JPH07130385A - Cylindrical lateral band type solid electrolyte electrolytic cell - Google Patents
Cylindrical lateral band type solid electrolyte electrolytic cellInfo
- Publication number
- JPH07130385A JPH07130385A JP5275139A JP27513993A JPH07130385A JP H07130385 A JPH07130385 A JP H07130385A JP 5275139 A JP5275139 A JP 5275139A JP 27513993 A JP27513993 A JP 27513993A JP H07130385 A JPH07130385 A JP H07130385A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- tube
- cylindrical
- interconnector
- electrolytic 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.)
- Withdrawn
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
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セル
（ＳＯＦＣ）やその逆反応の高温水蒸気電解セル（ＳＯ
ＦＥ）に使用される円筒横縞型固体電解質電解セルの改
良に関する。BACKGROUND OF THE INVENTION The present invention relates to a solid oxide fuel cell (SOFC) and a high temperature steam electrolysis cell (SO
It relates to an improvement of a cylindrical horizontal stripe type solid electrolyte electrolytic cell used for FE).
【０００２】[0002]
【従来の技術】従来の円筒横縞型固体電解質電解セルの
製造法をＳＯＦＣを例に採り、図４によって説明する。
基体管（例えばカルシア安定化ジルコニア：ＣＳＺ）１
上に、構成材料である燃料極｛例えばＮｉＯ／イットリ
ア安定化ジルコニア（ＹＳＺ）｝２、固体電解質（例え
ばＹＳＺ）３、インターコネクタ（例えばＮｉＣｒ／Ａ
ｌ2 Ｏ3 ）５、空気極（例えばＬａＣｏＯ3 ）４及び絶
縁材６を溶射法により成膜して製造している。このもの
ゝ外観は図５に示すようになるので円筒横縞型固体電解
質電解セルと呼ばれている。2. Description of the Related Art A conventional method for manufacturing a cylindrical horizontal stripe type solid electrolyte electrolytic cell will be described with reference to FIG. 4 by taking SOFC as an example.
Substrate tube (eg calcia-stabilized zirconia: CSZ) 1
In addition, a fuel electrode {eg, NiO / yttria-stabilized zirconia (YSZ)} 2, a solid electrolyte (eg, YSZ) 3, an interconnector (eg, NiCr / A) as constituent materials
1 2 O 3 ) 5, an air electrode (for example, LaCoO 3 ) 4 and an insulating material 6 are formed by a thermal spraying method. Since the appearance of this product is as shown in FIG. 5, it is called a cylindrical horizontal stripe type solid electrolyte electrolytic cell.
【０００３】[0003]
【発明が解決しようとする課題】従来の円筒横縞型ＳＯ
ＦＣは溶射法によって基体管の外周に構成材料を成膜す
るために原料粉の歩留りが非常に悪く、また、基体管に
原料粉の応力が加わるために基体管が破壊されることが
あり、また、基体管は必ず使用しなければならないた
め、コスト的に非常に大きな損失となる。また、溶射法
では、ピンホールの発生などが考えられ、固体電解質や
インターコネクタの緻密度に影響を与える恐れがある。[Problems to be Solved by the Invention] Conventional cylindrical horizontal stripe SO
FC has a very low yield of raw material powder because a constituent material is formed on the outer periphery of the base pipe by a thermal spraying method, and the base pipe may be broken due to the stress of the raw material powder applied to the base pipe. Further, since the substrate tube must be used without fail, it causes a great cost loss. Further, in the thermal spraying method, generation of pinholes is considered, which may affect the compactness of the solid electrolyte and the interconnector.
【０００４】さらに、また、溶射法では、固体電解質の
粒子を多孔質な燃料極に吹きつけるために図６に示すよ
うに、その表面のみに成膜され酸素イオンの反応の場で
あるとされる３相界面の量が少ないと考えられ、界面で
の性能向上は、見込めないという点がある。Further, in the thermal spraying method, as shown in FIG. 6, in order to spray the particles of the solid electrolyte to the porous fuel electrode, it is said that a film is formed only on the surface of the solid electrolyte and is a reaction field of oxygen ions. It is considered that the amount of the three-phase interface is small, and the performance improvement at the interface cannot be expected.
【０００５】本発明は上記技術水準に鑑み、従来技術の
コスト面及び界面での性能向上が計れる円筒横縞型固体
電解質電解セル及びその製造法を先に提案した（特願平
５−２７４１２０号）。該提案の円筒横縞型固体電解質
電解セル及びその製造法の要旨は下記のとおりである。 それぞれ円筒形に形成した燃料極管、絶縁性中間
材、インターコネクタ管及び導電性中間材の順序で重ね
た１組を複数組重ね合せて高温加圧してなる円筒形接合
体、該接合体表面に塗布・焼成して形成された固体電解
質膜及び該固体電解質膜の上に塗布・焼成して形成され
た空気極膜よりなることを特徴とする円筒横縞型固体電
解質電解セル。 それぞれ円筒形に形成された燃料極管、絶縁性中間
材、インターコネクタ管及び導電性中間材をこの順序で
重ねた１組を複数組重ね合せて、１４００〜１５００℃
の高温で加圧接合した後、該円筒形接合体を不必要部分
をマスキングして固体電解質スラリ中に浸漬して固体電
解質スラリ層を厚さ３〜１０μｍに塗布し、これを焼成
する工程を複数回繰返すことにより緻密で薄い３０〜１
００μｍ厚の固体電解質膜を成膜し、さらにその表面に
不必要部分をマスキングして空気極材料スラリをロール
プレート法により適用して１２００〜１３００℃で焼結
させて成膜することを特徴とする円筒横縞型固体電解質
電解セルの製造法。In view of the above-mentioned state of the art, the present invention has previously proposed a cylindrical horizontal stripe type solid electrolyte electrolytic cell which can improve the cost and the performance at the interface of the prior art and a manufacturing method thereof (Japanese Patent Application No. 5-274120). . The summary of the proposed cylindrical horizontal stripe type solid electrolyte electrolysis cell and its manufacturing method is as follows. Cylindrical bonded body formed by stacking a plurality of sets of a fuel electrode tube, an insulating intermediate material, an interconnector tube and a conductive intermediate material, which are each formed in a cylindrical shape, and pressurizing them at high temperature, and the surface of the bonded body A cylindrical horizontal striped solid electrolyte electrolytic cell comprising a solid electrolyte membrane formed by coating and baking on a solid electrolyte membrane and an air electrode membrane formed by coating and baking on the solid electrolyte membrane. Each of a plurality of sets of a fuel electrode tube, an insulating intermediate material, an interconnector tube and a conductive intermediate material, which are each formed in a cylindrical shape, are stacked in this order, and the temperature is 1400 to 1500 ° C.
After pressure-bonding at a high temperature, the cylindrical bonded body is immersed in a solid electrolyte slurry by masking unnecessary portions, and a solid electrolyte slurry layer is applied to a thickness of 3 to 10 μm, followed by firing. Precise and thin 30-1 by repeating multiple times
A solid electrolyte membrane having a thickness of 00 μm is formed, an unnecessary portion is masked on the surface, and a slurry of air electrode material is applied by a roll plate method and sintered at 1200 to 1300 ° C. to form a film. Method for manufacturing a cylindrical horizontal stripe type solid electrolyte electrolysis cell.
【０００６】しかしながら、円筒横縞型固体電解質セル
においては、固体電解質、空気極、燃料極及びインター
コネクタなどのすべての構成材料の熱膨張係数を一致さ
せることが重要であり、その中で、インターコネクタ材
料についてはＬａＣｒＯ3 系の材料が有力視されている
が、このものはインターコネクタ材料に要求される酸化
還元雰囲気下での安定性という面で劣っている。そのた
め、このＬａＣｒＯ3系の材料は低酸素分圧下で、導電
率が減少し固体電解質電解セルの性能劣化につながる。However, in the cylindrical horizontal stripe type solid electrolyte cell, it is important to match the thermal expansion coefficients of all the constituent materials such as the solid electrolyte, the air electrode, the fuel electrode and the interconnector. LaCrO 3 series materials are considered to be promising materials, but they are inferior in stability in an oxidation-reduction atmosphere required for interconnector materials. Therefore, this LaCrO 3 -based material has a reduced conductivity under a low oxygen partial pressure, leading to deterioration of the performance of the solid electrolyte electrolytic cell.
【０００７】本発明は上記技術水準に鑑み、前記提案の
円筒横縞型固体電解質電解セルをさらに改良し、酸化還
元雰囲気での安定性に優れたインターコネクタを有する
同固体電解質電解セルを提供しようとするものである。In view of the above state of the art, the present invention intends to further improve the above-mentioned proposed cylindrical horizontal stripe type solid electrolyte electrolytic cell and provide the same solid electrolyte electrolytic cell having an interconnector excellent in stability in a redox atmosphere. To do.
【０００８】[0008]
【課題を解決するための手段】本発明はそれぞれ円筒形
に形成した燃料極、絶縁性中間材、インターコネクタ管
及び導電性中間材の順序で重ねた１組を複数組重ね合せ
て高温加圧してなる円筒形接合体、該接合体表面に塗布
・焼成して形成された固体電解質膜及び該固体電解質膜
上に塗布・焼成して形成された空気極膜よりなる円筒横
縞型固体電解質電解セルにおいて、前記インターコネク
タ管の内側に他の構成部材と熱膨張係数が近似する材料
よりなる還元防止膜としての絶縁膜を施してなることを
特徴とする円筒横縞型固体電解質電解セルである。According to the present invention, a plurality of sets of a fuel electrode, an insulating intermediate material, an interconnector tube, and a conductive intermediate material, which are each formed in a cylindrical shape, are stacked in this order and are pressed at high temperature. Cylindrical bonded body comprising: a cylindrical bonded body, a solid electrolyte membrane formed by coating and firing on the surface of the bonded body, and a cylindrical horizontal striped solid electrolyte electrolytic cell comprising an air electrode membrane formed by coating and firing on the solid electrolyte membrane. 2. In the cylindrical horizontal striped solid electrolyte electrolytic cell, the interconnector tube is provided with an insulating film as a reduction prevention film made of a material having a thermal expansion coefficient similar to that of other constituent members inside the interconnector tube.
【０００９】本発明は従来の溶射法によるコストの損失
及び界面での性能向上を計るために、円筒形の基体管の
使用をなくし、円筒形に形成した燃料極管、絶縁性中間
材、内面に還元防止膜として作用する絶縁膜を施したイ
ンターコネクタ管及び導電性中間材の順序で重ねた１組
を複数組重ね合せて、高温加圧して接合してなる円筒形
接合体そのものを固体電解質膜及び空気極膜の支持管と
するものである。The present invention eliminates the use of a cylindrical base tube in order to reduce the cost and improve the performance at the interface by the conventional thermal spraying method, and the cylindrical fuel electrode tube, the insulating intermediate material, and the inner surface are formed. A cylindrical joined body itself is formed by stacking a plurality of pairs of an interconnector tube provided with an insulating film acting as a reduction prevention film and a conductive intermediate material in this order, and joining them by pressurizing at high temperature. It serves as a support tube for the membrane and the cathode membrane.
【００１０】本発明において使用される燃料極管の材料
の一例としてはＮｉＯとＹＳＺの混合物の焼結体（Ｎｉ
Ｏ／ＹＳＺ）、絶縁性中間材の材料の例としてはグリー
ンシート状態のＳｒＺｒＯ3 やＡｌ2 Ｏ3 、インターコ
ネクタ管の材料の例としてはＬａＣｒＭｇＯ3 やＬａＳ
ｒＣｒＯ3 の焼結体、導電性中間材の材料の例としては
Ｐｔや燃料極材料とインターコネクタ管材料のグリーン
シート状の混合物が使用される。As an example of the material of the anode used in the present invention, a sintered body of a mixture of NiO and YSZ (Ni
O / YSZ), SrZrO 3 or Al 2 O 3 in a green sheet state as an example of the material of the insulating intermediate material, and LaCrMgO 3 or LaS as an example of the material of the interconnector tube.
As an example of the material of the sintered body of rCrO 3 or the conductive intermediate material, Pt or a green sheet-like mixture of the fuel electrode material and the interconnector tube material is used.
【００１１】この際、インターコネクタ管の内面に施さ
れる還元防止膜として作用する絶縁膜の材料の例として
は、他の構成材料との熱膨張係数を一致させるためにＳ
ｒＺｒＯ3 ，Ｌａ2 Ｚｒ2 Ｏ7 などが使用される。At this time, as an example of the material of the insulating film acting as the reduction prevention film applied to the inner surface of the interconnector tube, S is used in order to match the thermal expansion coefficient with other constituent materials.
rZrO 3 , La 2 Zr 2 O 7, etc. are used.
【００１２】上記材料より構成された円筒形接合体に成
膜される固体電解質膜の材料の一例としてはＹＳＺが、
またその固体電解質膜の上に成膜される空気極材料の一
例としてはＬａ0.9 Ｓｒ0.1 ＭｎＯ3 があげられる。YSZ is an example of the material for the solid electrolyte membrane formed on the cylindrical assembly made of the above materials.
La 0.9 Sr 0.1 MnO 3 is an example of the air electrode material formed on the solid electrolyte membrane.
【００１３】グリーンシート状の絶縁性中間材はインタ
ーコネクタ管への燃料極管からの電気の流れを遮断する
目的と高温加圧接合時に用いる緩衝材として作用させる
ために使用される。また、グリーンシート状の導電性中
間材は有効発電部で発生した電気をつなぐインターコネ
クタ管から次の有効発電部へ電気を流すために使用さ
れ、高温加圧接合時に緩衝材として作用させるために使
用される。絶縁性中間材も導電性中間材も何れも約１０
０μｍ程度の厚さのものが使用される。The green sheet-shaped insulating intermediate material is used for the purpose of blocking the flow of electricity from the fuel electrode tube to the interconnector tube and for acting as a cushioning material used at the time of high temperature pressure bonding. In addition, the green sheet-shaped conductive intermediate material is used to flow electricity from the interconnector pipe that connects the electricity generated in the effective power generation section to the next effective power generation section, and to act as a buffer material during high temperature pressure bonding. used. Both insulating intermediate materials and conductive intermediate materials are about 10
A film having a thickness of about 0 μm is used.
【００１４】前記円筒形接合体に固体電解質膜を成膜す
るに際しては、低濃度の固体電解質材料スラリ中に不必
要部分をマスキングした該円筒形接合体を浸漬させ、固
体電解質材料が塗布された該円筒形接合体を１４００〜
１５００℃で焼成する工程を複数回繰返すことにより成
膜される。When depositing a solid electrolyte membrane on the cylindrical assembly, the solid electrolyte material was applied by immersing the cylindrical assembly with unnecessary portions masked in a low-concentration solid electrolyte material slurry. 1400 to the cylindrical bonded body
A film is formed by repeating the step of firing at 1500 ° C. a plurality of times.
【００１５】固体電解質膜を成膜された円筒形接合体に
空気極を成膜するに際しては、不必要部分をマスキング
した固体電解質膜形成円筒形接合体に空気極材料スラリ
をロールプレート法によって適用し、その後焼結するこ
とによって行われる。ロールプレート法とは不必要部分
にマスキングを施された固体電解質膜形成円筒形接合体
をジグにセットして回転させながら空気極材料スラリを
流し込み、流し込んだ空気極材料スラリの付着高さをマ
スキングの高さに合せ、その後、空気極材料スラリを付
着した円筒形接合体を乾燥する方法のことである。When forming an air electrode on a cylindrical assembly having a solid electrolyte membrane formed thereon, an air electrode material slurry is applied by a roll plate method to the solid electrolyte membrane-formed cylindrical assembly having unnecessary portions masked. And then sintering. What is the roll plate method? The solid electrolyte membrane-formed cylindrical assembly with masking unnecessary parts is set on a jig and the air electrode material slurry is poured while rotating, and the height of adhesion of the poured air electrode material slurry is masked. Of the cathode electrode material slurry, and then drying the cylindrical joined body to which the slurry of the cathode material is attached.
【００１６】[0016]
【作用】インターコネクタ管の内側（燃料側）に還元防
止膜を成膜することでインターコネタ材料の還元雰囲気
下における導電率の低下を防ぐことができ、安定な材料
となるので固体電解質電解セルの性能の劣化を防ぐこと
ができる。また、固体電解質材料及び空気極をスラリに
よって成膜するために、図２に示すように、固体電解質
材料のスラリが燃料極材料内に浸み込み、界面での反応
場が増加し電極の性能は向上する。[Function] By forming a reduction prevention film on the inside of the interconnector tube (fuel side), it is possible to prevent a decrease in conductivity of the interconnector material in a reducing atmosphere, and a stable material is obtained, so a solid electrolyte electrolytic cell It is possible to prevent the deterioration of the performance. Further, in order to form the solid electrolyte material and the air electrode by the slurry, as shown in FIG. 2, the slurry of the solid electrolyte material penetrates into the fuel electrode material, the reaction field at the interface increases, and the performance of the electrode increases. Will improve.
【００１７】[0017]
【実施例】以下、本発明の円筒横縞型固体電解質電解セ
ルの一実施例を図１によって説明する。初めに、燃料極
材料であるＮｉＯ／ＹＳＺスラリを押出し成形法によ
り、厚さ：２ｍｍ、長さ：６００〜８００ｍｍで内部を
燃料が通過可能な孔径を有する燃料極前駆体を製作し、
これを１４５０℃で焼成して多孔質で強度をもつように
し、単位セルに必要な長さに切断し、図１（ａ）に示す
燃料極管（内径：２２ｍｍ、肉厚：２ｍｍ）１とする。
次に、絶縁性中間材々料であるＳｒＺｒＯ3 スラリを押
出し成形法により成形し、これを焼成しないまゝ必要な
長さに切断し、図１（ａ）に示す絶縁性中間材（内径：
２２ｍｍ、肉厚：２ｍｍ）２とする。また、インターコ
ネクタ管材料であるＬａＣｒ0.9 Ｍｇ0.1 Ｏ3 スラリを
前記燃料極管１と同じ方法で製作し、図１（ａ）に示す
インターコネクタ管（内径：２２ｍｍ、肉厚：２ｍｍ）
３とする。さらに、導電性中間材々料であるＰｔスラリ
を前記絶縁性中間材２と同じ方法で製作し、図１（ａ）
に示す導電性中間材（内径：２２ｍｍ、肉厚：２ｍｍ）
４とする。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the cylindrical horizontal stripe type solid electrolyte electrolytic cell of the present invention will be described below with reference to FIG. First, a NiO / YSZ slurry, which is a fuel electrode material, is extruded to produce a fuel electrode precursor having a thickness of 2 mm and a length of 600 to 800 mm and a hole diameter through which the fuel can pass,
This was fired at 1450 ° C. to make it porous and strong, cut into a length required for a unit cell, and formed into a fuel electrode tube (inner diameter: 22 mm, wall thickness: 2 mm) 1 shown in FIG. To do.
Next, an SrZrO 3 slurry, which is an insulating intermediate material, is formed by an extrusion molding method, cut into a required length without firing, and the insulating intermediate material (inner diameter:
22 mm, wall thickness: 2 mm) 2. Further, LaCr 0.9 Mg 0.1 O 3 slurry, which is an interconnector tube material, was manufactured by the same method as the fuel electrode tube 1, and the interconnector tube shown in FIG. 1A (inner diameter: 22 mm, wall thickness: 2 mm).
Set to 3. Further, a Pt slurry, which is a conductive intermediate material, was manufactured by the same method as that for the insulating intermediate material 2,
Conductive intermediate material (inner diameter: 22 mm, wall thickness: 2 mm)
Set to 4.
【００１８】次に、上記のようにして製作したインター
コネクタ管３の内側（燃料側）の還元雰囲気にさらされ
る部分に、図１（ｂ）に示すように還元防止膜として作
用する絶縁膜５を成膜する。この絶縁膜５の材料として
は他の構成材料との熱膨張係数の一致性及び絶縁性とい
う点からＳｒＺｒＯ3 やＬａ2 Ｚｒ2 Ｏ7 が使用され
る。Next, as shown in FIG. 1 (b), an insulating film 5 acting as a reduction prevention film is formed on the portion of the inside of the interconnector tube 3 (fuel side) exposed as described above, which is exposed to the reducing atmosphere. To form a film. As the material of the insulating film 5, SrZrO 3 or La 2 Zr 2 O 7 is used from the viewpoint of matching the thermal expansion coefficient with other constituent materials and insulating properties.
【００１９】上述したように製作した燃料極管１、絶縁
性中間材２、絶縁膜５を有するインターコネクタ管３及
び導電性中間材４よりなる１組の単位セルを複数個組み
重ねて、接合温度：１４２０℃、接合圧力：０．２３７
ｋｇｆ／ｍｍ2 、接合時間：１時間の条件で高温加圧接
合して、図１（ｃ）に示すような１本の円筒形接合体を
得、これを従来の基体管と同じ作用をもつものとする。A plurality of one unit cell composed of the anode 1, the insulating intermediate material 2, the interconnector tube 3 having the insulating film 5 and the conductive intermediate material 4 manufactured as described above are stacked and joined. Temperature: 1420 ° C, bonding pressure: 0.237
High-temperature pressure bonding was performed under the conditions of kgf / mm 2 and bonding time: 1 hour to obtain a single cylindrical bonded body as shown in FIG. 1 (c), which has the same function as a conventional substrate tube. I shall.
【００２０】その後、インターコネクタ管３の絶縁性中
間材２側の一部を残し、インターコネクタ管の外周部に
マスキングを施こし、導電性中間材４、燃料極管１、絶
縁性中間材２及びインターコネクタ管３の一部外周面上
に、固体電解質材料であるＹＳＺが塗布されるように、
マスキングを施こした円筒形接合体を低濃度のＹＳＺス
ラリ（エタノール：９４ｗｔ％、ＹＳＺ：６ｗｔ％）中
に浸漬し、ＹＳＺの塗布後、１４５０℃で焼成する工程
を複数回繰り返すことによって、図１（ｄ）に示すよう
に緻密で約５０μｍの薄い固体電解質膜５を成膜する。
この固体電解質膜５の成膜方法によって、図２に示すよ
うに固体電解質であるＹＳＺは多孔質の燃料極管１の空
隙に浸み込むので、従来法の説明で言及した３相界面の
量が大となり、界面での性能向上が達成される。Thereafter, the outer peripheral portion of the interconnector tube is masked while leaving a part of the interconnector tube 3 on the side of the insulating intermediate material 2, and the conductive intermediate material 4, the fuel tube 1, and the insulating intermediate material 2 are provided. And so that YSZ, which is a solid electrolyte material, is applied to a part of the outer peripheral surface of the interconnector tube 3,
By immersing the masked cylindrical joint in a low-concentration YSZ slurry (ethanol: 94 wt%, YSZ: 6 wt%) and applying YSZ, firing at 1450 ° C. is repeated several times. As shown in FIG. 1 (d), a dense solid electrolyte membrane 5 having a thickness of about 50 μm is formed.
By this method of forming the solid electrolyte membrane 5, YSZ, which is a solid electrolyte, penetrates into the voids of the porous anode 1 as shown in FIG. 2, so that the amount of the three-phase interface mentioned in the description of the conventional method is increased. And the performance improvement at the interface is achieved.
【００２１】最後に、インターコネクタ管３の導電性中
間材４側のマスキングの一部を取り除き、空気極材料で
あるＬａ0.9 Ｓｒ0.1 ＭｎＯ3 スラリをロールプレート
法により、インターコネクタ管３の一部と固体電解質膜
５の外周部により塗布し、１３００℃で２時間焼結させ
て図１（ｅ）に示すように円筒横縞型固体電解質電解セ
ルを得る。Finally, a part of the masking on the side of the conductive intermediate material 4 of the interconnector tube 3 is removed, and a La 0.9 Sr 0.1 MnO 3 slurry which is an air electrode material is partially rolled by the roll plate method. And the outer peripheral portion of the solid electrolyte membrane 5 and then sintered at 1300 ° C. for 2 hours to obtain a cylindrical horizontal stripe type solid electrolyte electrolytic cell as shown in FIG.
【００２２】[0022]
【発明の効果】インターコネクタ管の内側（燃料側）
に、絶縁材を施すことで、インターコネクタ管の還元雰
囲気下における導電率の劣化を防ぐことが可能であり、
従来の固体電解質電解セルに比し、図３に示すように、
作動電圧の経時劣化を防ぐことができる。EFFECT OF THE INVENTION Inside the interconnector pipe (fuel side)
In addition, by applying an insulating material, it is possible to prevent the deterioration of the electrical conductivity of the interconnector tube in a reducing atmosphere.
Compared with the conventional solid electrolyte electrolytic cell, as shown in FIG.
It is possible to prevent deterioration of the operating voltage over time.
【図１】本発明の円筒横縞型固体電解質電解セルの製造
法の一実施例の説明図。FIG. 1 is an explanatory view of an embodiment of a method for manufacturing a cylindrical horizontal stripe type solid electrolyte electrolytic cell of the present invention.
【図２】本発明の円筒横縞型固体電解質電解セルの３相
界面の状況の説明図。FIG. 2 is an explanatory view of a state of a three-phase interface of a cylindrical horizontal stripe type solid electrolyte electrolytic cell of the present invention.
【図３】本発明の円筒横縞型ＳＯＦＣの作動電圧の経時
変化を示す図表。FIG. 3 is a chart showing changes over time in operating voltage of a cylindrical horizontal stripe SOFC of the present invention.
【図４】従来の円筒横縞型固体電解質電解セルの製造法
の一態様の説明図。FIG. 4 is an explanatory view of one embodiment of a method for manufacturing a conventional cylindrical horizontal stripe type solid electrolyte electrolytic cell.
【図５】円筒横縞型固体電解質電解セルの外観図。FIG. 5 is an external view of a cylindrical horizontal stripe type solid electrolyte electrolytic cell.
【図６】従来の円筒横縞型固体電解質電解セルの３相界
面の状況の説明図。FIG. 6 is an explanatory diagram of a state of a three-phase interface of a conventional cylindrical horizontal stripe type solid electrolyte electrolytic cell.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 永田 勝巳 長崎県長崎市飽の浦町１番１号 三菱重工 業株式会社長崎造船所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsumi Nagata 1-1 1-1 Atsunoura-machi, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd. Nagasaki Shipyard Co., Ltd.
Claims (1)
性中間材、インターコネクタ管及び導電性中間材の順序
で重ねた１組を複数組重ね合せて高温加圧してなる円筒
形接合体、該接合体表面に塗布、焼成して形成された固
体電解質膜及び該固体電解質膜上に塗布、焼成して形成
された空気極膜よりなる円筒横縞型固体電解質電解セル
において、前記インターコネクタ管の内側に他の構成部
材と熱膨張係数が近似する材料よりなる還元防止膜とし
ての絶縁膜を施してなることを特徴とする円筒横縞型固
体電解質電解セル。1. A cylindrical joined body formed by stacking a plurality of sets of a fuel electrode, an insulating intermediate material, an interconnector tube, and a conductive intermediate material, which are each formed in a cylindrical shape, in order, and pressurizing them at high temperature. A cylindrical horizontal striped solid electrolyte electrolytic cell comprising a solid electrolyte membrane formed by coating and firing on the surface of the bonded body and an air electrode membrane formed by coating and firing on the solid electrolyte membrane. A cylindrical horizontal striped solid electrolyte electrolysis cell, characterized in that an insulating film as a reduction prevention film made of a material having a thermal expansion coefficient similar to that of other constituent members is provided inside.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5275139A JPH07130385A (en) | 1993-11-04 | 1993-11-04 | Cylindrical lateral band type solid electrolyte electrolytic cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5275139A JPH07130385A (en) | 1993-11-04 | 1993-11-04 | Cylindrical lateral band type solid electrolyte electrolytic cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07130385A true JPH07130385A (en) | 1995-05-19 |
Family
ID=17551237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5275139A Withdrawn JPH07130385A (en) | 1993-11-04 | 1993-11-04 | Cylindrical lateral band type solid electrolyte electrolytic cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07130385A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09245819A (en) * | 1996-03-07 | 1997-09-19 | Tanaka Kikinzoku Kogyo Kk | Fuel cell and electrolytic cell and cooling and dehumidifying method therefor |
| WO2009008979A1 (en) * | 2007-07-05 | 2009-01-15 | Corning Incorporated | Insulation for sofc systems |
| JP2013157254A (en) * | 2012-01-31 | 2013-08-15 | Mitsubishi Heavy Ind Ltd | Solid oxide fuel cell stack |
| JP2013182708A (en) * | 2012-02-29 | 2013-09-12 | Toto Ltd | Fuel cell device |
| JP2014089847A (en) * | 2012-10-29 | 2014-05-15 | Mitsubishi Heavy Ind Ltd | Solid oxide fuel cell |
| EP3331080A1 (en) | 2016-12-02 | 2018-06-06 | Toto Ltd. | Fuel cell stack device and fuel cell device |
-
1993
- 1993-11-04 JP JP5275139A patent/JPH07130385A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09245819A (en) * | 1996-03-07 | 1997-09-19 | Tanaka Kikinzoku Kogyo Kk | Fuel cell and electrolytic cell and cooling and dehumidifying method therefor |
| WO2009008979A1 (en) * | 2007-07-05 | 2009-01-15 | Corning Incorporated | Insulation for sofc systems |
| JP2013157254A (en) * | 2012-01-31 | 2013-08-15 | Mitsubishi Heavy Ind Ltd | Solid oxide fuel cell stack |
| JP2013182708A (en) * | 2012-02-29 | 2013-09-12 | Toto Ltd | Fuel cell device |
| JP2014089847A (en) * | 2012-10-29 | 2014-05-15 | Mitsubishi Heavy Ind Ltd | Solid oxide fuel cell |
| EP3331080A1 (en) | 2016-12-02 | 2018-06-06 | Toto Ltd. | Fuel cell stack device and fuel cell device |
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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: 20010130 |