JP3285856B2 - Solid oxide fuel cell - Google Patents
Solid oxide fuel cellInfo
- Publication number
- JP3285856B2 JP3285856B2 JP2001206065A JP2001206065A JP3285856B2 JP 3285856 B2 JP3285856 B2 JP 3285856B2 JP 2001206065 A JP2001206065 A JP 2001206065A JP 2001206065 A JP2001206065 A JP 2001206065A JP 3285856 B2 JP3285856 B2 JP 3285856B2
- Authority
- JP
- Japan
- Prior art keywords
- joining jig
- cell
- powder
- cell body
- fuel cell
- 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.)
- Expired - Fee Related
Links
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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有底筒状の固体電
解質型燃料電池セルに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bottomed cylindrical solid oxide fuel cell.
【０００２】[0002]
【従来技術】従来より、固体電解質型燃料電池はその作
動温度が９００〜１０５０℃と高温であるため発電効率
が高く、第３世代の発電システムとして期待されてい
る。2. Description of the Related Art Conventionally, since a solid oxide fuel cell has a high operating temperature of 900 to 1050 ° C., it has a high power generation efficiency and is expected as a third generation power generation system.
【０００３】一般に、固体電解質型燃料電池セル（以下
セルと略す）には、円筒型と平板型が知られている。平
板型セルは、発電の単位体積当りの出力密度が高いとい
う特長を有するが、実用化に関してはガスシ−ル不完全
性やセル内の温度分布の不均一性などの問題がある。そ
れに対して、円筒型セルでは、出力密度は低いものの、
セルの機械的強度が高く、またセル内の温度の均一性が
保てるという特長がある。両形状のセルとも、それぞれ
の特長を生かして積極的に研究開発が進められている。[0003] In general, solid oxide fuel cells (hereinafter abbreviated as "cells") are known to be cylindrical and flat. The flat cell has the feature that the output density per unit volume of power generation is high, but there are problems such as imperfect gas seal and non-uniformity of the temperature distribution in the cell in practical use. In contrast, a cylindrical cell has a low power density,
It has the features that the mechanical strength of the cell is high and that the temperature inside the cell can be kept uniform. Both types of cells are being actively researched and developed taking advantage of their respective features.
【０００４】図２、図３は従来の円筒型セルＣの構成を
示すもので、図３は一端に封止部材６、他端にガス導入
管３及び接合治具２をそれぞれ設けた円筒型セルＣの斜
視図、図２は図３の円筒型セルＣの中心軸を横切るＢ−
Ｂ線における接合治具２付近の断面図である。FIGS. 2 and 3 show the configuration of a conventional cylindrical cell C. FIG. 3 shows a cylindrical cell having a sealing member 6 at one end and a gas introducing pipe 3 and a joining jig 2 at the other end. FIG. 2 is a perspective view of the cell C, and FIG.
It is sectional drawing in the vicinity of the joining jig 2 in the B line.
【０００５】円筒型セルＣのガス導入管３との接合は、
図２に示すように、円筒状のセル本体１と円筒状のガス
導入管３を、通気孔１０を有する節１１を設けた円筒状
の接合治具２にそれぞれ挿入セットし、接合治具２の節
１１に予め形成されたガラス層４をセル本体１の他端及
びガス導入管３の一端に当接し、発電を行う際の昇温時
に前記ガラス層４を軟化溶融させ、セル本体１の他端及
びガス導入管３の一端を前記接合治具２により接合して
いた。[0005] The joining of the cylindrical cell C with the gas inlet tube 3 is as follows.
As shown in FIG. 2, the cylindrical cell body 1 and the cylindrical gas inlet tube 3 are inserted and set in a cylindrical bonding jig 2 provided with a node 11 having a vent hole 10. The glass layer 4 previously formed in the section 11 is brought into contact with the other end of the cell body 1 and one end of the gas introduction pipe 3, and the glass layer 4 is softened and melted at the time of temperature rise during power generation. The other end and one end of the gas introduction pipe 3 were joined by the joining jig 2.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、セル本
体１の一端及び他端をガラス材を用いて接合する従来の
方法では、実際に発電を行う際に封止、接合することに
なるため完全に封止されているか否かの確認が困難であ
り、シール不良によるセル出力の低下が生じ易い。特
に、セルをスタック化した場合には封止箇所の増加によ
るシール不良が発生し易く、結果として出力が低下する
という問題点があった。However, in the conventional method of joining one end and the other end of the cell body 1 using a glass material, the cell body 1 is completely sealed and joined when power is actually generated. It is difficult to confirm whether or not the cell is sealed, and the cell output is likely to decrease due to poor sealing. In particular, when the cells are stacked, there is a problem that a sealing failure is likely to occur due to an increase in the number of sealing portions, and as a result, the output is reduced.
【０００７】また、一般的に、燃料電池は約１０００℃
という高温で数万時間も動作する耐久性が要求される。
従来のガラスシールでは、ガラスを約１０００℃で軟化
溶融させることによりガスシールを行っているが、長時
間運転すると溶融成分が滲み出しガスシールができなく
なるといった問題、更には溶融成分がセル本体１の周り
の部品等にまで広がりガラスシールそのものができなく
なるといった問題があった。加えて、ガラス材を軟化溶
融することにより揮発成分が生じ、それがセル本体１内
に付着したり、セル本体１内の酸素と反応して、セルの
性能を劣化させるという問題もあった。In general, a fuel cell is operated at about 1000 ° C.
It is required to have durability to operate for tens of thousands of hours at such a high temperature.
In the conventional glass seal, gas sealing is performed by softening and melting the glass at about 1000 ° C. However, if the operation is performed for a long time, the molten component oozes out and gas sealing cannot be performed. There is a problem that the glass seal itself cannot be formed because it spreads to parts and the like around the glass. In addition, the softening and melting of the glass material generates volatile components, which adhere to the inside of the cell body 1 or react with oxygen in the cell body 1 to deteriorate the performance of the cell.
【０００８】このようなガラスシールには、もう一つ大
きな問題点がある。それは、１回の熱サイクルにしか確
実に対応できないことである。つまり、燃料電池の運転
中に、様々なトラブルにより動作温度の約１０００℃か
ら室温まで降温しなければならないときに、ガラスシー
ルの降温時にガラス層の内部残留応力と表面応力が緩和
されにくく、セルの接合部が破壊されることがあった。[0008] Such a glass seal has another major problem. That is, it can reliably handle only one heat cycle. In other words, during operation of the fuel cell, when the temperature must be lowered from the operating temperature of about 1000 ° C. to room temperature due to various troubles, the internal residual stress and the surface stress of the glass layer are not easily relaxed when the temperature of the glass seal is lowered, and the cell Was sometimes destroyed.
【０００９】本発明は、上記事情に鑑みて完成されたも
のであり、その目的は円筒型セルのガスシールの確認が
容易で、ガスシールを容易かつ確実に行うことができる
とともに、ガスシール不良やガラスの揮発成分による出
力低下及び性能劣化を防止し、更には、動作温度から室
温までの降温時にシールされた接合部が破壊されること
のない円筒型セルを提供することを目的とする。The present invention has been completed in view of the above circumstances, and it is an object of the present invention to make it easy to confirm the gas seal of a cylindrical cell, to perform the gas seal easily and reliably, and to make the gas seal defective. It is another object of the present invention to provide a cylindrical cell that prevents a decrease in output and performance degradation due to volatile components of glass and glass and prevents a sealed joint from being destroyed when the temperature is lowered from an operating temperature to room temperature.
【００１０】[0010]
【課題を解決するための手段】本発明の固体電解質型燃
料電池セルは、通気孔を有する節を設けた円筒状の接合
治具の両方の開口に、円筒状の固体電解質型燃料電池セ
ル本体の他端と円筒状のガス導入管の一端とを、各々挿
入して前記節に当接させ、前記接合治具内側面と固体電
解質型燃料電池セル本体外周面との隙間及び接合治具内
側面とガス導入管外周面との隙間を２ｍｍ以下とし、該
隙間にセラミック粉末及び／又は金属粒子から成り、平
均粒径が０．１〜１０μｍの粉体を介装して成ることを
特徴とする。According to the present invention, there is provided a solid oxide fuel cell having a cylindrical solid oxide fuel cell body provided at both openings of a cylindrical joining jig provided with a node having a vent hole. And the other end of the cylindrical gas inlet tube is inserted and brought into contact with the node, and the gap between the inner surface of the joining jig and the outer peripheral surface of the solid oxide fuel cell body and the inside of the joining jig are removed. The gap between the side surface and the outer peripheral surface of the gas inlet pipe is set to 2 mm or less, and the gap is made of ceramic powder and / or metal particles, and has a mean particle size of 0.1 to 10 μm. I do.
【００１１】上記の発明において、前記接合治具の熱膨
張率が固体電解質型燃料電池セル本体の熱膨張率より小
さいか、及び／又は、前記粉体の熱膨張率が固体電解質
型燃料電池セル本体及び接合治具の熱膨張率よりも大き
いことが、固体電解質型燃料電池セル本体と接合治具の
ガスシールを確実にするうえで好適である。In the above invention, the coefficient of thermal expansion of the joining jig is smaller than the coefficient of thermal expansion of the solid oxide fuel cell body, and / or the coefficient of thermal expansion of the powder is a solid oxide fuel cell. It is preferable that the coefficient of thermal expansion is larger than the thermal expansion coefficient of the main body and the joining jig in order to ensure the gas seal between the solid oxide fuel cell body and the joining jig.
【００１２】[0012]
【発明の実施の形態】本発明のセルの構成を、図１に示
す。図１は図３のＢ−Ｂ線に相当する接合治具２ａ付近
の断面図である。尚、図１において、図２と同じ箇所に
は同一の符号を付している。FIG. 1 shows the configuration of a cell according to the present invention. FIG. 1 is a cross-sectional view near the joining jig 2a corresponding to the line BB in FIG. In FIG. 1, the same parts as those in FIG. 2 are denoted by the same reference numerals.
【００１３】図１においては、セル本体１の他端を、通
気孔１０を有する節１１を設けた円筒状の接合治具２ａ
の開口に挿入して前記節１１に当接させ、かつ円筒状の
ガス導入管３の一端を接合治具２ａの反対側開口に挿入
して節１１に当接させ、接合治具２ａ内側面とセル本体
１外周面との隙間及び接合治具２ａ内側面とガス導入管
３外周面との隙間にセラミック粉末又は金属粒子からな
る粉体５を介装させ、それらの隙間を封止しセル本体１
とガス導入管を接合している。In FIG. 1, the other end of the cell body 1 is connected to a cylindrical joining jig 2a provided with a node 11 having a vent hole 10.
And the one end of the cylindrical gas introduction pipe 3 is inserted into the opening on the opposite side of the joining jig 2a and abuts on the node 11, and the inner surface of the joining jig 2a is inserted. A powder 5 made of ceramic powder or metal particles is interposed in the gap between the cell body 1 and the outer peripheral surface and the gap between the inner surface of the joining jig 2a and the outer peripheral surface of the gas introduction pipe 3 to seal the gap. Body 1
And the gas inlet tube.
【００１４】本発明のセルは、少なくとも前記構成の接
合治具２ａを備えていればよい。The cell of the present invention only needs to include at least the joining jig 2a having the above-described configuration.
【００１５】本発明において、前記接合治具２ａはガス
リークを防止するため緻密質セラミックからなるのがよ
く、例えば、Ａｌ2Ｏ3、部分安定化ＺｒＯ2、安定化Ｚ
ｒＯ2、ＬａＣｒＯ3系等のＡｌ、Ｚｒ等を主成分とする
セラミックから成る。また、その開気孔率は１０％以下
であることが好ましい。前記の緻密質セラミック以外の
セラミックは動作温度の雰囲気中で還元されやすく、開
気孔率が１０％超の場合ガスリークが生じ、セルの性能
劣化やセルの破壊につながる。より好ましくは、開気孔
率を５％以下とするのがよい。In the present invention, the joining jig 2a is preferably made of a dense ceramic in order to prevent gas leakage, for example, Al 2 O 3 , partially stabilized ZrO 2 , stabilized Zr.
It is made of a ceramic mainly composed of Al, Zr or the like such as rO 2 or LaCrO 3 . Further, the open porosity is preferably 10% or less. Ceramics other than the above-mentioned dense ceramics are easily reduced in an atmosphere at an operating temperature, and when the open porosity is more than 10%, a gas leak occurs, which leads to deterioration of cell performance and breakage of the cell. More preferably, the open porosity is 5% or less.
【００１６】前記粉体５は、Ａｌ、Ｚｒ、Ｎｉ、Ｙ、Ｃ
ｒ、Ｃａ、Ｍｇ、Ｓｒ、Ｆｅ又は希土類元素（Ｓｃ、
Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇ
ｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ又はＬｕ）の
１種以上を主成分とし、その平均粒径が０．１〜１０μ
ｍであることが重要である。前記以外の元素が主成分の
場合、動作温度の約１０００℃でセル本体１と接合治具
２ａの成分が溶融し合って接合部が脆くなり、セルが破
壊され易い。また、平均粒径が０．１μｍ未満の場合、
隙間に介装しても粒子が飛散したり落下し易く、１０μ
ｍ超の場合粒子の隙間からガスがリークし易い。The powder 5 is made of Al, Zr, Ni, Y, C
r, Ca, Mg, Sr, Fe or a rare earth element (Sc,
Y, La, Ce, Pr, Nd, Pm, Sm, Eu, G
d, Tb, Dy, Ho, Er, Tm, Yb or Lu) as a main component and an average particle size of 0.1 to 10 μm.
It is important that m. When an element other than the above is the main component, the components of the cell body 1 and the bonding jig 2a melt at an operating temperature of about 1000 ° C., so that the bonding portion becomes brittle and the cell is easily broken. When the average particle size is less than 0.1 μm,
Even if interposed in a gap, particles are easily scattered and fall, 10μ
If it exceeds m, gas leaks easily from gaps between particles.
【００１７】本発明のガスシールは、セル本体１と接合
治具２ａとの熱膨張率の差を利用した機械的な締めつけ
により行うのが、確実なシールができ好ましい。セル本
体１は、室温から動作温度の約１０００℃までの昇温に
より、熱膨張する。このとき、接合治具２ａの熱膨張率
がセル本体１のそれより小さいと、接合部分が機械的に
締めつけられる。The gas seal of the present invention is preferably performed by mechanical tightening utilizing the difference in the coefficient of thermal expansion between the cell body 1 and the joining jig 2a, since a reliable seal can be obtained. The cell body 1 thermally expands by increasing the temperature from room temperature to an operating temperature of about 1000 ° C. At this time, if the coefficient of thermal expansion of the joining jig 2a is smaller than that of the cell body 1, the joining portion is mechanically tightened.
【００１８】また、接合治具２ａの熱膨張率がセル本体
１の熱膨張率よりも小さくてもその差が僅かな場合や、
逆に接合治具２ａの熱膨張率がセル本体１の熱膨張率よ
りも大きい場合には、粉体５の熱膨張率が、セル本体
１、接合治具２ａの熱膨張率のいずれよりも大きいこと
が好適である。Further, even if the coefficient of thermal expansion of the joining jig 2a is smaller than the coefficient of thermal expansion of the cell body 1, if the difference is small,
Conversely, when the coefficient of thermal expansion of the joining jig 2a is larger than the coefficient of thermal expansion of the cell body 1, the coefficient of thermal expansion of the powder 5 is larger than that of either the cell body 1 or the joining jig 2a. Preferably, it is large.
【００１９】更に、構造的には、セル本体１と接合治具
２ａとの隙間が、ガスの流速方向に平行なこと、つま
り、セル本体１の外周面と接合治具２ａの内側面との隙
間に粉体５を介装することが好ましい。この場合、隙間
にかかるガス圧を最小限にできる。Further, structurally, the gap between the cell body 1 and the joining jig 2a is parallel to the gas flow direction, that is, the gap between the outer peripheral surface of the cell body 1 and the inner surface of the joining jig 2a. It is preferable to interpose the powder 5 in the gap. In this case, the gas pressure applied to the gap can be minimized.
【００２０】本発明のセル本体１の具体的構成及び製造
方法について以下に詳述する。まず、支持管１ａを兼ね
た円筒状の空気極成形体を押出成形法により作製する。
この空気極成形体は、ペロブスカイト型結晶相を主相と
するＬａＭｎＯ3系の材料で、その主結晶相の平均粒径
は３〜２０μｍ、特に５〜１５μｍであることが好まし
い。これは、主結晶相の粒径が３μｍより小さいと強度
は高いもののガス透過性が低く、２０μｍを越えるとガ
ス透過性は高くなるものの強度が不十分となるためであ
る。なお、空気極１ｂの開気孔率は２０〜４５％がよ
く、特に３０〜４０％が好適である。また、その平均細
孔径は、１．０〜５．０μｍの範囲がガス透過性に優れ
る。The specific structure and manufacturing method of the cell body 1 of the present invention will be described below in detail. First, a cylindrical air electrode molded body also serving as the support tube 1a is manufactured by an extrusion molding method.
The air electrode compact is a LaMnO 3 -based material having a perovskite-type crystal phase as a main phase, and the main crystal phase preferably has an average particle size of 3 to 20 μm, particularly preferably 5 to 15 μm. This is because if the particle diameter of the main crystal phase is smaller than 3 μm, the gas permeability is low although the strength is high, and if it exceeds 20 μm, the gas permeability is high but the strength is insufficient. The open porosity of the air electrode 1b is preferably 20 to 45%, particularly preferably 30 to 40%. The average pore diameter in the range of 1.0 to 5.0 μm is excellent in gas permeability.
【００２１】次に、空気極成形体の表面に固体電解質１
ｃの成形体層を形成する。この固体電解質成形体層は、
平均粒径が０．５〜３μｍのＹ2Ｏ3等の公知の安定化剤
により安定化されたＺｒＯ2からなる粉体のスラリーを
調製し、その後ドクターブレード法等により前記スラリ
ーから作製されたグリーンシートを、空気極成形体の外
表面に巻き付けて形成する。Next, the solid electrolyte 1 is placed on the surface of the air electrode molded body.
The molded body layer of c is formed. This solid electrolyte molded layer,
A slurry of powder made of ZrO 2 stabilized with a known stabilizer such as Y 2 O 3 having an average particle size of 0.5 to 3 μm was prepared, and then prepared from the slurry by a doctor blade method or the like. The green sheet is formed by winding the green sheet around the outer surface of the air electrode molded body.
【００２２】そして、空気極成形体／固体電解質成形体
を１０００〜１３００℃の温度で１〜３時間程度仮焼
し、その後、集電体の積層箇所となる固体電解質１ｃ及
び空気極１ｂの表面の一部を平滑に研磨し、集電体成形
体を積層する。集電体用成形体はＬａＣｒＯ3系の材料
を使用し、固体電解質成形体と同様にグリーンシートを
積層して形成する。Then, the air electrode molded body / solid electrolyte molded body is calcined at a temperature of 1000 to 1300 ° C. for about 1 to 3 hours, and thereafter, the surfaces of the solid electrolyte 1c and the air electrode 1b which are to be the laminated portions of the current collector are provided. Is polished smoothly, and a current collector molded body is laminated. The molded body for the current collector uses a LaCrO 3 -based material, and is formed by laminating green sheets in the same manner as the solid electrolyte molded body.
【００２３】このようにして作製した空気極１ｂ／固体
電解質１ｃ／集電体成形体は、大気等の酸化性雰囲気中
で、１３００〜１６００℃の温度で３〜１５時間程度同
時焼成することにより共焼結させる。そして、燃料極１
ｄは、Ｎｉを３０〜８０重量％含有し、その残部がＹ2
Ｏ3等の安定化剤で安定化されたＺｒＯ2からなる多孔質
のサーメット材料を使用し、前記空気極１ｂ／固体電解
質１ｃ／集電体成形体の所定箇所に燃料極成形体層を形
成して焼結させ、円筒状のセル本体１を作製する。又
は、空気極成形体／固体電解質成形体／集電体成形体を
作製した後、更に燃料極成形体を積層し、これらを同時
焼成してセル本体１を作製することもできる。The air electrode 1b / solid electrolyte 1c / collector molded body thus manufactured is simultaneously fired at a temperature of 1300 to 1600 ° C. for about 3 to 15 hours in an oxidizing atmosphere such as air. Co-sinter. And fuel electrode 1
d contains 30 to 80% by weight of Ni and the remainder is Y 2
Using a porous cermet material made of ZrO 2 stabilized by a stabilizer such as O 3 , a fuel electrode molded body layer is formed at a predetermined position of the air electrode 1b / solid electrolyte 1c / current collector molded body. And sintering to produce a cylindrical cell body 1. Alternatively, the cell body 1 can be manufactured by stacking a fuel electrode formed body after forming the air electrode formed body / solid electrolyte formed body / current collector formed body and firing them simultaneously.
【００２４】次に、緻密質セラミックの焼結体からなる
接合治具２ａを作製する。これら接合治具２ａは、発電
時のガスシール性が要求されるため、例えば、結晶相の
平均粒径が０．５〜３μｍ程度のＡｌ2Ｏ3、部分安定化
ＺｒＯ2、安定化ＺｒＯ2、ＬａＣｒＯ3等を主成分とす
る、ＺｒＯ2系、ＬａＣｒＯ3系酸化物の形成粉末を、押
出成形法や静水圧成形法（ラバープレス法）等により成
形し、各々所定の形状に切削加工を行う。この後、大気
等の酸化性雰囲気中で、１３００〜１６００℃の温度で
３〜５時間程度焼成して作製する。Next, a bonding jig 2a made of a sintered body of dense ceramic is manufactured. Since these joining jigs 2a are required to have gas sealing properties at the time of power generation, for example, Al 2 O 3 having an average grain size of about 0.5 to 3 μm, partially stabilized ZrO 2 , stabilized ZrO 2 Forming powder of ZrO 2 -based or LaCrO 3 -based oxide mainly composed of LaCrO 3 , LaCrO 3, etc. by extrusion molding or isostatic pressing (rubber pressing), etc. Do. After that, it is baked in an oxidizing atmosphere such as the air at a temperature of 1300 to 1600 ° C. for about 3 to 5 hours to produce.
【００２５】最後に、以下のようにして、セル本体１と
接合治具２ａとの隙間に粉体５を介装し、ガスシールを
行う。まず、接合治具２ａにセル本体１を挿入するが、
このときセル本体１の底面と接合治具２ａとの接触部に
ガラスを介装して、ガスシール性を高めてもよい。ただ
し、ガラスは多数回の熱サイクルで使用するのが難しい
ので、数回程度の熱サイクルで使用する場合に好適であ
る。Finally, the powder 5 is interposed in the gap between the cell body 1 and the joining jig 2a to perform gas sealing as follows. First, the cell body 1 is inserted into the joining jig 2a.
At this time, glass may be interposed at the contact portion between the bottom surface of the cell body 1 and the joining jig 2a to enhance the gas sealing property. However, since it is difficult to use glass in a large number of thermal cycles, it is suitable when used in several thermal cycles.
【００２６】次に、前記隙間に粉体５を介装する場合、
粉体５を隙間に充填して圧力を加え固めたり、粉体５を
スラリー状にして隙間に注入し、圧力を加えながら乾燥
させ固めてもよい。そして、隙間に介装された粉体５
は、発電前の室温では固められた状態であり、発電可能
な約１０００℃では固められた状態で熱膨張した状態、
あるいは少なくとも部分的に焼結した状態となり、強固
に固着しているものと考えられる。Next, when the powder 5 is interposed in the gap,
The powder 5 may be filled into the gap and pressurized to harden it, or the powder 5 may be slurried and poured into the gap, dried and hardened while applying pressure. And the powder 5 interposed in the gap
Is in a state of solidification at room temperature before power generation, and in a state of thermal expansion in a state of solidification at about 1000 ° C. where power can be generated,
Alternatively, it is considered that it is at least partially sintered and firmly fixed.
【００２７】かくして、本発明は、ガスシールの確認が
容易で、ガスシールを容易かつ確実に行うことができ、
ガスシール不良やガラスの揮発成分による出力低下及び
性能劣化を防止し、また動作温度から室温までの降温時
に接合部が破壊されることがなく、その結果、何回もの
熱サイクルで使用可能になるという作用効果を有する。Thus, according to the present invention, the gas seal can be easily confirmed, and the gas seal can be performed easily and reliably.
Prevents output degradation and performance degradation due to defective gas seals and volatile components of the glass.Also, the joint is not destroyed when the temperature is lowered from the operating temperature to room temperature, so that it can be used in many thermal cycles. It has the function and effect.
【００２８】尚、本発明は上記の実施形態に限定される
ものではなく、本発明の要旨を逸脱しない範囲で種々の
変更は差し支えない。It should be noted that the present invention is not limited to the above embodiment, and various changes may be made without departing from the gist of the present invention.
【００２９】[0029]
【実施例】（実施例）本発明の実施例を以下に示す。ま
ず、図１の構成を有する円筒状のセル本体１を以下のよ
うな共焼結により作製した。EXAMPLES (Examples) Examples of the present invention are shown below. First, a cylindrical cell body 1 having the configuration shown in FIG. 1 was produced by the following co-sintering.
【００３０】純度９９．９％以上のＬａ2Ｏ3、Ｙ2Ｏ3、
ＣａＣＯ3、Ｍｎ2Ｏ3を出発原料として、これをＬａ
0.56Ｙ0.14Ｃａ0.3ＭｎＯ3の組成になるように秤量混合
した後、１５００℃で３時間仮焼して粉砕し、平均粒径
が約５μｍの固溶体粉末を得た。この固溶体粉末にバイ
ンダーを添加し、押出成形法で円筒状の空気極成形体を
作製した。La 2 O 3 , Y 2 O 3 having a purity of 99.9% or more,
Starting from CaCO 3 , Mn 2 O 3 ,
After weighing and mixing so as to have a composition of 0.56 Y 0.14 Ca 0.3 MnO 3, the mixture was calcined at 1500 ° C. for 3 hours and pulverized to obtain a solid solution powder having an average particle size of about 5 μm. A binder was added to the solid solution powder, and a cylindrical air electrode molded body was produced by an extrusion molding method.
【００３１】次に、共沈法により得られたＹ2Ｏ3を８ｍ
ｏｌ％の割合で含有する平均粒径が約１μｍのＺｒＯ2
粉末に、トルエンとバインダーを添加してスラリーを調
製し、ドクターブレード法により前記スラリーから厚み
約１３０μｍのシート状の固体電解質成形体を作製し
た。Next, 8 m of Y 2 O 3 obtained by the coprecipitation method was used.
ol% of ZrO 2 having an average particle size of about 1 μm.
A slurry was prepared by adding toluene and a binder to the powder, and a sheet-like solid electrolyte molded body having a thickness of about 130 μm was prepared from the slurry by a doctor blade method.
【００３２】そして、純度９９．９％以上のＬａ2Ｏ3、
Ｃｒ2Ｏ3、ＭｇＯを出発原料として、これをＬａ（Ｍｇ
0.3Ｃｒ0.7）0.97Ｏ3の組成になるように秤量混合した
後、１５００℃で３時間仮焼し粉砕して、平均粒径が約
２μｍの固溶体粉末を得た。この固溶体粉末にトルエン
とバインダーを添加してスラリーを調製し、ドクターブ
レード法によりスラリーから厚み約１４０μｍのシート
状の集電体用成形体を作製した。And La 2 O 3 having a purity of 99.9% or more,
Starting from Cr 2 O 3 and MgO, the starting material is La (Mg
After weighing and mixing so as to have a composition of 0.3 Cr 0.7 ) 0.97 O 3, the mixture was calcined at 1500 ° C. for 3 hours and pulverized to obtain a solid solution powder having an average particle size of about 2 μm. Toluene and a binder were added to the solid solution powder to prepare a slurry, and a sheet-like molded body for a current collector having a thickness of about 140 μm was prepared from the slurry by a doctor blade method.
【００３３】この後、空気極成形体に固体電解質成形体
をロール状に巻き付け、１１００℃で１時間の仮焼を行
なった。仮焼後、集電体の積層箇所となる空気極仮焼体
及び固体電解質仮焼体のそれぞれの表面の一部を平面研
磨し、前記集電体用成形体を研磨部に帯状に設置した。
その後、大気中において１５００℃で６時間の条件で共
焼結した。焼結後、ＮｉＯ粉末に１０ｍｏｌ％Ｙ2Ｏ3を
含むＺｒＯ2粉末を、（ＮｉＯ粉末）：（ＺｒＯ2粉末）
＝８０：２０重量比の割合で混合した混合粉末に、水を
溶媒として加えて作製した燃料極スラリーを、焼結体表
面に塗布し乾燥した。その後、大気中において１４００
℃で２時間焼結を行うことにより、厚み５０μｍの燃料
極１ｄを作製し、円筒状のセル本体１を作製した。Thereafter, the solid electrolyte molded body was wound around the air electrode molded body in a roll shape and calcined at 1100 ° C. for 1 hour. After calcination, a part of the surface of each of the air electrode calcined body and the solid electrolyte calcined body to be the laminating portion of the current collector was polished in a plane, and the molded body for the current collector was placed in a band shape on the polishing part. .
Thereafter, co-sintering was performed in the air at 1500 ° C. for 6 hours. After sintering, ZrO 2 powder containing 10 mol% Y 2 O 3 in NiO powder was added to (NiO powder): (ZrO 2 powder)
= 80: 20 A fuel electrode slurry prepared by adding water as a solvent to a mixed powder mixed at a weight ratio of 80:20 was applied to the surface of the sintered body and dried. Then, 1400 in air
By performing sintering at 2 ° C. for 2 hours, a fuel electrode 1 d having a thickness of 50 μm was produced, and a cylindrical cell body 1 was produced.
【００３４】次に、図１の接合治具２ａを以下のように
作製した。平均粒径が約１μｍのＡｌ2Ｏ3、平均粒径が
約１μｍのＺｒＯ2粉末、３ｍｏｌ％のＹ2Ｏ3を含む平
均粒径が約２μｍのＺｒＯ2粉末（3mol Yttrium Stabil
ized Zirconium ：３ＹＳＺ）、８ｍｏｌ％のＹ2Ｏ3を
含む平均粒径が約２μｍのＺｒＯ2粉末（８ＹＳＺ）、
１ｍｏｌ％のＣａＯを含む平均粒径が約２μｍのＺｒＯ
2粉末（Calcium Stabilized Zirconium；ＣＳＺ）のい
ずれかを、静水圧成形法（ラバープレス法）により成形
し、所定の形状に切削加工して、セラミック成形体を作
製した。この接合治具２ａ用セラミック成形体を、大気
中において１４００℃で２時間の条件で焼成した。Next, the joining jig 2a shown in FIG. 1 was manufactured as follows. The average particle size of about 1μm Al 2 O 3, ZrO 2 powder having an average particle size of about 1 [mu] m, 3 mol% of Y mean particle size of about 2 [mu] m ZrO 2 powder containing 2 O 3 (3mol Yttrium Stabil
Zirconium: 3YSZ), ZrO 2 powder containing 8 mol% of Y 2 O 3 and having an average particle size of about 2 μm (8YSZ),
ZrO having an average particle size of about 2 μm containing 1 mol% of CaO
One of the two powders (Calcium Stabilized Zirconium; CSZ) was molded by a hydrostatic molding method (rubber press method), and cut into a predetermined shape to produce a ceramic molded body. The ceramic molded body for the joining jig 2a was fired in the atmosphere at 1400 ° C. for 2 hours.
【００３５】このとき、接合治具２ａの熱膨張率がセル
本体１のそれよりも小さくなるように各々の部品を組み
合わせて、室温でセル本体１と接合治具２ａ間の隙間が
０．５〜２ｍｍになるようにした。例えば、上記のよう
に作製したセル本体１の熱膨張率は１０．８×１０-6／
Ｋで、Ａｌ2Ｏ3の接合治具２ａは８．０×１０-6／Ｋ
で、Ｎｉ粒子から成る粉体５は１６．７８×１０-6／Ｋ
である。At this time, the components are combined so that the coefficient of thermal expansion of the joining jig 2a is smaller than that of the cell body 1, and the gap between the cell body 1 and the joining jig 2a is 0.5 at room temperature. ２2 mm. For example, the cell body 1 manufactured as described above has a coefficient of thermal expansion of 10.8 × 10 −6 /
K, the bonding jig 2a of Al 2 O 3 is 8.0 × 10 −6 / K
The powder 5 composed of Ni particles is 16.78 × 10 −6 / K
It is.
【００３６】セル本体１と接合治具２ａ間の隙間に、表
１に示すような、平均粒径が０．１μｍ〜１０μｍの８
ＹＳＺ、Ａｌ2Ｏ3、ＺｒＯ2、Ｎｉ等の粉体５をスラリ
ー状にし、介装する。スラリー状の粉体５が乾燥するま
で圧力を加え続け、固化するようにする。そして、約１
０００℃まで昇温して、セル内に空気、セル外に水素を
流し、開放起電力を測定することにより、ガスのシール
性を判定した。このとき、開放起電力が０．８Ｖ以上の
ものをガスのシール性が良好と判断した。In the gap between the cell body 1 and the joining jig 2a, as shown in Table 1, 8 particles having an average particle diameter of 0.1 μm to 10 μm
A powder 5 of YSZ, Al 2 O 3 , ZrO 2 , Ni or the like is formed into a slurry and interposed. The pressure is continuously applied until the slurry-like powder 5 dries, so that the slurry 5 solidifies. And about 1
The temperature was raised to 000 ° C., air was flown into the cell and hydrogen was flown outside the cell, and the open electromotive force was measured to determine the gas sealing property. At this time, those having an open electromotive force of 0.8 V or more were judged to have good gas sealing properties.
【００３７】[0037]
【表１】 [Table 1]
【００３８】表１に示すように、隙間が２ｍｍ以下、開
気孔率が１０％未満、粉体５の平均粒径が０．１〜１０
μｍで、開放起電力が０．８Ｖ以上であった。また、前
記の条件を満足するものは、室温と約１０００℃間の昇
温及び降温の熱サイクルを５回行った後でも、０．８Ｖ
以上の開放起電力を保持した。As shown in Table 1, the gap is 2 mm or less, the open porosity is less than 10%, and the average particle size of the powder 5 is 0.1 to 10%.
In μm, the open electromotive force was 0.8 V or more. Further, those satisfying the above-mentioned conditions can be obtained at a voltage of 0.8 V even after performing a heat cycle of raising and lowering the temperature between room temperature and about 1000 ° C five times.
The above open electromotive force was maintained.
【００３９】（比較例１）接合治具２ａの組成をＡｌ2
Ｏ3、その開気効率を１％、隙間の距離を３．０ｍｍ、
粉体５の組成を８ＹＳＺ、その平均粒径を１μｍとした
以外は、実施例と同様にセル本体１，接合治具２ａを作
製した。(Comparative Example 1) The composition of the joining jig 2a was changed to Al 2
O 3 , its opening efficiency is 1%, the distance of the gap is 3.0 mm,
A cell body 1 and a bonding jig 2a were produced in the same manner as in Example, except that the composition of the powder 5 was 8YSZ and the average particle size was 1 μm.
【００４０】この場合の開放起電力は、熱サイクル前で
０．８Ｖ、５回の熱サイクル後で０．７Ｖであった。The open electromotive force in this case was 0.8 V before the thermal cycle and 0.7 V after the five thermal cycles.
【００４１】（比較例２）接合治具２ａの組成をＡｌ2
Ｏ3、その開気孔率を１％、隙間の距離を０．５ｍｍ、
粉体５の組成をＺｒＯ2、その平均粒径を０．０１μｍ
とした以外は、実施例と同様にセル本体１、接合治具２
ａを作製した。(Comparative Example 2) The composition of the bonding jig 2a was changed to Al 2
O 3 , the open porosity is 1%, the gap distance is 0.5 mm,
Powder 5 has a composition of ZrO 2 and an average particle size of 0.01 μm
Cell body 1 and joining jig 2
a was produced.
【００４２】この場合の開放起電力は、熱サイクル前で
０Ｖ、５回の熱サイクル後で０Ｖであった。The open electromotive force in this case was 0 V before the heat cycle and 0 V after the five heat cycles.
【００４３】（比較例３）接合治具２ａの組成をＡｌ2
Ｏ3、その開気孔率を１％、隙間の距離を０．５ｍｍ、
粉体５の組成をＺｒＯ2、その平均粒径を２０μｍとし
た以外は、実施例と同様にセル本体１、接合部材２ａを
作製した。(Comparative Example 3) The composition of the joining jig 2a was changed to Al 2
O 3 , the open porosity is 1%, the gap distance is 0.5 mm,
A cell body 1 and a joining member 2a were produced in the same manner as in Example, except that the composition of the powder 5 was ZrO 2 and the average particle size was 20 μm.
【００４４】この場合の開放起電力は、熱サイクル前で
０Ｖ、５回の熱サイクル後で０Ｖであった。The open electromotive force in this case was 0 V before the heat cycle and 0 V after the five heat cycles.
【００４５】[0045]
【発明の効果】本発明は、円筒状のセル本体の一端を有
底円筒状の接合治具に挿入し、接合治具内側面とセル本
体外周面との隙間にセラミック粉末又は金属粒子から成
る粉体を介装することにより、発電の際のガスシール性
を完全にかつ容易に行うことができるとともに、封止状
態の確認も容易であり、その結果、セル性能を安定させ
ることができ、発電性能を向上させることができる。ま
た、動作温度から室温までの降温時に、封止部及び接合
部に従来使用されていたガラスの熱応力により破壊され
ることがなく、これにより、何回もの熱サイクルで使用
可能になる。According to the present invention, one end of a cylindrical cell body is inserted into a bottomed cylindrical joining jig, and a gap between an inner surface of the joining jig and an outer peripheral surface of the cell body is made of ceramic powder or metal particles. By interposing the powder, it is possible to completely and easily perform gas sealing at the time of power generation, and it is also easy to confirm the sealing state. As a result, the cell performance can be stabilized, Power generation performance can be improved. Further, when the temperature is lowered from the operating temperature to the room temperature, the glass is not broken by the thermal stress of the glass conventionally used for the sealing portion and the bonding portion, so that it can be used in many thermal cycles.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の円筒状セルの接合部付近の構造を示
し、図３のＢ−Ｂ線における断面図である。FIG. 1 is a cross-sectional view taken along the line BB of FIG. 3 showing a structure near a joint of a cylindrical cell of the present invention.
【図２】従来の円筒状セルの接合部付近の断面図であ
る。FIG. 2 is a cross-sectional view of the vicinity of a joint of a conventional cylindrical cell.
【図３】円筒状セルの基本構成の部分斜視図である。FIG. 3 is a partial perspective view of a basic configuration of a cylindrical cell.
１：セル本体 １ａ：支持管 １ｂ：空気極 １ｃ：固体電解質 １ｄ：燃料極 ２ａ：接合治具 ３：ガス導入管 ５：粉体 １０：通気孔 １１：節 1: Cell body 1a: Support tube 1b: Air electrode 1c: Solid electrolyte 1d: Fuel electrode 2a: Joining jig 3: Gas introduction tube 5: Powder 10: Vent hole 11: Node
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−170359（ＪＰ，Ａ) 特開 平４−104475（ＪＰ，Ａ) 特開 平10−162847（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 8/02,8/12 ────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-2-170359 (JP, A) JP-A-4-104475 (JP, A) JP-A-10-162847 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01M 8 / 02,8 / 12
Claims (2)
具の両方の開口に、円筒状の固体電解質型燃料電池セル
本体の他端と円筒状のガス導入管の一端とを、各々挿入
して前記節に当接させ、前記接合治具内側面と固体電解
質型燃料電池セル本体外周面との隙間及び接合治具内側
面とガス導入管外周面との隙間を２ｍｍ以下とし、該隙
間にセラミック粉末及び／又は金属粒子から成り、平均
粒径が０．１〜１０μｍの粉体を介装して成ることを特
徴とする固体電解質型燃料電池セル。1. The other end of a cylindrical solid oxide fuel cell body and one end of a cylindrical gas inlet tube are provided at both openings of a cylindrical joining jig provided with a node having a vent hole. Each is inserted and brought into contact with the node, the gap between the inner surface of the joining jig and the outer peripheral surface of the solid oxide fuel cell body and the gap between the inner surface of the joining jig and the outer peripheral surface of the gas inlet tube are set to 2 mm or less, A solid oxide fuel cell comprising a ceramic powder and / or metal particles interposed in the gap and having an average particle diameter of 0.1 to 10 μm.
料電池セル本体の熱膨張率より小さいか、及び／又は、
前記粉体の熱膨張率が固体電解質型燃料電池セル本体及
び接合治具の熱膨張率よりも大きいことを特徴とする請
求項１記載の固体電解質型燃料電池セル。2. The thermal expansion coefficient of the joining jig is smaller than the thermal expansion coefficient of the solid oxide fuel cell body, and / or
2. The solid oxide fuel cell according to claim 1, wherein the thermal expansion coefficient of the powder is larger than that of the solid oxide fuel cell body and the joining jig.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001206065A JP3285856B2 (en) | 2001-07-06 | 2001-07-06 | Solid oxide fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001206065A JP3285856B2 (en) | 2001-07-06 | 2001-07-06 | Solid oxide fuel cell |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35007396A Division JP3238087B2 (en) | 1996-12-27 | 1996-12-27 | Solid oxide fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002110203A JP2002110203A (en) | 2002-04-12 |
| JP3285856B2 true JP3285856B2 (en) | 2002-05-27 |
Family
ID=19042259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001206065A Expired - Fee Related JP3285856B2 (en) | 2001-07-06 | 2001-07-06 | Solid oxide fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3285856B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4587659B2 (en) * | 2003-11-26 | 2010-11-24 | 京セラ株式会社 | Manufacturing method of fuel cell stack |
| JP2010257947A (en) * | 2009-03-30 | 2010-11-11 | Mitsubishi Heavy Ind Ltd | Cell tube for solid electrolyte fuel cells, and the solid electrolyte fuel cell |
-
2001
- 2001-07-06 JP JP2001206065A patent/JP3285856B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002110203A (en) | 2002-04-12 |
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