬＮＧ）など、
酸化剤として酸累（空気）を用い、約１０００℃で作動
させる燃料電池である。この型の燃料電池の構造として
は、ウェスチングハウス社及び電子技術総合研究所から
第６図に示す円筒型の構造が提案されている。同図にお
いて、管状体ｌの内部に燃料ガスが送られるとともに、
外部を酸化剤ガスが通る。同図中の管壁部分の拡大図に
見られるように、管壁部分に主要構造が形成され、支持
管をなす多孔性アルミナ壁２上に、多孔性Ｎｉ アノー
ド３、インターコネクタ４、電解質５、複合酸化物カソ
ード６、アルミナ気密被膜７からなるセルの集積構造が
形成されている。A solid electrolyte fuel cell uses a solid having oxygen ion conductivity as an electrolyte, and uses hydrogen, carbon oxide, naphtha gas, naphtha reformed gas, liquefied natural gas (LNG), etc. as a fuel gas.
This is a fuel cell that uses acid accumulation (air) as an oxidant and operates at approximately 1000°C. As the structure of this type of fuel cell, a cylindrical structure shown in FIG. 6 has been proposed by the Westinghouse Company and the Electronic Technology Research Institute. In the figure, fuel gas is sent inside the tubular body l, and
Oxidizing gas passes through the outside. As seen in the enlarged view of the tube wall in the same figure, the main structures are formed in the tube wall, with a porous Ni anode 3, an interconnector 4, an electrolyte 5 on a porous alumina wall 2 forming a support tube. , a composite oxide cathode 6 , and an alumina airtight coating 7 .
そのほか、ウェスチングハウス社から別の円筒型構造及
びその連結構造が開発され、またアルゴンヌ国立研究所
からモノシリツク型の構造が開発されている（後者を第
７図に示す）。In addition, another cylindrical structure and its connection structure have been developed by Westinghouse, and a monolithic structure has been developed by Argonne National Laboratory (the latter is shown in FIG. 7).
第６図に示した円筒型構造では、円筒の半径方向にカソ
ード−固体電解質−アノード間で電流が流れるが、集積
構造体としては、単位セルで発生した電流はカソード−
インターコネクターアノードと円筒の長さ方向に流れる
ため、シート抵抗の大きいカソード、アノード中の長い
電流路を流れる必要があり、その間のオーム損が大きい
という問題がある。固体電解質型燃料電池では高温で作
動されるため電極の腐食の問題が激しく、電極材料とし
て面積抵抗の大きい材料を使わざるを得ないからである
。ウェスチングハウス社の別の円筒型構造タイプの固体
電解質型燃料電池でも、面積抵抗の大きいカソード、ア
ノードの長い電流路によるオーム損の問題は解決されて
いない。In the cylindrical structure shown in Figure 6, current flows between the cathode, solid electrolyte and anode in the radial direction of the cylinder, but as an integrated structure, the current generated in a unit cell flows between the cathode and the solid electrolyte.
Since the current flows in the longitudinal direction of the interconnector anode and the cylinder, it needs to flow through a long current path in the cathode and anode, which have high sheet resistance, and there is a problem in that the ohmic loss between them is large. This is because solid oxide fuel cells are operated at high temperatures, so electrode corrosion is a serious problem, and a material with high sheet resistance must be used as the electrode material. Even with Westinghouse's other cylindrical structure type solid oxide fuel cell, the problem of ohmic loss due to the long current path of the cathode and anode, which have high sheet resistance, remains unsolved.
一方、アルインタ国立研究所のモノシリツク型燃料電池
では、円筒型では達成されない高い集積度と短かい電流
路を実現しているが、構造が複雑で高度な構成技術を要
するものであるため、信頼性に問題があり、実用化には
ほど遠い。On the other hand, the monolithic fuel cell at Al Inta National Laboratory achieves a high degree of integration and a short current path that cannot be achieved with a cylindrical type, but because it has a complex structure and requires advanced construction technology, it is not reliable. There are problems with this, and it is far from practical use.
そこで、本発明は高抵抗部分の電流路が短かく、集積度
が高く、しかも信頼性の高い固体電解質型燃料電池の構
造を提供することを目的とする。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a structure of a solid oxide fuel cell that has a short current path in a high resistance portion, has a high degree of integration, and is highly reliable.
本発明は、上記目的を達成するために、１面に多孔性カ
ソード層、他面に多孔性アノード層を付着した平板状固
体電解質板を、両面にガス通路を構成する溝をそれぞれ
形成した導電性インターコネクタ板を介して複数個積層
し、それらの溝を通してカソード側に酸化剤ガス、アノ
ード側に燃料ガスを供給し、そして積層セルの上下端の
アノードとカソードより電流を取り出す構造を有する固
体電解質型燃料電池を提供する。In order to achieve the above object, the present invention provides a flat solid electrolyte plate having a porous cathode layer attached to one side and a porous anode layer attached to the other side. A solid cell having a structure in which multiple cells are stacked together via a conductive interconnect plate, oxidant gas is supplied to the cathode side and fuel gas is supplied to the anode side through the grooves, and current is extracted from the anode and cathode at the upper and lower ends of the stacked cell. Provides electrolyte fuel cells.
このようなプラナ−型構造の燃料電池は、炭酸塩型燃料
電池などでは知られているが、固体電解質型燃料電池で
は知られていない。その理由は次のように考えられる。Fuel cells with such a planar structure are known as carbonate fuel cells, but are not known as solid oxide fuel cells. The reason may be as follows.
従来インターコネクタとしては、クロマイト系の複合酸
化物（例えば：Ｌａ＋ ＪＪｇｘＣｒＯｓ又はしａ、
、Ａ１．Ｃｒ０３）等を用いているが、これらはち密な
焼結が難しく、またきわめて脆い為、本発明で主張する
様な構造を制作する事ができなかった。又、インターコ
ネクタに金属を用いようとすると、酸化剤側での１００
０℃における金属の酸化の為、インターコネクタと電極
間の接触抵抗が増大してしまい、セル特性を著しく悪化
する。Conventional interconnectors include chromite-based composite oxides (for example: La+ JJgxCrOs or Shia,
, A1. Cr03) etc. are used, but these materials are difficult to sinter in a dense manner and are extremely brittle, making it impossible to produce the structure claimed in the present invention. Also, if you try to use metal for the interconnector, 100
Due to metal oxidation at 0° C., the contact resistance between the interconnector and the electrode increases, significantly degrading the cell characteristics.
そこで、本発明者は前記目的を達成するために鋭意検討
する過程で、耐熱性耐食性のインターコネクタ用の材質
を開発するなどの工夫をすることによって固体電解質型
燃料電池においてもプラナ−型構造が実現可能であるこ
と、またこのようなプラナ−型構造によれば高抵抗部分
の電流路が短かく、集積度が高く、かつ信頼性の高い固
体電解質型燃料電池を提供することが可能であることを
見い出し、そして本発明を完成した。Therefore, in the process of intensive study to achieve the above object, the inventor of the present invention developed a heat-resistant and corrosion-resistant material for interconnectors, thereby creating a planar structure in solid oxide fuel cells. It is possible to realize this, and with such a planar structure, it is possible to provide a solid oxide fuel cell with a short current path in a high resistance portion, a high degree of integration, and high reliability. They discovered this and completed the present invention.
第１図に３段室列セルの集合様式を展開して示す。各セ
ルにおいて平板状固体電解質板１１は両面にそれぞれカ
ソード１２及びアノード１３が形成されている。固体電
解質板１１は酸素伝導性のある固体電解質、例えば、部
分安定化ジルコニア（イントリアを２〜５ ｍｏｆ％含
有するジルコニア）安定化ジルコニアなど公知の固体電
解質で作った板状物からなり、厚さは０．０５〜０．３
ｍｍ程度、より好ましくは０．０８〜０．２５ｍｍ程
度が適当である。０．０５ｍｍよりも薄いと強度上問題
があり、０．３ ｍｍを越えると電流路が長くなり好ま
しくない。カソード１２は酸素通路側なので高温下で酸
素に対して耐食性のある導電性材料を用い、多孔状に形
成する。FIG. 1 shows the arrangement of three-tier cells in an expanded manner. In each cell, a cathode 12 and an anode 13 are formed on both sides of the flat solid electrolyte plate 11, respectively. The solid electrolyte plate 11 is made of a plate-like material made of a known solid electrolyte such as an oxygen-conducting solid electrolyte, such as partially stabilized zirconia (zirconia containing 2 to 5 mof% of Intoria), and stabilized zirconia. is 0.05-0.3
Approximately 0.08 to 0.25 mm is appropriate. If it is thinner than 0.05 mm, there is a problem in terms of strength, and if it exceeds 0.3 mm, the current path becomes long, which is not preferable. Since the cathode 12 is on the oxygen passage side, it is made of a conductive material that is resistant to oxygen corrosion at high temperatures, and is formed in a porous shape.
例えば、しａイＳｒ＋−Ｊ００３などの導電性複合酸化
物粉末を塗布する。塗布の手法としてははけ塗り法、ス
クリーン印刷法がある。その他、多孔状膜の作製方法と
してはＣＶＤ法、プラズマＣＶＤ法、スパッタ法、溶射
法等が可能である。カソード１２はガス透過性となる程
度に多孔性に形成する。アノード１３は水素通路側で、
高温下で水素に対して耐食性のある導電性材料（例えば
、Ｎｉ／２ｒＯ２サーメツトなど）を多孔状に形成する
。例えば、す−ノット粉末混合物を塗布して形成する。For example, a conductive composite oxide powder such as Sr+-J003 is applied. Application methods include brushing and screen printing. Other possible methods for producing the porous film include CVD, plasma CVD, sputtering, and thermal spraying. The cathode 12 is formed to be porous to the extent that it is gas permeable. The anode 13 is on the hydrogen passage side,
A conductive material (for example, Ni/2rO2 cermet) that is resistant to hydrogen corrosion at high temperatures is formed into a porous shape. For example, it is formed by applying a knot powder mixture.
アノード１３もガス透過性に形成する。また、カソード
、アノードは多孔性の板状化が可能であれば、それを固
体電解質と付着させて使用することも可能である。The anode 13 is also formed to be gas permeable. Further, if the cathode and anode can be formed into porous plates, they can also be used by attaching them to a solid electrolyte.
各セルの両面にカソード１２とアノード１３を形成され
た固体電解質板１１はインターコネクタ１４を介して集
積し、両端には外部端子１５．１６をそれぞれ設ける。Solid electrolyte plates 11 having cathodes 12 and anodes 13 formed on both sides of each cell are integrated via interconnectors 14, and external terminals 15 and 16 are provided at both ends, respectively.
第１図に見られる如く、インターコネクタ１４は隣接す
るセルの電極間を電気的に接続するとともに、両面に溝
１４ａ、１４ｂが形成されて隣接するセルのカソード側
及びアノード側のそれぞれのガス通路を形成するもので
ある。インターコネクタ１４は高温下で使用するガスに
耐食性を有しかつ導電性の良好な材料で形成する。As seen in FIG. 1, the interconnector 14 electrically connects the electrodes of adjacent cells, and has grooves 14a and 14b formed on both sides to provide gas passages on the cathode side and anode side of the adjacent cells. It forms the The interconnector 14 is made of a material that is resistant to corrosion by gases used at high temperatures and has good electrical conductivity.
このインターコネクタ１４は本出願人が先に開示した導
電性耐熱部品で構成することができる（特願昭６２−２
５７２７４号及び同６２−２５８３２０号及びその国内
優先権主張出願明細書）。この耐熱部品はクロム、コバ
ルト、ニッケル、鉄又はマンガンヲ含ム耐熱合金基材を
用いて表面にＬａ＋−ｘＭ’、Ｍ２０ｚ （式中、Ｍｌ
はアルカリ土類金属、Ｍ２はクロム、コバルト、ニッケ
ル、鉄、マンガン等、０≦ｘ〈１である）の複合酸化物
を形成したものである。また、耐熱合金の表面に耐食性
があり、高融点の被膜、例えば白金などの貴金属の被膜
を施したものも好ましく用いることができる。これらの
耐熱部品であれば使用温度が１０００℃を越えても熱膨
張による変形が小さく、またその表面には複合酸化物や
耐食性被膜を有するので、電極間の接触抵抗が堆犬せず
、セル特性を低下させることがない。This interconnector 14 can be constructed from a conductive heat-resistant component previously disclosed by the applicant (Japanese Patent Application No. 62-2
No. 57274 and No. 62-258320 and their domestic priority application specifications). This heat-resistant part uses a heat-resistant alloy base material containing chromium, cobalt, nickel, iron, or manganese, and the surface is coated with La+-xM', M20z (in the formula, Ml
is an alkaline earth metal, and M2 is a composite oxide of chromium, cobalt, nickel, iron, manganese, etc. (0≦x<1). Also preferably used is a heat-resistant alloy whose surface is coated with a coating having corrosion resistance and a high melting point, such as a coating of a noble metal such as platinum. These heat-resistant parts have little deformation due to thermal expansion even when the operating temperature exceeds 1000°C, and their surfaces are coated with complex oxides and corrosion-resistant coatings, so the contact resistance between electrodes does not build up and the cell No deterioration of properties.
インターコネクタ１４と固体電解質板１１とは、ガスシ
ール性や寸法設計上、熱膨張率の差ができるだけ小さい
ことが有利である。そこで、固体電解質としてジルコニ
ア電解質を用いる場合に、これと熱膨張率の近い導電性
材料として金属クロムが好ましいことが見い出された。It is advantageous for the interconnector 14 and the solid electrolyte plate 11 to have as small a difference in thermal expansion coefficient as possible in terms of gas sealing properties and dimensional design. Therefore, when using a zirconia electrolyte as a solid electrolyte, it has been found that metallic chromium is preferable as a conductive material having a coefficient of thermal expansion close to that of the zirconia electrolyte.
ジルコニア電解質の熱膨張率は約１０ＸＩＯ−６／にで
あり、一方金属クロムのそれは約９．４ Ｘｌ０−６／
にである。因みに、酸化クロムのそれは９．６ ＸＩＯ
’／ Ｋ、 Ｎｉ 基耐熱合金やＣＯ基耐熱合金のそれ
は約１３〜１７ Ｘ １０−６／にである。また、金属
クロムの腐食（酸化）を防止するためには、Ｌａ＋−ｘ
Ｌｃｒ０３（式中、Ｍはアルカリ土類金属）をコーティ
ングする。この材料の熱膨張率もジルコニア電解質のそ
れに近く、代表例を示すと下記の通りである。The coefficient of thermal expansion of zirconia electrolyte is about 10XIO-6/, while that of metallic chromium is about 9.4XIO-6/
It is. By the way, that of chromium oxide is 9.6 XIO
'/K, that of Ni-based heat-resistant alloys and CO-based heat-resistant alloys is approximately 13 to 17 x 10-6/. In addition, in order to prevent corrosion (oxidation) of metal chromium, La+-x
Coat Lcr03 (where M is an alkaline earth metal). The coefficient of thermal expansion of this material is also close to that of zirconia electrolyte, and typical examples are as follows.
ｌａ ｌ−Ｘ ！ＩＩ Ｘ Ｃｒ Ｏ３の熱膨張率（２
５〜１０００℃間）しａ。、９ｃａＱ、＋ＣｒＯ３９，
２
ＬａＯ，８ＳｃａＯ，ｌ５ＣｒＬ
９，３ＬａＯ−ａｃａａ、 ２ＣｒＯ＊
９．７ＬａＯ，８４ｓｒＯ，＋ＢＩ
ＪＯ３９゜６しａｏ、７５ＳＩ’０．ｚｓｃｒｏ３
１０．４１、ａｏ、 ７ｏｓｒ
ｏ、３ｃｒＱ３ １０．６Ｎ１基合金や
Ｃｏ基合金を使用したインターコネクタの場合、ジルコ
ニア電解質との熱膨張率の大きい相違点を吸収するため
にガラスなどの溶融タイプの接着剤を使う必要があるが
、それに対し、金属クロム系のインターコネクタの場合
には、ジルコニアと熱膨張差がないのでさらに接着剤の
熱膨張率をこれに合わせれば剥がれることがなくなるの
で、有利である。こうして、金属クロムでインターコネ
クタを作り、Ｌａ＋−ｘＭｘｃｒ０３（Ｍはアルカリ土
類金属）をスパッタリング等で緻密にコーティングした
ものは、ジルコニア固体電解質との適合性に浸れ、耐酸
化性も良好であり、シール性、高信頼性である。la l-X! II X Coefficient of thermal expansion of Cr O3 (2
Between 5 and 1000°C) a. , 9caQ, +CrO39,
2 LaO, 8ScaO, l5CrL
9,3LaO-acaa, 2CrO*
9.7LaO, 84srO, +BI
JO39゜6shiao, 75SI'0. zscro3
10.41, ao, 7osr
o, 3crQ3 In the case of interconnectors using 10.6N1-based alloys or Co-based alloys, it is necessary to use a melting type adhesive such as glass to absorb the large difference in thermal expansion coefficient from zirconia electrolyte. On the other hand, in the case of a metallic chromium interconnector, there is no difference in thermal expansion from zirconia, so if the coefficient of thermal expansion of the adhesive is adjusted to this, it is advantageous because it will not peel off. In this way, the interconnector made of metallic chromium and densely coated with La+-xMxcr03 (M is an alkaline earth metal) by sputtering etc. is highly compatible with the zirconia solid electrolyte and has good oxidation resistance. Sealing performance and high reliability.
インター コネクタ１４は両面に溝１４ａ・１４ｂを形
成してそれぞれガス通路を構成している。溝１４ａ、１
４ｂはそれぞれの溝に燃料ガスと酸化剤ガスをそれぞれ
供給できれば、溝の形状、配置は問わないが、最も簡単
で合理的な構成は、第１図及び第２図に示す如く、それ
ぞれの溝１４ａ、１４ｂを平行溝とし、それらを直角方
向に配置することである。このようにすれば、セルを集
積後、燃料ガスの入口及び出口、酸化剤ガスの入口及び
出口をそれぞれ同じ面上に配置することができ、集積セ
ルとしてのガス供給・排出系の構成が容易である。The interconnector 14 has grooves 14a and 14b formed on both sides to form gas passages, respectively. Groove 14a, 1
4b, the shape and arrangement of the grooves do not matter as long as fuel gas and oxidizing gas can be supplied to each groove, but the simplest and rational configuration is as shown in Figs. 1 and 2. 14a and 14b are parallel grooves, and they are arranged in a right angle direction. In this way, after the cells are integrated, the fuel gas inlet and outlet and the oxidant gas inlet and outlet can be arranged on the same plane, making it easy to configure the gas supply and exhaust system as an integrated cell. It is.
第２図において（ア）は平面図、（イ）は正面図、（つ
）は左側面図である。このようなインターコネクタ１４
を介して両面に電極１２．１３を形成した固体電解質板
を集積すると、電流路は基本的に外部端子１５−カソー
ド１２一固体電解質板１１−アノード１３→インターコ
ネクタ１４→カソード１２→固体電解質板１１−アノー
ド１３→固体電解質板１１→アノード１３→外部端子１
６の最短距離、すなわち、セルの集積方向に形成される
ので、電気抵抗の大きいカソード１２、アノード１３を
面方向に流れる成分が最小限化されることができる。し
かしながら、インターコネクタ１４の溝１４ａ、１４ｂ
、外部端子１５．１６の溝１５ｂ。In FIG. 2, (A) is a plan view, (B) is a front view, and (T) is a left side view. Such an interconnector 14
When solid electrolyte plates with electrodes 12 and 13 formed on both sides are integrated via 11-Anode 13 → Solid electrolyte plate 11 → Anode 13 → External terminal 1
6, that is, in the cell integration direction, components flowing in the planar direction through the cathode 12 and anode 13 having high electrical resistance can be minimized. However, the grooves 14a, 14b of the interconnector 14
, groove 15b of external terminal 15.16.
１６ａの部分では、カソード１２、アノード１３とイン
ターコネクタ１４又は外部端子１５，１６とは直接に接
触していないので、電流はカソード１２、アノード１３
の面方向に流れることが避けられない。そこで、溝１．
４ａ 、１４ｂ 、１５ｂ 、１６ａの形状、寸法と溝
の間隔を適当に選択することによって、ガスの圧力損失
を防ぎながら、電流路の長さが最短になるようにする。In the portion 16a, the cathode 12 and anode 13 are not in direct contact with the interconnector 14 or the external terminals 15 and 16, so the current flows between the cathode 12 and the anode 13.
Flowing in the direction of the plane is unavoidable. Therefore, groove 1.
By appropriately selecting the shapes and dimensions of 4a, 14b, 15b, and 16a and the spacing between the grooves, the length of the current path can be minimized while preventing gas pressure loss.
また、溝Ｌ４ａ ＝ １４ｂ 、Ｌ５ｂ。Also, groove L4a = 14b, L5b.
１６ａの幅が大きくなる場合に、第３図に示すように、
インターコネクタ１４とカソード１２及びアノード１３
の間に導電性の高いメツシュ板１７を挿入することによ
って高抵抗のカソード１２やアノード１３中の電流路の
長さを短かくしてもよい。When the width of 16a becomes larger, as shown in FIG.
Interconnector 14, cathode 12 and anode 13
The length of the current path in the high-resistance cathode 12 and anode 13 may be shortened by inserting a highly conductive mesh plate 17 between them.
メツシュ板の材質とじ−では白金、ニッケル、ニクロム
などが使用できるが、特に白金が好ましい。Platinum, nickel, nichrome, etc. can be used for binding the mesh plate, but platinum is particularly preferred.
また、溝１４ａ 、１４ｂ 、１５ｂ、 １６ａの断面
形状も矩形である必要はなく、三角形などでもよい。Further, the cross-sectional shape of the grooves 14a, 14b, 15b, and 16a does not necessarily have to be rectangular, but may be triangular or the like.
第４図に外部端子の形状を示す。同図中、（ア）は平面
図、（イ）は正面図である。溝の形状はインターコネク
タ１４の片面と同じである。Figure 4 shows the shape of the external terminal. In the figure, (A) is a plan view, and (B) is a front view. The shape of the groove is the same as that of one side of the interconnector 14.
固体電解質板１１、インターコネクタ１４、外部端子１
５・１６を集積して組立てるときには、固体電解質板１
１ （正確には電極１２．１３）とインターコネクタ１
４又は外部端子１５．１６の間でガスの漏れがないよう
に封止する必要がある。これは例えば軟化点が約８００
℃のガラスペーストで封止すればよい。このガラスペー
ストは電池の作動温度（９００〜１０００℃）では十分
に軟化してガスを封止するが、インターコネクタ１４又
は外部端子１５．１６と電極１２．１３との接触を妨げ
ない。Solid electrolyte plate 11, interconnector 14, external terminal 1
When assembling 5 and 16, solid electrolyte plate 1
1 (to be exact, electrodes 12 and 13) and interconnector 1
4 or external terminals 15 and 16 must be sealed to prevent gas leakage. For example, this has a softening point of about 800
It can be sealed with glass paste at ℃. This glass paste softens sufficiently at battery operating temperatures (900-1000° C.) to seal gas, but does not prevent contact between interconnector 14 or external terminals 15.16 and electrodes 12.13.
こうして組立てた電池に燃料ガス及び酸化剤ガスを併結
するためには、電池の多溝１４ａ、１４ｂの両端がそれ
ぞれ同一面に来るように配置されているので、それらの
面にマニホールドを取付ける。In order to combine fuel gas and oxidant gas into the battery thus assembled, both ends of the multi-channels 14a and 14b of the battery are arranged on the same surface, and a manifold is attached to those surfaces.
第５図に、マニホールドの取付例を示す。上記の如く組
立てた集積型電池本体２１を円筒状マニホールド２２の
管内に挿入し、溝１４ａ・１４ｂの出口が管壁に面する
ように配置する。電池本体２１とマニホールド２２の接
触箇所（４ケ所）をガス封止すれば、溝１４ａ、１４ｂ
のそれぞれの両端がそれぞれマニホールド２２の円筒壁
と電池本体２１で形成された４つのガス通路２３〜２６
と対応する。FIG. 5 shows an example of mounting the manifold. The integrated battery main body 21 assembled as described above is inserted into the tube of the cylindrical manifold 22 and arranged so that the outlets of the grooves 14a and 14b face the tube wall. If the contact points (4 points) between the battery body 21 and the manifold 22 are sealed with gas, the grooves 14a and 14b
There are four gas passages 23 to 26 whose respective ends are formed by the cylindrical wall of the manifold 22 and the battery body 21.
corresponds to
実施例１
第１図の集合様式に従い３段直列セルの固定電解質型燃
料電池を製作した。インターコネクタ１４、外部端子１
５．１６にはヘインズ合金Ｎｏ、２５（ヘインズ社の商
品Ｌ ６０５ ； Ｎ１１０．０％、Ｃ０５０，９
％、Ｃｒ２Ｏ，０％、Ｗ１５．０％、その他の合金）を
用い、表面の腐食を抑えるために表面を約６声の白金ス
パッタ膜で被覆した。インターコネクタ１４及び外部端
子１５．１６の形状は第２図及び第４図に示した通りで
あるが、どちらも５０ Ｘ５０ Ｘ ５ ｍｍの正方形
の板に溝幅７．５ｍｍ、溝深さ２ｔｎｍの平行溝１４ａ
＝ １４ｂ −１５ｂ −１６ａを溝間隔３ｍｍ（ピ
ンチ１０．５ｍｍ）で４本形成した。これらの寸法は、
機成的強度やガスの流通条件などにより適宜設定される
。例えば、同じ正方形の板であれば、溝幅４〜３ｍｍ、
溝深さ１〜３証、溝間隔０．５ ％ ５ ｍｍの範囲と
するとよい。インターコネクタ１４では両面に形成する
溝１４ａ＝１４ｂの方向を直交させた。Example 1 A fixed electrolyte fuel cell with three stages of series cells was manufactured according to the assembly pattern shown in FIG. Interconnector 14, external terminal 1
5.16 is Haynes alloy No. 25 (Haynes product L 605; N110.0%, C050,9
%, Cr2O, 0%, W15.0%, and other alloys), and the surface was coated with a platinum sputtered film of about 6 tones to suppress surface corrosion. The shapes of the interconnector 14 and the external terminals 15 and 16 are as shown in FIGS. 2 and 4, and both are made of a 50 x 50 x 5 mm square plate with a groove width of 7.5 mm and a groove depth of 2 tnm. Parallel groove 14a
= 14b - 15b - 16a were formed with a groove interval of 3 mm (pinch of 10.5 mm). These dimensions are
It is set appropriately depending on mechanical strength, gas flow conditions, etc. For example, for the same square plate, the groove width is 4 to 3 mm,
It is preferable that the groove depth is 1 to 3 mm, and the groove interval is 0.5% to 5 mm. In the interconnector 14, the directions of the grooves 14a and 14b formed on both surfaces are orthogonal to each other.
固体電解質板１１にはイツトリアを３モルパーセント添
加したジルコニアである部分安定化ジルコニアからなる
寸法は５０ Ｘ５０ Ｘ Ｏ，２ｍｍの板状物を用いた
。そして、酸素通路側にＬａｏ、 ｇｓｒ。、 １！、
ＩｎＯ３’ｔ’９末（平均粒径約５廁）をはけ塗り法で
厚さ０．０５ｍｍに塗布してカソード１２とし、水素通
路側にＮｉ／Ｚｒ０２（９／１重量比）のサーメット混
合扮末をはけ塗り法で厚さ０，０１〜０．０５ ｍ＋＋
＋に塗布してアノード１３とした。The solid electrolyte plate 11 was made of partially stabilized zirconia, which is zirconia to which 3 mole percent of ittria was added, and had dimensions of 50 x 50 x O and 2 mm. And Lao and GSR on the oxygen passage side. , 1! ,
InO3't'9 powder (average particle size of about 5 yuan) was applied to a thickness of 0.05 mm using a brush coating method to form the cathode 12, and a cermet mixture of Ni/Zr02 (9/1 weight ratio) was applied on the hydrogen passage side. Thickness 0.01 to 0.05 m++ by brush coating method
+ to form anode 13.
この固体電解質板１１とインターコネクタ１４、外部端
子１５・１６を第１図の如く集積し、固体電解質板１１
とインターコネクタ１４の側面まわりに軟化点が約８０
０℃のガラスペーストを塗布してガス封止用とした。前
記の如く、このガラスペーストは電池の作動温度で軟化
してガス封止する。This solid electrolyte plate 11, interconnector 14, and external terminals 15 and 16 are integrated as shown in FIG.
The softening point around the side surface of the interconnector 14 is approximately 80.
Glass paste at 0°C was applied to seal the gas. As mentioned above, this glass paste softens at the operating temperature of the cell to form a gas seal.
こうして集積した電池を第５図に示し、円筒状アルミナ
製マニホールド２２に納めた。マニホールド２２と電池
本体２１との接触部分はセラミ・ツクペースを塗布乾燥
して接合した後、さらにガラスペーストを塗布してガス
封止した。The battery thus assembled is shown in FIG. 5 and housed in a cylindrical alumina manifold 22. The contact portion between the manifold 22 and the battery body 21 was coated with ceramic paste, dried, and bonded, and then glass paste was further coated to seal the area with gas.
外部端子１５．１６に穴をあけ、白金リード端子２７゜
２８を挿入し、電気的接続を行なった。Holes were made in the external terminals 15 and 16, and platinum lead terminals 27 and 28 were inserted to establish electrical connection.
このようにして作製した燃料電池を加熱した。The fuel cell thus produced was heated.
室温から１５０℃までは１℃／ｍ ｉ ｎで加熱し、ガ
ラスペーストの溶媒を蒸発させた。１５０℃〜３００℃
までは５℃／ ｍ ｉ ｎで昇温した。３００℃以上で
は水素通路側には、アノードの酸化を防止する為、窒素
ガスを流し、１０℃／ ｍ ｉ ｎで１０００℃まで昇
温した。その後、１０００℃に保持してナノード側に水
素、カソード側に酸素を流し、発電を開始した。開放電
圧は３． ＯＶであった。放電特性を下記表に示す。The glass paste was heated at a rate of 1° C./min from room temperature to 150° C. to evaporate the solvent of the glass paste. 150℃～300℃
The temperature was raised at a rate of 5°C/min. At 300°C or higher, nitrogen gas was flowed into the hydrogen passage side to prevent oxidation of the anode, and the temperature was raised to 1000°C at a rate of 10°C/min. Thereafter, the temperature was maintained at 1000° C., hydrogen was flowed to the nanode side, and oxygen was flowed to the cathode side, and power generation was started. The open circuit voltage is 3. It was OV. The discharge characteristics are shown in the table below.
ガスクロスリークは水素の約１０％であった。Gas cross leakage was approximately 10% of hydrogen.
なお、被覆しないヘインズ合金をインターコネクタとし
て用いた以外は全く同様にして構成した固体電解質型燃
料電池を製作した。この場合、放電特性は１．５Ｖで０
．２１Ａであった。A solid oxide fuel cell was manufactured in exactly the same manner except that uncoated Haynes alloy was used as an interconnector. In this case, the discharge characteristics are 0 at 1.5V.
．． It was 21A.
実施例２
インターコネクタとして、金属クロムの表面にＬａｏ、
９ｃａ（１，１Ｃｒ０３を約５声スパツタにより被覆
したものを用いて、他は実施例１と全く同様にして燃料
電池を作製した。Example 2 As an interconnector, Lao,
A fuel cell was prepared in the same manner as in Example 1 except that 9ca (1,1Cr03) was coated with about 5 sputters.
実施例１と同一の条件で発電を開始したところ開放電圧
は、３．２Ｖであった。また、放電特性は下表のとおり
で、ガスクロスリークは水素の約１％であった。When power generation was started under the same conditions as in Example 1, the open circuit voltage was 3.2V. Further, the discharge characteristics are as shown in the table below, and the gas cross leak was approximately 1% of hydrogen.
本発明により、・プレーナ型集積構造の固体電解質型燃
料電池が提供され、電気抵抗の高いカソード、アノード
中を通る電流路の長さを最小限化してオーム損失を大幅
に低減し、また電池の集積度が高く、しかも構造及び製
造が簡単で高信頼性の固体電解質型燃料電池である。According to the present invention, a solid oxide fuel cell with a planar integrated structure is provided, which minimizes the length of the current path passing through the cathode and anode, which have high electrical resistance, and greatly reduces ohmic losses, and This solid oxide fuel cell has a high degree of integration, is simple in structure and manufacture, and has high reliability.
【図面の簡単な説明】
第１図は本発明の固体電解質型燃料電池の集合様式を示
す模式展開図、第２図はインターコネクタを示す三面図
、第３図は第１図の集合様式の変形例を示す側面図、第
４図は外部端子を示す２面図、第５図は電池をマニホー
ルドに取付だ様子を示す模式図、第６図及び第７図は従
来例の固体電解質型燃料電池の構造を示す図である。
１１・・・固体電解質板、 １２・・・カソード、１
３・・・アノード、
１４・・・インターコネクタ、
１４ａ 、 １４ｂ・・・溝、 １５ 、１６・・
・外部端子、１５ｂ、１６ａ・・・溝、 １７・
・・メツシュ板、２１・・・電池本体、 ２２・・
・マニホールド、２３〜２６・・・ガス通路、 ２７
．２８・・・リード端子。[BRIEF DESCRIPTION OF THE DRAWINGS] Fig. 1 is a schematic development diagram showing the assembly style of the solid oxide fuel cell of the present invention, Fig. 2 is a three-sided view showing the interconnector, and Fig. 3 is a schematic development diagram showing the assembly style of the solid oxide fuel cell of the present invention. Figure 4 is a side view showing the modified example, Figure 4 is a two-sided view showing the external terminal, Figure 5 is a schematic diagram showing how the battery is attached to the manifold, Figures 6 and 7 are the conventional solid electrolyte fuel. FIG. 3 is a diagram showing the structure of a battery. 11... Solid electrolyte plate, 12... Cathode, 1
3...Anode, 14...Interconnector, 14a, 14b...Groove, 15, 16...
・External terminal, 15b, 16a...groove, 17・
...Mesh plate, 21...Battery body, 22...
・Manifold, 23-26...Gas passage, 27
．． 28...Lead terminal.
Claims (1)
を付着した平板状のジルコニア質固体電解質板を、両面
にガス通路を構成する溝をそれぞれ形成した導電性耐熱
部品であるインターコネクタ板を介して複数個積層し、
それらの溝を通してカソード側に酸化剤ガス、アノード
側に燃料ガスを供給し、そして積層セルの上下端のアノ
ードとカソードより電流を取り出す構造を有する固体電
解質型燃料電池。1. An interconnector that is a conductive heat-resistant component that has a flat zirconia solid electrolyte plate with a porous cathode layer attached to one side and a porous anode layer attached to the other side, with grooves forming gas passages formed on both sides. Laminate multiple pieces through plates,
A solid oxide fuel cell has a structure in which oxidant gas is supplied to the cathode side and fuel gas is supplied to the anode side through these grooves, and current is extracted from the anode and cathode at the upper and lower ends of the stacked cell.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63329105A JPH0237669A (en) | 1988-04-21 | 1988-12-28 | Fuel cell of solid electrolyte type |
| US07/340,306 US4950562A (en) | 1988-04-21 | 1989-04-19 | Solid electrolyte type fuel cells |
| DE68917192T DE68917192T2 (en) | 1988-04-21 | 1989-04-20 | Solid electrolyte fuel cells. |
| EP89303918A EP0338823B1 (en) | 1988-04-21 | 1989-04-20 | Solid electrolyte type fuel cells |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-96757 | 1988-04-21 | ||
| JP9675788 | 1988-04-21 | ||
| JP63329105A JPH0237669A (en) | 1988-04-21 | 1988-12-28 | Fuel cell of solid electrolyte type |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0237669A true JPH0237669A (en) | 1990-02-07 |
Family
ID=26437938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63329105A Pending JPH0237669A (en) | 1988-04-21 | 1988-12-28 | Fuel cell of solid electrolyte type |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0237669A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04282566A (en) * | 1991-03-11 | 1992-10-07 | Ngk Insulators Ltd | Interconnector for solid electrolyte type fuel cell and this interconnector-provided solid electrolyte type fuel cell |
| JPH0525659U (en) * | 1991-09-17 | 1993-04-02 | 三菱重工業株式会社 | Solid electrolyte fuel cell |
| US5686197A (en) * | 1994-06-29 | 1997-11-11 | Aisin Seiki Kabushiki Kaisha | Fuel cell |
| US5824428A (en) * | 1994-10-27 | 1998-10-20 | Aisin Seiki Kabushiki Kaisha | Fuel cell |
-
1988
- 1988-12-28 JP JP63329105A patent/JPH0237669A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04282566A (en) * | 1991-03-11 | 1992-10-07 | Ngk Insulators Ltd | Interconnector for solid electrolyte type fuel cell and this interconnector-provided solid electrolyte type fuel cell |
| JPH0525659U (en) * | 1991-09-17 | 1993-04-02 | 三菱重工業株式会社 | Solid electrolyte fuel cell |
| US5686197A (en) * | 1994-06-29 | 1997-11-11 | Aisin Seiki Kabushiki Kaisha | Fuel cell |
| US5824428A (en) * | 1994-10-27 | 1998-10-20 | Aisin Seiki Kabushiki Kaisha | Fuel cell |
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