JPH10223243A - Base pipe for solid electrolyte fuel cell - Google Patents
Base pipe for solid electrolyte fuel cellInfo
- Publication number
- JPH10223243A JPH10223243A JP9021584A JP2158497A JPH10223243A JP H10223243 A JPH10223243 A JP H10223243A JP 9021584 A JP9021584 A JP 9021584A JP 2158497 A JP2158497 A JP 2158497A JP H10223243 A JPH10223243 A JP H10223243A
- Authority
- JP
- Japan
- Prior art keywords
- nio
- fuel cell
- base tube
- electrolyte fuel
- 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.)
- Withdrawn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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は固体電解質燃料電池
用基体管に関し、固体電解質燃料電池又は高温水蒸気電
解セルに用いられる基体管に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base tube for a solid electrolyte fuel cell, and more particularly to a base tube used for a solid electrolyte fuel cell or a high-temperature steam electrolysis cell.
【０００２】[0002]
【従来の技術】従来、基体管材料としては、電子導電性
がほとんどないＣａＯで安定化したＺｒＯ2 やＡｌ2 Ｏ
3 が用いられてきた。基体管であるＣａＯで安定化した
ＺｒＯ2 は、熱膨脹係数が固体電解質であるＹ2 Ｏ3 に
より安定化したＺｒＯ2 に近いという特徴がある。これ
は、固体電解質燃料電池に発停時のクラック低減に有効
であるためである。図２は、こうした基体管を用いた固
体電解質燃料電池の断面図を示す。2. Description of the Related Art Conventionally, as a base tube material, ZrO 2 or Al 2 O stabilized with CaO having almost no electronic conductivity has been used.
3 has been used. ZrO 2 stabilized with CaO as a base tube has a characteristic that its thermal expansion coefficient is close to that of ZrO 2 stabilized with Y 2 O 3 as a solid electrolyte. This is because the solid oxide fuel cell is effective in reducing cracks when starting and stopping. FIG. 2 shows a cross-sectional view of a solid oxide fuel cell using such a base tube.
【０００３】図中の符号１は基体管を示す。この基体管
１の外周面には、一部が基体管１の一端部側の内周面に
まで延出した燃料極２が選択的に設けられている。この
燃料極２上には、電解質３，空気極４が順次設けられて
いる。前記基体管１と前記空気極４の一部間には、イン
タコネクタ５が設けられている。図中の左側に位置する
前記燃料極２の端部、及び右図の右側に位置して基体管
内部まで延出した燃料極２端部には、それぞれ集電部品
としてのリード線６，７が接続されている。[0003] Reference numeral 1 in the figure denotes a base tube. On the outer peripheral surface of the base tube 1, a fuel electrode 2 partially extending to the inner peripheral surface on one end side of the base tube 1 is selectively provided. An electrolyte 3 and an air electrode 4 are sequentially provided on the fuel electrode 2. An interconnector 5 is provided between the base tube 1 and a part of the air electrode 4. Lead wires 6 and 7 as current collecting components are respectively provided at the end of the fuel electrode 2 located on the left side in the figure and the end of the fuel electrode 2 extending to the inside of the base tube on the right side of the right figure. Is connected.
【０００４】こうした構成の固体電解質燃料電池では、
集電に通常金属部材を用いるため、還元雰囲気中で用い
なければならない。このため、基体管１の片側を還元状
態にする。図２では、基体管１の左側には燃料を流して
還元雰囲気にしてある。In the solid electrolyte fuel cell having such a structure,
Since a metal member is usually used for current collection, it must be used in a reducing atmosphere. Therefore, one side of the base tube 1 is brought into a reduced state. In FIG. 2, a fuel is flowed on the left side of the base tube 1 to make a reducing atmosphere.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、従来用
いられてきた基体管材料は電子導電性がないため、基体
管表面に作られたセル部からの集電が難しい。また、集
電用の集電部材によりコストが向上するという問題があ
る。However, since the base tube material conventionally used has no electronic conductivity, it is difficult to collect current from a cell portion formed on the surface of the base tube. Further, there is a problem that the cost is increased by the current collecting member for current collection.
【０００６】本発明はこうした事情を考慮してなされた
もので、基体管の材料としてＮｉＯの重量が７７．３ｗ
ｔ％以上８７．５ｗｔ％以下であり残部がＡｌ2 Ｏ3 と
することにより、集電部材を少なくしてコスト低減を図
り、もって低コストの固体電解質燃料電池又は高温水蒸
気電解セルが得られる固体電解質燃料電池用基体管を提
供することを目的とする。The present invention has been made in view of such circumstances, and the weight of NiO is 77.3 watts as the material of the base tube.
A solid component fuel cell or a high-temperature steam electrolytic cell which can be obtained at a low cost by reducing the number of current collecting members by making t 2% or more and 87.5 wt% or less and the balance being Al 2 O 3. An object of the present invention is to provide a substrate tube for an electrolyte fuel cell.
【０００７】[0007]
【課題を解決するための手段】本発明は、ＮｉＯとＡｌ
2 Ｏ3 より構成され、ＮｉＯの重量が７７．３ｗｔ％以
上８７．５ｗｔ％以下であり残部がＡｌ2 Ｏ3 であるこ
とを特徴とする固体電解質燃料電池用基体管である。SUMMARY OF THE INVENTION The present invention provides NiO and Al.
A substrate tube for a solid oxide fuel cell, characterized by being composed of 2 O 3 , wherein the weight of NiO is 77.3 wt% or more and 87.5 wt% or less, and the balance is Al 2 O 3 .
【０００８】本発明において、ＮｉＯとＡｌ2 Ｏ3 より
構成される基体管材料において、発電環境中で基体管中
に含まれるＮｉＯの還元により発生するＮｉにより電子
導電性を付与する。本発明に係る基体管材料は、発電状
態では固体電解質燃料製造時の熱処理により発生するＮ
ｉＡｌ2 Ｏ4 と還元によりＮｉＯから発生するＮｉとの
混合物で構成される。そして、ＮｉとＮｉＡｌ2 Ｏ4 と
の混合物の熱膨脹係数は、ＮｉＯとＡｌ2 Ｏ3 組成によ
り決定される。従って、本発明の基体管材料においても
熱膨脹係数をなるべく固体電解質のＹ2 Ｏ3 により安定
化したＺｒＯ2に近付ける必要がある。このとき、Ｎｉ
Ｏの含有量を少なくしすぎると電子導電性が低下し、集
電抵抗が大きくなり効率が低下する。このため、ＮｉＯ
の重量を７７．３ｗｔ％以上８７．５ｗｔ％以下とし
た。In the present invention, in a base tube material composed of NiO and Al 2 O 3 , electronic conductivity is imparted by Ni generated by reduction of NiO contained in the base tube in a power generation environment. The base tube material according to the present invention is capable of generating N 2 generated by heat treatment during production of a solid electrolyte fuel in a power generation state.
It is composed of a mixture of iAl 2 O 4 and Ni generated from NiO by reduction. The thermal expansion coefficient of the mixture of Ni and NiAl 2 O 4 is determined by the composition of NiO and Al 2 O 3 . Therefore, it is necessary that the coefficient of thermal expansion of the base tube material of the present invention be as close as possible to ZrO 2 stabilized by Y 2 O 3 of the solid electrolyte. At this time, Ni
If the O content is too low, the electronic conductivity decreases, the current collecting resistance increases, and the efficiency decreases. For this reason, NiO
Was 77.3 wt% or more and 87.5 wt% or less.
【０００９】［作用］本発明の基体管の組成であるＮｉ
ＯとＡｌ2 Ｏ3 は、固体電解質燃料電池製造時にＮｉＯ
とＡｌ2 Ｏ3 が反応してＮｉＡｌ2 Ｏ4 が生成する。本
発明の組成では、ＮｉＯの配合量が７７．３ｗｔ％〜８
７．５ｗｔ％と多くなっており、固体電解質燃料電池製
造時には、基体管の結晶相はＮｉＡｌ2 Ｏ4 とＮｉＯに
より構成される。さらに、発電状態においては、ＮｉＯ
が還元されてＮｉが生成する。したがって、発電状態に
おける基体管の結晶相はＮｉＡｌ2 Ｏ4 とＮｉである。[Action] Ni, which is the composition of the substrate tube of the present invention,
O and Al 2 O 3 are converted into NiO during solid electrolyte fuel cell production.
Reacts with Al 2 O 3 to produce NiAl 2 O 4 . In the composition of the present invention, the content of NiO is from 77.3% by weight to 8%.
When the solid oxide fuel cell is manufactured, the crystal phase of the base tube is composed of NiAl 2 O 4 and NiO. Further, in the power generation state, NiO
Is reduced to produce Ni. Therefore, the crystal phases of the base tube in the power generation state are NiAl 2 O 4 and Ni.
【００１０】また、本発明の基体管の電子導電性即ち導
電率はＮｉの量により決定され、更に熱膨脹係数におい
てもＮｉとＮｉＡｌ2 Ｏ4 の量比により決定される。本
発明のＮｉＯとＡｌ2 Ｏ3 の組成割合は、これらの適正
な範囲より決定されている。このようにして熱膨脹係数
と導電率について条件を満たす基体管は、集電部材とし
ての機能性が付与されており、集電材料の部品点数の低
減に有効であると考えられる。The electronic conductivity of the substrate tube of the present invention is determined by the amount of Ni, and the coefficient of thermal expansion is also determined by the ratio of Ni to NiAl 2 O 4 . The composition ratio of NiO and Al 2 O 3 of the present invention is determined from these proper ranges. The base tube that satisfies the conditions for the coefficient of thermal expansion and the electrical conductivity in this way has the function as a current collecting member, and is considered to be effective in reducing the number of components of the current collecting material.
【００１１】[0011]
【発明の実施の形態】以下、本発明に係る固体電解質燃
料電池について図１を参照して説明する。図中の符号11
は基体管である。この基体管11は、Ａｌ2 Ｏ3 のような
酸化物でも、焼成温度以下で分解し酸化物となるＡｌ
（ＯＨ）3 のような水酸化物でもよい。前記基体管11の
外周面には、絶縁体12を介して一部が基体管11の一端部
側にまで延出したＮｉＯとＹＳＺ（８ mol％Ｙ2 Ｏ3 −
ＺｒＯ2 ）のサーメットからなる燃料極13が選択的に設
けられている。この燃料極13上には、ＹＳＺからなる電
解質14，Ｌａ0.9 Ｓｒ0.1 ＭｎＯ3 からなる空気極15が
順次設けられている。前記基体管11と空気極15の一部間
には、Ｌａ0.9 Ｓｒ0.1 ＣｒＯ3 からなるインタコネク
タ16が設けられている。図中の左側に位置する前記燃料
極13の端部、及び図中の左側に位置する前記基体管11の
端部には、夫々集電部品としてのリード線17，18が接続
されている。ここで、基体管11の片側を還元状態にする
ため、基体管11の左側には燃料を流して還元雰囲気にし
てある。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a solid electrolyte fuel cell according to the present invention will be described with reference to FIG. Reference numeral 11 in the figure
Is a base tube. The base tube 11 is made of an oxide such as Al 2 O 3 , which is decomposed at a temperature lower than the firing temperature to become an oxide.
A hydroxide such as (OH) 3 may be used. On the outer peripheral surface of the base tube 11, NiO and YSZ (8 mol% Y 2 O 3 −) partially extended to one end side of the base tube 11 via an insulator 12 are provided.
A fuel electrode 13 made of ZrO 2 ) cermet is selectively provided. On this anode 13, an air electrode 15 made of the electrolyte 14, La 0.9 Sr 0.1 MnO 3 made of YSZ is sequentially provided. An interconnector 16 made of La 0.9 Sr 0.1 CrO 3 is provided between the base tube 11 and a part of the air electrode 15. Lead wires 17 and 18 as current collecting components are connected to an end of the fuel electrode 13 located on the left side in the figure and an end of the base tube 11 located on the left side in the figure, respectively. Here, in order to put one side of the base tube 11 in a reducing state, a fuel is flowed on the left side of the base tube 11 to make a reducing atmosphere.
【００１２】[0012]
【実施例】実施例１〜３では、下記表１に示す組成の基
体管を準備した。まず、基体管の原料１００ｗｔ％，例
えばＮｉＯとＡｌ2 Ｏ3 を適量混合した後、メチルセル
ロースのような成形助剤４ｗｔ％を添加する。なお、基
体管として機能するときに酸化物であれば、出発原料は
水酸化物でも、あるいは酸化物と水酸化物の混合物でも
よい。つづいて、水やグリセリンのような添加物１５ｗ
ｔ％（水：１０ｗｔ％、グリセリン５ｗｔ％）を入れ混
練後、管状に押出し成形する。但し、基体管は押出し成
形のみならず、静水圧プレス法でも成形可能である。次
に、このようにして得た基体管上にセルを印刷法により
成膜し１４００℃，２時間の条件下で焼成して、固体電
解質燃料電池を製作する。あるいは、押出し成形した後
焼成し溶射法にてセルを構成することも考えられる。本
実施例では、上述のように成形後の基体管を焼成し気孔
率を３０％程度（通常２０〜４０％）にした。焼成後の
基体管を切断し、熱膨張係数と導電率を測定した。更
に、セルを成膜し焼成した基体管は、９００℃発電温度
まで昇温し、再度室温まで降温した後、クラックの発生
の有無を調査した。また、比較例１，２についても表１
に示す組成の基体管を準備し、実施例と同様にしてクラ
ックの発生の有無を調査した。EXAMPLES In Examples 1 to 3, base tubes having the compositions shown in Table 1 below were prepared. First, 100 wt% of the raw material for the base tube, for example, NiO and Al 2 O 3 are mixed in an appropriate amount, and then 4 wt% of a molding aid such as methyl cellulose is added. In addition, as long as it is an oxide when functioning as a base tube, the starting material may be a hydroxide or a mixture of an oxide and a hydroxide. Next, add 15 w of additives such as water and glycerin
After mixing and kneading t% (water: 10 wt%, glycerin 5 wt%), the mixture is extruded into a tubular shape. However, the base tube can be formed not only by extrusion but also by an isostatic pressing method. Next, a cell is formed on the thus obtained base tube by a printing method and fired at 1400 ° C. for 2 hours to produce a solid oxide fuel cell. Alternatively, it is also conceivable to construct the cell by a thermal spraying method after extrusion molding and firing. In this example, the molded base tube was fired as described above to reduce the porosity to about 30% (normally 20 to 40%). The fired base tube was cut, and the coefficient of thermal expansion and the electrical conductivity were measured. Further, the temperature of the base tube obtained by forming and firing the cell was raised to a power generation temperature of 900 ° C., and was again lowered to room temperature. Then, the presence or absence of cracks was examined. Table 1 also shows Comparative Examples 1 and 2.
Was prepared, and the presence or absence of cracks was examined in the same manner as in the examples.
【００１３】[0013]
【表１】 [Table 1]
【００１４】表１より、導電性とクラック発生の有無よ
り適正な組成範囲が存在し、ＮｉＯ量が少ないと導電性
が低くなり、逆にＡｌ2 Ｏ3 量が少ないとクラックが発
生する。しかるに、クラックの発生がなく、さらに導電
性の高い領域は、ＮｉＯの配合量が７７．３ｗｔ％〜８
７．５ｗｔ％の本発明の範囲であることが明らかであ
る。From Table 1, it can be seen that there is an appropriate composition range depending on the conductivity and the presence or absence of cracks. If the amount of NiO is small, the conductivity will be low, and if the amount of Al 2 O 3 is small, cracks will occur. However, in a region where no crack is generated and the conductivity is higher, the content of NiO is 77.3 wt% to 8%.
It is clear that the range of the present invention is 7.5 wt%.
【００１５】[0015]
【発明の効果】以上詳述したように本発明によれば、基
体管の材料としてＮｉＯの重量が７７．３ｗｔ％以上８
７．５ｗｔ％以下であり残部がＡｌ2 Ｏ3 とすることに
より、集電部材を少なくしてコスト低減を図り、もって
低コストの固体電解質燃料電池又は高温水蒸気電解セル
が得られる固体電解質燃料電池用基体管を提供できる。As described above in detail, according to the present invention, the weight of NiO is 77.3 wt% or more as the material of the base tube.
When the content is 7.5 wt% or less and the balance is Al 2 O 3 , the cost can be reduced by reducing the number of current collecting members, so that a low-cost solid electrolyte fuel cell or a high-temperature steam electrolytic cell can be obtained. A base tube for use can be provided.
【図１】本発明の一実施例に係る固体電解質燃料電池用
基体管を用いた固体電解質燃料電池の断面図。FIG. 1 is a cross-sectional view of a solid electrolyte fuel cell using a solid electrolyte fuel cell base tube according to one embodiment of the present invention.
【図２】従来の固体電解質燃料電池の断面図。FIG. 2 is a cross-sectional view of a conventional solid oxide fuel cell.
11…基体管、 12…絶縁体、 13…燃料極、 14…電解質、 15…空気極、 16…インタコネクタ、 17，18…リード線。 11 ... base tube, 12 ... insulator, 13 ... fuel electrode, 14 ... electrolyte, 15 ... air electrode, 16 ... interconnector, 17, 18 ... lead wire.
Claims (1)
Ｏの重量が７７．３ｗｔ％以上８７．５ｗｔ％以下であ
り残部がＡｌ2 Ｏ3 であることを特徴とする固体電解質
燃料電池用基体管。1. An electronic device comprising NiO and Al 2 O 3 , wherein Ni
A substrate tube for a solid oxide fuel cell, characterized in that the weight of O is not less than 77.3 wt% and not more than 87.5 wt%, and the balance is Al 2 O 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9021584A JPH10223243A (en) | 1997-02-04 | 1997-02-04 | Base pipe for solid electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9021584A JPH10223243A (en) | 1997-02-04 | 1997-02-04 | Base pipe for solid electrolyte fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10223243A true JPH10223243A (en) | 1998-08-21 |
Family
ID=12059095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9021584A Withdrawn JPH10223243A (en) | 1997-02-04 | 1997-02-04 | Base pipe for solid electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10223243A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109613A (en) * | 2001-09-28 | 2003-04-11 | Mitsubishi Heavy Ind Ltd | Method of manufacturing fuel cell pipe and ceramics manufacturing device |
| JP2004253376A (en) * | 2003-01-27 | 2004-09-09 | Kyocera Corp | Fuel battery cell and method for manufacturing same, and fuel battery |
| JP2005071948A (en) * | 2003-08-28 | 2005-03-17 | National Institute Of Advanced Industrial & Technology | Hybrid porous tube, and manufacturing method of same |
| JPWO2004082058A1 (en) * | 2003-03-13 | 2006-06-15 | 東京瓦斯株式会社 | Solid oxide fuel cell module |
| JP2007329132A (en) * | 2007-07-20 | 2007-12-20 | National Institute Of Advanced Industrial & Technology | Hybrid porous tube |
| CN102394307A (en) * | 2011-10-12 | 2012-03-28 | 景德镇陶瓷学院 | Preparation method for anode support layer of solid oxide fuel cell |
| JP2014520368A (en) * | 2011-06-15 | 2014-08-21 | エルジー フューエル セル システムズ インク | Fuel cell system having interconnects |
| WO2015182518A1 (en) * | 2014-05-28 | 2015-12-03 | 京セラ株式会社 | Cell, cell stack, module, and module accommodation device |
-
1997
- 1997-02-04 JP JP9021584A patent/JPH10223243A/en not_active Withdrawn
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109613A (en) * | 2001-09-28 | 2003-04-11 | Mitsubishi Heavy Ind Ltd | Method of manufacturing fuel cell pipe and ceramics manufacturing device |
| JP2004253376A (en) * | 2003-01-27 | 2004-09-09 | Kyocera Corp | Fuel battery cell and method for manufacturing same, and fuel battery |
| JPWO2004082058A1 (en) * | 2003-03-13 | 2006-06-15 | 東京瓦斯株式会社 | Solid oxide fuel cell module |
| JP4541296B2 (en) * | 2003-03-13 | 2010-09-08 | 東京瓦斯株式会社 | Solid oxide fuel cell module |
| JP2005071948A (en) * | 2003-08-28 | 2005-03-17 | National Institute Of Advanced Industrial & Technology | Hybrid porous tube, and manufacturing method of same |
| JP2007329132A (en) * | 2007-07-20 | 2007-12-20 | National Institute Of Advanced Industrial & Technology | Hybrid porous tube |
| JP2014520368A (en) * | 2011-06-15 | 2014-08-21 | エルジー フューエル セル システムズ インク | Fuel cell system having interconnects |
| US9531013B2 (en) | 2011-06-15 | 2016-12-27 | Lg Fuel Cell Systems Inc. | Fuel cell system with interconnect |
| US10050285B2 (en) | 2011-06-15 | 2018-08-14 | Lg Fuel Cell Systems Inc. | Fuel cell system with interconnect |
| CN102394307A (en) * | 2011-10-12 | 2012-03-28 | 景德镇陶瓷学院 | Preparation method for anode support layer of solid oxide fuel cell |
| WO2015182518A1 (en) * | 2014-05-28 | 2015-12-03 | 京セラ株式会社 | Cell, cell stack, module, and module accommodation device |
| JP5933135B2 (en) * | 2014-05-28 | 2016-06-08 | 京セラ株式会社 | Cell, cell stack and module, and module housing device |
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