JP3339998B2 - Cylindrical fuel cell - Google Patents
Cylindrical fuel cellInfo
- Publication number
- JP3339998B2 JP3339998B2 JP25343595A JP25343595A JP3339998B2 JP 3339998 B2 JP3339998 B2 JP 3339998B2 JP 25343595 A JP25343595 A JP 25343595A JP 25343595 A JP25343595 A JP 25343595A JP 3339998 B2 JP3339998 B2 JP 3339998B2
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- current collector
- fuel cell
- cylindrical
- intermediate layer
- 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
-
- 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
Landscapes
- Fuel Cell (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、円筒型燃料電池セ
ルに関するもので、特に固体電解質と集電体との間に中
間層を形成した固体電解質型燃料電池セルに関する。The present invention relates to a cylindrical fuel cell, and more particularly to a solid electrolyte fuel cell having an intermediate layer formed between a solid electrolyte and a current collector.
【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1000〜1050℃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, a solid oxide fuel cell has a high power generation efficiency because its operating temperature is as high as 1000 to 1050 ° C., 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には円
筒型と平板型が知られている。平板型燃料電池セルは、
発電の単位体積当り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
筒型燃料電池セルでは、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。両形状の固体電解質型燃料電池セル
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, a solid oxide fuel cell is known to be a cylindrical type or a flat type. Flat fuel cells are
Although it has the feature that the power density per unit volume of power generation is high, there are problems such as incomplete gas seals and non-uniformity of the temperature distribution in the cell in practical use. On the other hand, the cylindrical fuel cell has the features that the output density is low, but the mechanical strength of the cell is high and the temperature uniformity in the cell can be maintained. Both types of solid oxide fuel cells are being actively researched and developed utilizing their respective features.
【0004】円筒型燃料電池の単セルは、図3に示した
ように開気孔率40%程度のCaO安定化ZrO2 を支
持管1とし、その上にLaMnO3 系材料からなる多孔
性の空気極2を形成し、その表面にY2 O3 安定化Zr
O2 からなる固体電解質3を被覆し、さらにこの表面に
多孔性のNi−ジルコニアの燃料極4が設けられてい
る。燃料電池のモジュ−ルにおいては、各単セルはLa
CrO3 系の集電体(インタ−コネクタ)5を介して接
続される。As shown in FIG. 3, a single cell of a cylindrical fuel cell has a support tube 1 made of CaO-stabilized ZrO 2 having an open porosity of about 40%, and a porous air made of a LaMnO 3 -based material thereon. A pole 2 is formed, and Y 2 O 3 stabilized Zr is formed on its surface.
A solid electrolyte 3 made of O 2 is covered, and a porous Ni-zirconia fuel electrode 4 is provided on this surface. In the fuel cell module, each single cell is La
It is connected via a CrO 3 -based current collector (inter-connector) 5.
【0005】このような燃料電池の発電は、各単セルを
1000〜1050℃の温度で保持するとともに、支持
管1内部に空気(酸素)6を、外部に燃料(水素)7を
供給することにより行われる。In such fuel cell power generation, each unit cell is maintained at a temperature of 1000 to 1050 ° C., and air (oxygen) 6 is supplied to the inside of the support tube 1 and fuel (hydrogen) 7 is supplied to the outside. It is performed by
【0006】そして、近年、セル作製の工程においてプ
ロセスを単純化するため、空気極材料であるLaMnO
3 系材料を直接多孔性の支持管として使用する試みがな
されている。空気極としての機能を合わせ持つ支持管材
料としては、LaをCaで20原子%又はSrで10〜
15原子%置換したLaMnO3 固溶体材料が用いられ
ている。In recent years, in order to simplify the process in the cell fabrication process, LaMnO, which is an air electrode material, has been used.
Attempts to use 3-based material as a direct porous support tube have been made. As a support tube material having the function as an air electrode, La is 20 at% by Ca or 10 to 10 at Sr.
A LaMnO 3 solid solution material substituted with 15 atomic% is used.
【0007】このような円筒状燃料電池セルは、例えば
固体電解質粉末を押出成形などにより円筒状に成形し、
焼成することにより円筒状焼結体を作製し、その焼結体
の内周面や外周面にスラリーコート法などにより空気極
層あるいは燃料極層を形成して焼成する方法により製造
されたり、またはセラミックスの多孔質支持管を焼成し
てなる円筒状焼結体の表面に、スラリーコート法や電気
化学蒸着法(EVD法)、プラズマ溶射法などにより空
気極層、固体電解質層、燃料極層を順次形成する方法に
より製造される。Such a cylindrical fuel cell is formed by, for example, molding a solid electrolyte powder into a cylindrical shape by extrusion molding or the like.
It is manufactured by a method of forming a cylindrical sintered body by firing, forming an air electrode layer or a fuel electrode layer on the inner peripheral surface or outer peripheral surface of the sintered body by a slurry coating method or the like, or firing, or An air electrode layer, a solid electrolyte layer, and a fuel electrode layer are formed on the surface of a cylindrical sintered body obtained by firing a ceramic porous support tube by a slurry coating method, an electrochemical deposition method (EVD method), a plasma spraying method, or the like. It is manufactured by a method of sequentially forming.
【0008】一方、本発明者等は、電気絶縁性円筒状基
体の表面に、少なくとも空気極および固体電解質を具備
してなる円筒型燃料電池セルを製造する方法であって、
電気絶縁性の粉末により円筒状基体用成形体を作製する
工程と、空気極形成用粉末および固体電解質形成用粉末
によりそれぞれシート状成形体を作製する工程と、前記
円筒状基体用成形体の表面に前記空気極用および固体電
解質用シート状成形体を巻き付けて積層して円筒型積層
物を作製する工程と、該円筒型積層物を同時に焼成する
工程とを具備する円筒型燃料電池セルの製造方法につい
て、先に出願した(特願平6−73025号)。この方
法では、非常に簡単なプロセスで、且つ少ない工程数で
燃料電池セルが歩留まりよく作製できる。また、空気極
成形体表面に電解質材料、集電体材料のグリ−ンシ−ト
を順次巻き付け積層した後に同時に焼成する(以下共焼
結と呼ぶこともある)技術についても、前述の出願に開
示した。On the other hand, the present inventors provide a method of manufacturing a cylindrical fuel cell comprising at least an air electrode and a solid electrolyte on the surface of an electrically insulating cylindrical substrate,
A step of preparing a molded body for a cylindrical substrate from an electrically insulating powder; a step of producing a molded sheet for each of a powder for forming an air electrode and a powder for forming a solid electrolyte; Manufacturing a cylindrical fuel cell, comprising: winding a sheet-like molded body for an air electrode and a solid electrolyte for lamination to form a cylindrical laminate; and simultaneously firing the cylindrical laminate. The method was previously filed (Japanese Patent Application No. 6-73025). According to this method, fuel cells can be manufactured with a very simple process and with a small number of steps with a high yield. The above-mentioned application also discloses a technique of sequentially winding and laminating green sheets of an electrolyte material and a current collector material on the surface of the air electrode molded body and simultaneously firing (hereinafter sometimes referred to as co-sintering). did.
【0009】[0009]
【発明が解決しようとする課題】上記の共焼結によるセ
ル製造においてはプロセスが簡単で、且つ少ない工程数
で燃料電池セルが歩留まりよく作製できるという特徴が
あるが、固体電解質層と集電体層の間の化学的反応性が
小さいため接合が悪く、ガスリ−クを起こし易く、長時
間の発電において出力が低下したり、あるいは発電中に
円筒型燃料電池セルが破損する虞があった。In the above-described cell production by co-sintering, there is a feature that the process is simple and the fuel cell can be produced with a small number of steps with a high yield. However, the solid electrolyte layer and the current collector Due to the low chemical reactivity between the layers, the bonding was poor, gas leaks were likely to occur, the output was reduced during long-term power generation, or the cylindrical fuel cell could be damaged during power generation.
【0010】[0010]
【課題を解決するための手段】本発明者等は上記問題点
に対して検討を重ねた結果、燃料電池セルにおいて固体
電解質層と集電体層を、Y,希土類元素およびアルカリ
土類金属のうちの少なくとも一種とZrを含有する複合
酸化物の中間層を介して接合することにより、固体電解
質層と集電体層とを強固に接合することができ、ガスリ
−クを防止し、高出力で長期安定性のある円筒型燃料電
池セルを作製できることを見出し、本発明に至った。Means for Solving the Problems As a result of repeated studies on the above problems, the present inventors have found that a solid electrolyte layer and a current collector layer in a fuel cell are formed of Y, a rare earth element and an alkaline earth metal. By joining at least one of them through the intermediate layer of the composite oxide containing Zr, the solid electrolyte layer and the current collector layer can be firmly joined, preventing gas leakage and high output. Thus, the present inventors have found that a cylindrical fuel cell having long-term stability can be produced by using the method described above, and have reached the present invention.
【0011】本発明の円筒型燃料電池セルは、円筒状の
固体電解質の片面に燃料極、他面に空気極が形成された
燃料電池セル本体の外面に、前記固体電解質の内面に形
成された前記燃料極または前記空気極と電気的に接続す
る集電体を設けてなり、少なくとも前記固体電解質と、
前記集電体とを同時焼成してなる円筒型燃料電池セルに
おいて、前記固体電解質の一部に切欠部を設けて該固体
電解質の内面に形成されている前記燃料極または前記空
気極の一部を露出させるとともに、この露出面および前
記切欠部近傍の前記固体電解質の端面を前記集電体によ
り被覆し、さらに、前記固体電解質と前記集電体との間
に、Y,希土類元素およびアルカリ土類金属から選択さ
れる少なくとも一種とZrとを含有する複合酸化物から
なる厚み0.05〜100μmの中間層が形成されてい
るものである。The cylindrical fuel cell of the present invention is formed on the outer surface of a fuel cell body in which a fuel electrode is formed on one surface of a cylindrical solid electrolyte and the air electrode is formed on the other surface, and on the inner surface of the solid electrolyte. A current collector electrically connected to the fuel electrode or the air electrode is provided, at least the solid electrolyte,
In the cylindrical fuel cell unit obtained by co-firing the current collector, a part of the solid electrolyte is provided with a cutout part, and a part of the fuel electrode or the air electrode is formed on the inner surface of the solid electrolyte. And the exposed surface and the end face of the solid electrolyte in the vicinity of the cutout are covered with the current collector. Further, between the solid electrolyte and the current collector, Y, a rare earth element and an alkaline earth are provided. An intermediate layer having a thickness of 0.05 to 100 [mu] m is formed of a composite oxide containing at least one selected from a class of metals and Zr.
【0012】[0012]
【作用】本発明では、燃料電池セルにおいて固体電解質
層と集電体層を、Y,希土類元素およびアルカリ土類金
属のうちの少なく一種とZrとを含有する複合酸化物の
中間層を介して接合することにより強固に接合でき、そ
の結果、ガスリ−クが防止され、高出力で長期安定性の
ある燃料電池セルを作製できるようになる。According to the present invention, in the fuel cell unit, the solid electrolyte layer and the current collector layer are connected via an intermediate layer of a composite oxide containing Zr and at least one of Y, rare earth element and alkaline earth metal. By joining, the fuel cell can be firmly joined. As a result, gas leakage is prevented, and a fuel cell having high output and long-term stability can be manufactured.
【0013】中間層は、Y,希土類元素およびアルカリ
土類金属のうちの少なく一種とZrとからなる複合酸化
物、または、Y,希土類元素およびアルカリ土類金属の
うちの少なく一種とZrとからなる複合酸化物の固溶体
であっても良い。The intermediate layer is made of a composite oxide comprising at least one of Y, a rare earth element and an alkaline earth metal and Zr, or a composite oxide comprising at least one of Y, a rare earth element and an alkaline earth metal and Zr. May be a solid solution of the composite oxide.
【0014】本発明のもう一つの大きな特徴はセラミッ
クスの多孔質支持管からなる仮焼体に空気極材料、固体
電解質材料、集電体材料のグリ−ンシ−トを順次巻き付
け積層する工程において、あるいは、支持管として機能
する空気極成形体に、固体電解質材料、集電体材料のグ
リ−ンシ−トを順次巻き付け積層する工程において、固
体電解質の表面に、スラリ−ディップ法,印刷法により
中間層を形成する上述の物質を塗布し、共焼結により中
間層を形成することができ、大きな工程の変更を必要と
しないことである。これは、工業的な観点から大きな特
徴といえる。Another major feature of the present invention is that a green sheet of an air electrode material, a solid electrolyte material, and a current collector material is sequentially wound and laminated on a calcined body formed of a ceramic porous support tube. Alternatively, in a step of sequentially winding and laminating a green sheet of a solid electrolyte material and a current collector material on an air electrode molded body functioning as a support tube, an intermediate is formed on the surface of the solid electrolyte by a slurry dipping method or a printing method. An intermediate layer can be formed by applying the above-mentioned material for forming a layer and co-sintering, and does not require a large process change. This is a great feature from an industrial point of view.
【0015】[0015]
【発明の実施の形態】以下に、本発明を詳述する。本発
明の円筒型燃料電池セルは、図1および図2に示すよう
に、円筒状の固体電解質31の内面に空気極32、外面
に燃料極33を形成して燃料電池セル本体34が構成さ
れており、この燃料電池セル本体34の外面に、空気極
32と電気的に接続する集電体35を設けてなるもので
ある。即ち、固体電解質31の一部に切欠部36が形成
され、固体電解質31の内面に形成されている空気極3
2の一部が露出しており、この露出面37および切欠部
36近傍の固体電解質31の表面が集電体35により被
覆されている。そして、固体電解質31の端部表面と集
電体35との間には、中間層38が形成されている。
尚、本発明の円筒型燃料電池セルは、多孔質支持管を形
成し、この多孔質支持管の外面に空気極32,固体電解
質31,燃料極33を順次積層して構成しても良い。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As shown in FIGS. 1 and 2, the cylindrical fuel cell of the present invention has an air electrode 32 formed on an inner surface of a cylindrical solid electrolyte 31 and a fuel electrode 33 formed on an outer surface thereof to form a fuel cell main body 34. A current collector 35 electrically connected to the air electrode 32 is provided on the outer surface of the fuel cell main body 34. That is, the notch 36 is formed in a part of the solid electrolyte 31, and the air electrode 3 formed on the inner surface of the solid electrolyte 31 is formed.
2 is exposed, and the surface of the solid electrolyte 31 near the exposed surface 37 and the notch 36 is covered with the current collector 35. An intermediate layer 38 is formed between the end surface of the solid electrolyte 31 and the current collector 35.
The cylindrical fuel cell of the present invention may be formed by forming a porous support tube, and sequentially stacking the air electrode 32, the solid electrolyte 31, and the fuel electrode 33 on the outer surface of the porous support tube.
【0016】空気極32と電気的に接続する集電体35
は、燃料電池セル本体34の外面に形成され段差のない
連続同一面39を覆うように形成されており、燃料極3
3とは電気的に連続されていない。連続同一面39は、
固体電解質31の内面に形成されている空気極32の一
部を露出させるとともに、固体電解質31の端面41と
空気極32の露出面37とを連続した同一面(固体電解
質31の端面41と空気極32の露出面37とが段差の
ない平面状態)となして構成されている。この連続同一
面39は固体電解質成形体の一部と空気極成形体の一部
とが連続した同一面となるまでセル本体の外周面を研摩
することにより形成されている。Current collector 35 electrically connected to air electrode 32
Are formed on the outer surface of the fuel cell main body 34 so as to cover the continuous same surface 39 with no step, and the fuel electrode 3
3 is not electrically continuous. The continuous same plane 39 is
A part of the air electrode 32 formed on the inner surface of the solid electrolyte 31 is exposed, and the end surface 41 of the solid electrolyte 31 and the exposed surface 37 of the air electrode 32 are continuously connected to the same surface (the end surface 41 of the solid electrolyte 31 and the air surface). The exposed surface 37 of the pole 32 is a flat state without any step. The continuous same surface 39 is formed by polishing the outer peripheral surface of the cell body until a part of the solid electrolyte molded body and a part of the air electrode molded body become the same continuous surface.
【0017】本発明の中間層38は、Y,希土類元素お
よびアルカリ土類金属から選択される少なくとも一種と
Zrとを含有する複合酸化物からなるものである。希土
類元素としては、Sc,La,Ce,Pr,Nd,P
m,Sm,Eu,Gd,Tb,Dy,Ho,Er,T
m,Yb,Luがある。この中でも、経済的観点から、
La,Y,Yb,Ndが特に好ましい。The intermediate layer 38 of the present invention is made of a composite oxide containing at least one selected from Y, rare earth elements and alkaline earth metals and Zr. As rare earth elements, Sc, La, Ce, Pr, Nd, P
m, Sm, Eu, Gd, Tb, Dy, Ho, Er, T
m, Yb, and Lu. Among them, from an economic point of view,
La, Y, Yb and Nd are particularly preferred.
【0018】アルカリ土類金属としては、Be,Mg,
Ca,Sr,Ba,Ra等がある。As the alkaline earth metal, Be, Mg,
There are Ca, Sr, Ba, Ra and the like.
【0019】Y,希土類元素およびアルカリ土類金属か
ら選択される少なくとも一種とZrとを含有する複合酸
化物としては、例えば、La2 Zr2 O7 ,Y2 Zr2
O7 ,Yb2 Zr2 O7 ,Nd2 Zr2 O7 ,CaZr
O3 ,SrZrO3 等がある。Examples of the composite oxide containing Zr and at least one selected from the group consisting of Y, a rare earth element and an alkaline earth metal include La 2 Zr 2 O 7 and Y 2 Zr 2.
O 7 , Yb 2 Zr 2 O 7 , Nd 2 Zr 2 O 7 , CaZr
O 3 , SrZrO 3 and the like.
【0020】Y,希土類元素およびアルカリ土類金属の
うちの少なく一種とZrとからなる複合酸化物の固溶体
であっても良い。このような固溶体としては、(Y、L
a)Zr2 O7 等がある。A solid solution of a composite oxide comprising Zr and at least one of Y, a rare earth element and an alkaline earth metal may be used. Such solid solutions include (Y, L
a) Zr 2 O 7 and the like.
【0021】中間層38は、電気的には絶縁体あるいは
電気伝導度がかなり小さいものである。仮にこの中間層
38が電気伝導性が大きいと、固体電解質31から集電
体35への漏れ電流が発生して出力低下の原因となる。
このような理由から中間層は、電気的に絶縁体、あるい
はそれに近いもので、かつ固体電解質31と集電体35
を強固に接合してガスリ−クを防止しなければならな
い。The intermediate layer 38 is an electrically insulating material or a material having a considerably small electric conductivity. If the intermediate layer 38 has a large electric conductivity, a leakage current from the solid electrolyte 31 to the current collector 35 occurs, causing a decrease in output.
For this reason, the intermediate layer is an electrically insulating material or a material that is close to the insulating material, and has a solid electrolyte 31 and a current collector 35.
Must be joined firmly to prevent gas leakage.
【0022】本発明の燃料電池セルには、例えば、固体
電解質31として3〜20モル%のY2 O3 あるいはY
b2 O3 を含有した部分安定化あるいは安定化ZrO2
が用いられる。また、空気極32としては、主としてL
aをCa,Srで10〜30原子%置換したLaMnO
3 が、燃料極33としては50〜80重量%Niを含む
ZrO2 (Y2 O3 )サ−メットが用いられる。また、
集電体35としては主としてLaを10〜20原子%の
Ca,Srで、あるいはCrを10〜30原子%のMg
で置換したLaCrO3 が用いられる。In the fuel cell of the present invention, for example, 3 to 20 mol% of Y 2 O 3 or Y
Partially stabilized or stabilized ZrO 2 containing b 2 O 3
Is used. The air electrode 32 is mainly L
LaMnO in which a is substituted with 10 to 30 atomic% of Ca and Sr
As the fuel electrode 33, a ZrO 2 (Y 2 O 3 ) cermet containing 50 to 80% by weight of Ni is used. Also,
As the current collector 35, La is mainly composed of 10 to 20 atomic% of Ca or Sr, or Cr is composed of 10 to 30 atomic% of Mg.
LaCrO 3 substituted in is used.
【0023】本発明の円筒型燃料電池セルの製造方法
は、空気極成形体の外周面に固体電解質のシート状成形
体を巻き付けて積層したものを、酸化性雰囲気で100
0〜1300℃の温度1〜3時間程度仮焼し、集電体3
5の積層箇所となる固体電解質仮焼体の表面を固体電解
質仮焼体の一部と空気極仮焼体の一部とがほぼ連続した
同一面平面となるように研摩する。In the method for manufacturing a cylindrical fuel cell according to the present invention, a sheet formed body of a solid electrolyte is wound around an outer surface of an air electrode formed body and laminated, and the resulting structure is oxidized in an oxidizing atmosphere.
Calcined at a temperature of 0 to 1300 ° C. for about 1 to 3 hours,
The surface of the solid electrolyte calcined body to be the lamination point 5 is polished so that a part of the solid electrolyte calcined body and a part of the air electrode calcined body are substantially continuous on the same plane.
【0024】そして、集電体35が積層される固体電解
質仮焼体の端面41に、Y,希土類元素およびアルカリ
土類金属から選択される少なくとも一種とZrとを含有
する複合酸化物の中間層成形体を形成し、空気極成形体
の露出面および中間層成形体の表面に集電体のシート状
成形体を積層する。中間層成形体の表面と空気極成形体
の露出面とが連続した同一面(平面)となるように、予
め固体電解質仮焼体の端面41の研摩量を多くすること
が望ましい。An intermediate layer of a composite oxide containing Zr and at least one selected from the group consisting of Y, a rare earth element and an alkaline earth metal is provided on an end face 41 of the calcined solid electrolyte body on which the current collector 35 is laminated. A molded body is formed, and a sheet-like molded body of a current collector is laminated on the exposed surface of the air electrode molded body and the surface of the intermediate layer molded body. It is desirable to increase the amount of polishing of the end face 41 of the calcined solid electrolyte body in advance so that the surface of the intermediate layer compact and the exposed surface of the cathode compact are continuous and the same plane (plane).
【0025】この中間層38を形成する方法としては、
例えば、La2 Zr2 O7 ,Y2 Zr2 O7 等を含有す
るスラリーを塗布して直接焼成により形成してもよい
し、Y2 O3 ,Yb2 O3 等を含有するスラリーを塗布
して高温でこれと集電体であるLaCrO3 と反応させ
Laを析出させた後、このLaと電解質中のZrと反応
させて、所望の中間層を形成させる方法がある。ガスリ
−ク抑制の観点からは後者の方法がより緻密質の中間層
が形成されるため優れている。The method of forming the intermediate layer 38 is as follows.
For example, a slurry containing La 2 Zr 2 O 7 , Y 2 Zr 2 O 7 or the like may be applied and formed by direct firing, or a slurry containing Y 2 O 3 or Yb 2 O 3 may be applied. Then, this is reacted with LaCrO 3 as a current collector at a high temperature to deposit La, and then this La is reacted with Zr in the electrolyte to form a desired intermediate layer. From the viewpoint of suppressing gas leakage, the latter method is excellent because a denser intermediate layer is formed.
【0026】即ち、中間層を形成するには固体電解質と
集電体のグリ−ンシ−ト間に予めLa2 Zr2 O7 ,Y
2 Zr2 O7 ,Yb2 Zr2 O7 ,Nd2 Zr2 O7 ,
等を含有するスラリーあるいはそれらの固溶体を含有す
るスラリーを塗布した後、高温度で処理することにより
それぞれの複合酸化物からなる中間層が形成される。That is, in order to form the intermediate layer, La 2 Zr 2 O 7 , Y is previously provided between the solid electrolyte and the green sheet of the current collector.
2 Zr 2 O 7 , Yb 2 Zr 2 O 7 , Nd 2 Zr 2 O 7 ,
And the like, or a slurry containing a solid solution thereof is applied, and then treated at a high temperature to form an intermediate layer made of each composite oxide.
【0027】具体的な塗布方法としてはスラリ−ディッ
プ法、印刷法により行う。As a specific coating method, a slurry dipping method and a printing method are used.
【0028】また、その他の方法としてLa,Y,Y
b,Nd,Dy,Scの酸化物、例えばLa2 O3 ,Y
2 O3 ,Yb2 O3 ,Nd2 O3 ,Dy2 O3 ,Sc2
O3 を含有するスラリーを塗布してもよい。あるいは高
温の酸化雰囲気中において酸化物を形成する上述の元素
を含有する炭酸塩,臭酸塩,酢酸塩などの化合物を塗布
してもよい。これらのY,Yb等の元素は上述のように
Laを除き高温において集電体であるLaCrO3 結晶
中のLaと置換してLaが析出し、このLaは固体電解
質中のZrと反応して固体電解質と集電体間にLa2 Z
r2 O7 を形成する。一方、Laは直接電解質中のZr
と直接反応して固体電解質と集電体間にLa2 Zr2 O
7 を形成する。後者の方法においては,添加したLa,
Y,Ybからなる酸化物が残存する場合があるが、本発
明の中間層が層状に形成されていれば特に問題とならな
い。また、La2 Zr2 O7 中にY,Yb等を含有する
固溶体層が形成される場合もあるが特にこれも問題にな
らない。As another method, La, Y, Y
oxides of b, Nd, Dy, Sc, for example, La 2 O 3 , Y
2 O 3 , Yb 2 O 3 , Nd 2 O 3 , Dy 2 O 3 , Sc 2
A slurry containing O 3 may be applied. Alternatively, a compound such as a carbonate, a bromate, or an acetate containing the above-described element which forms an oxide in a high-temperature oxidizing atmosphere may be applied. As described above, these elements such as Y and Yb replace La in the LaCrO 3 crystal as a current collector and precipitate La at high temperatures, except for La, and this La reacts with Zr in the solid electrolyte. La 2 Z between the solid electrolyte and the current collector
Form r 2 O 7 . On the other hand, La is directly
Reacts directly with La 2 Zr 2 O between the solid electrolyte and the current collector.
Form 7 . In the latter method, the added La,
An oxide composed of Y and Yb may remain, but this does not pose any particular problem if the intermediate layer of the present invention is formed in a layered form. In some cases, a solid solution layer containing Y, Yb or the like is formed in La 2 Zr 2 O 7 , but this is not a problem.
【0029】La2 Zr2 O7 ,Y2 Zr2 O7 ,Yb
2 Zr2 O7 ,Nd2 Zr2 O7 等のスラリーを予め塗
布する場合は、原料粉末の平均粒子径は0.1〜10μ
m、特に0.5〜2μmの大きさがよい。粉末の平均粒
子径が0.1μmより小さいと粉末同士の凝集が大きく
均一に塗布することが困難である。また、粉末の平均粒
子径が10μmを越えると、焼結性が悪くなりガスリ−
クが発生し易くなる。La 2 Zr 2 O 7 , Y 2 Zr 2 O 7 , Yb
2 Zr 2 O 7, Nd 2 Zr 2 if you previously applied a slurry of O 7 or the like, the average particle diameter of the raw material powder is 0.1~10μ
m, and particularly preferably a size of 0.5 to 2 μm. If the average particle diameter of the powder is smaller than 0.1 μm, it is difficult to apply the powder uniformly due to a large agglomeration between the powders. On the other hand, if the average particle diameter of the powder exceeds 10 μm, the sinterability deteriorates, and
Cracks are likely to occur.
【0030】La,Y,Yb等の酸化物あるいはその化
合物を塗布する場合は、粉末の平均粒子径は0.1〜2
0μm、特に0.5〜5μmの大きさがよい。粉末の平
均粒子径が0.1μmより小さいと粉末の凝集が大きく
均一に塗布することが困難である。逆に、20μmを越
えると、塗布した元素とLaとの置換反応が小さく中間
層の形成が不十分となり、ガスリ−クが起こり易くなる
ためである。When an oxide such as La, Y, Yb or a compound thereof is applied, the average particle diameter of the powder is 0.1 to 2
A size of 0 μm, especially 0.5 to 5 μm is good. If the average particle diameter of the powder is smaller than 0.1 μm, it is difficult to apply the powder uniformly due to large agglomeration of the powder. Conversely, if the thickness exceeds 20 μm, the substitution reaction between the applied element and La becomes small and the formation of the intermediate layer becomes insufficient, and gas leakage easily occurs.
【0031】La2 Zr2 O7 等の中間層の厚さは0.
05〜100μm、特には1〜50μmが最も好まし
い。中間層の厚みが0.05μmより薄いとガスリ−ク
に対する抑制効果が小さく、また100μmを越えると
電解質および集電体と中間層の熱膨張係数の違いから中
間層内にクラックが発生し易くなり、ガスリ−クが起こ
り易くなる。The thickness of the intermediate layer, such as La 2 Zr 2 O 7, is about 0.3.
It is most preferably from 0.5 to 100 μm, particularly preferably from 1 to 50 μm. If the thickness of the intermediate layer is less than 0.05 μm, the effect of suppressing gas leakage is small, and if it exceeds 100 μm, cracks tend to occur in the intermediate layer due to differences in the thermal expansion coefficients of the electrolyte, the current collector and the intermediate layer. And gas leaks are likely to occur.
【0032】このようにして作製した空気極/固体電解
質/集電体積層体は、大気等の酸化性雰囲気中、130
0〜1700℃の温度で1〜15時間程度同時焼成する
ことにより焼結させ、本発明の円筒型燃料電池セルが得
られる。The air electrode / solid electrolyte / current collector laminate thus manufactured is placed in an oxidizing atmosphere such as the air at 130.degree.
By sintering by simultaneous firing at a temperature of 0 to 1700 ° C. for about 1 to 15 hours, a cylindrical fuel cell of the present invention is obtained.
【0033】尚、集電体を形成する面は、固体電解質の
端面41と空気極32の露出面37との間に段差がない
方が好ましいが、例えば、連続同一面39は曲面であっ
ても良い。さらに、研摩せずに、固体電解質の端面41
と空気極32の露出面37との間に段差が生じている場
合でも、本発明は有効であるが、集電体の接合強度向上
の点から段差がない方が望ましい。The surface on which the current collector is formed preferably has no step between the end surface 41 of the solid electrolyte and the exposed surface 37 of the air electrode 32. For example, the continuous same surface 39 is a curved surface. Is also good. Further, without polishing, the end face 41 of the solid electrolyte
The present invention is effective even when a step is generated between the current collector and the exposed surface 37 of the air electrode 32, but it is desirable that there be no step from the viewpoint of improving the joining strength of the current collector.
【0034】また、本発明の円筒型燃料電池セルは、従
来、固体電解質と集電体とを当接して接合していた部分
を、本発明の中間層を介して接合するものであれば、ど
のような方法で製造されたものでも良い。Further, the cylindrical fuel cell of the present invention may be any one that joins a portion where a solid electrolyte and a current collector are conventionally contacted and joined via an intermediate layer of the present invention. It may be manufactured by any method.
【0035】[0035]
実施例1 空気極を形成する粉末としてLa2 O3 ,MnO2 ,C
aCO3 の粉末をLa0.85Ca0.15MnO3 となるよう
に秤量混合した後に1500℃で仮焼して(La、C
a)MnO3 粉末を得た。この後、これを粉砕して平均
粒子径が6μmの粉末を作製した。また、固体電解質を
形成する粉末として平均粒子径0.5μmのY2 O3 を
10モル%の割合で含有する共沈法ZrO2 粉末を準備
した。さらに、燃料極を形成する粉末としてNiO粉末
とZrO2 (Y2 O3 含有)粉末を重量比で80:20
の割合で混合したものを、集電体を形成する粉末として
平均粒子径1μmのLa0.8 Ca0.21CrO3 からなる
化合物粉末を準備した。Example 1 La 2 O 3 , MnO 2 , C
The aCO 3 powder was weighed and mixed to obtain La 0.85 Ca 0.15 MnO 3 and then calcined at 1500 ° C. (La, C
a) MnO 3 powder was obtained. Thereafter, this was pulverized to produce a powder having an average particle diameter of 6 μm. In addition, a coprecipitated ZrO 2 powder containing 10 mol% of Y 2 O 3 having an average particle diameter of 0.5 μm was prepared as a powder for forming a solid electrolyte. Further, NiO powder and ZrO 2 (containing Y 2 O 3 ) powder as the powder for forming the fuel electrode are in a weight ratio of 80:20.
The compound powder composed of La 0.8 Ca 0.21 CrO 3 having an average particle diameter of 1 μm was prepared as a powder for forming a current collector by mixing the powders in the ratio described above.
【0036】まず、上記の6μmの(La,Ca)Mn
O3 粉末を水を溶媒としてスラリーを作製し、このスラ
リーを用いて押出成形装置により内径13mm、外径1
6mmの円筒状の空気極成形体を得た。一方、固体電解
質については、上記Y2 O3安定化ZrO2 粉末を水を
溶媒としてスラリーを作製し、これをドクターブレード
法により厚み150μmのシート状成形体を作製した。
燃料極については上記NiO粉末とZrO2 (Y2 O3
含有)粉末を同様に水を溶媒としてスラリーを作製し、
これをドクターブレード法により厚み100μmのシー
ト状成形体を作製した。First, the 6 μm (La, Ca) Mn
A slurry was prepared from O 3 powder using water as a solvent, and the slurry was used to form an inner diameter of 13 mm and an outer diameter of 1 using an extrusion molding apparatus.
A 6 mm cylindrical air electrode molding was obtained. On the other hand, as for the solid electrolyte, a slurry was prepared from the above Y 2 O 3 stabilized ZrO 2 powder using water as a solvent, and a slurry was formed into a 150 μm thick sheet by a doctor blade method.
For the fuel electrode, the above NiO powder and ZrO 2 (Y 2 O 3
Similarly, a slurry is prepared from the powder using water as a solvent,
This was formed into a sheet-like molded body having a thickness of 100 μm by a doctor blade method.
【0037】そして、円筒状の空気極成形体の表面にア
クリル樹脂からなる接着材を介して、電解質シ−トを巻
き付け、空気極の露出面と電解質シ−トの表面に中間層
を形成し、集電体シ−ト、燃料極シ−トを順次巻き付
け、図1に示したように円筒状積層体を作製した。電解
質シ−トと集電体シ−トの間の中間層には表1の複合酸
化物となる平均粒子径0.6〜2.5μmの複合酸化物
粉末を厚み1〜95μmになるようにスクリ−ン印刷に
て塗布した。その後、この円筒状積層体を大気中におい
て1500℃で5時間焼成して、図1に示したような円
筒状セルを作製した。Then, an electrolyte sheet is wound around the surface of the cylindrical air electrode molded body via an adhesive made of acrylic resin to form an intermediate layer on the exposed surface of the air electrode and the surface of the electrolyte sheet. Then, a current collector sheet and a fuel electrode sheet were sequentially wound to form a cylindrical laminate as shown in FIG. In the intermediate layer between the electrolyte sheet and the current collector sheet, a composite oxide powder having an average particle diameter of 0.6 to 2.5 μm, which becomes the composite oxide shown in Table 1, having a thickness of 1 to 95 μm. It was applied by screen printing. Thereafter, the cylindrical laminate was fired in the air at 1500 ° C. for 5 hours to produce a cylindrical cell as shown in FIG.
【0038】作製したセルについて、市販のHeリーク
試験機を用いて、25℃におけるHeの透過速度を測定
した。また、円筒状セルの内側に酸素を、外側に水素を
流して1000℃で1000時間毎に4000時間発電
を行い出力密度を測定した。The permeation rate of He at 25 ° C. was measured using a commercially available He leak tester for the produced cell. In addition, oxygen was supplied to the inside of the cylindrical cell and hydrogen was supplied to the outside, and power was generated at 1000 ° C. every 1000 hours for 4000 hours to measure the output density.
【0039】また、中間層の種類はX線回折により同定
し,中間層の厚みは走査型電子顕微鏡により測定した。
この結果を表1に示す。The type of the intermediate layer was identified by X-ray diffraction, and the thickness of the intermediate layer was measured by a scanning electron microscope.
Table 1 shows the results.
【0040】[0040]
【表1】 [Table 1]
【0041】この表1より、中間層を形成していない試
料No.1に対して、中間層を形成した本発明の試料は
いずれも高出力であった。From Table 1, it can be seen that Sample No. having no intermediate layer was formed. On the other hand, the samples of the present invention in which the intermediate layer was formed had a high output.
【0042】実施例2 実施例1に従い、空気極材料からなる円筒状の成形体表
面に電解質シ−ト、集電体シ−ト、燃料極シ−トを順次
巻き付け円筒状積層体を作製した後、1550℃で3時
間焼成して、図1に示したような電池セルを作製した。
この際、電解質シ−トと集電体シ−トの間には表2に示
した平均粒子径0.6〜1.3μmの酸化物、炭酸塩粉
末を厚み0.1〜90μmになるように塗布した。作製
したセルについては、実施例1と同様にHeの透過速度
を測定した。また、円筒状セルの内側に酸素を、外側に
水素を流して1000℃で1000時間発電を行い出力
密度を測定した。また、中間層の種類はX線回折により
同定した。この結果を表2に示す。Example 2 According to Example 1, an electrolyte sheet, a current collector sheet, and a fuel electrode sheet were sequentially wound around the surface of a cylindrical molded body made of an air electrode material to produce a cylindrical laminated body. Thereafter, the resultant was fired at 1550 ° C. for 3 hours to produce a battery cell as shown in FIG.
At this time, an oxide or carbonate powder having an average particle diameter of 0.6 to 1.3 [mu] m shown in Table 2 having a thickness of 0.1 to 90 [mu] m is provided between the electrolyte sheet and the current collector sheet. Was applied. For the fabricated cell, the transmission rate of He was measured in the same manner as in Example 1. In addition, oxygen was supplied to the inside of the cylindrical cell, and hydrogen was supplied to the outside thereof, and power was generated at 1000 ° C. for 1000 hours to measure the output density. The type of the intermediate layer was identified by X-ray diffraction. Table 2 shows the results.
【0043】[0043]
【表2】 [Table 2]
【0044】この表2より中間層を形成していない表1
の試料No.1に対して、中間層を形成した試料はいず
れも高出力であった。From Table 2, it can be seen that Table 1 having no intermediate layer was formed.
Sample No. On the other hand, the samples in which the intermediate layer was formed had a high output with respect to 1.
【0045】[0045]
【発明の効果】本発明の円筒型燃料電池セルでは、固体
電解質層と集電体層を、Y,希土類元素およびアルカリ
土類金属のうちの少なく一種とZrとを含有する複合酸
化物の中間層を介して接合することにより強固に接合で
き、その結果、ガスリ−クが防止され、高出力で長期安
定性のある燃料電池セルを作製できる。According to the cylindrical fuel cell of the present invention, the solid electrolyte layer and the current collector layer are formed between a composite oxide containing Y, at least one of rare earth elements and alkaline earth metals and Zr. By joining through the layers, the fuel cell can be firmly joined. As a result, gas leakage is prevented, and a fuel cell having high output and long-term stability can be manufactured.
【図1】本発明の円筒型燃料電池セルの断面図である。FIG. 1 is a sectional view of a cylindrical fuel cell according to the present invention.
【図2】図1の要部拡大図である。FIG. 2 is an enlarged view of a main part of FIG.
【図3】従来の円筒型燃料電池セルの斜視図である。FIG. 3 is a perspective view of a conventional cylindrical fuel cell.
31・・・固体電解質 32・・・空気極 33・・・燃料極 34・・・燃料電池セル本体 35・・・集電体 36・・・切欠部 37・・・露出面 38・・・中間層 39・・・連続同一面 41・・・端面 DESCRIPTION OF SYMBOLS 31 ... Solid electrolyte 32 ... Air electrode 33 ... Fuel electrode 34 ... Fuel cell main body 35 ... Current collector 36 ... Notch 37 ... Exposed surface 38 ... Middle Layer 39: continuous same plane 41: end face
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平2−309565(JP,A) 特開 平7−130379(JP,A) 特開 平7−111157(JP,A) 特開 平7−282825(JP,A) (58)調査した分野(Int.Cl.7,DB名) H01M 8/02 H01M 8/12 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-309565 (JP, A) JP-A-7-130379 (JP, A) JP-A-7-111157 (JP, A) JP-A-7-130 282825 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 8/02 H01M 8/12
Claims (1)
に空気極が形成された燃料電池セル本体の外面に、前記
固体電解質の内面に形成された前記燃料極または前記空
気極と電気的に接続する集電体を設けてなり、少なくと
も前記固体電解質と、前記集電体とを同時焼成してなる
円筒型燃料電池セルにおいて、前記固体電解質の一部に
切欠部を設けて該固体電解質の内面に形成されている前
記燃料極または前記空気極の一部を露出させるととも
に、この露出面および前記切欠部近傍の前記固体電解質
の端面を前記集電体により被覆し、さらに、前記固体電
解質と前記集電体との間に、Y,希土類元素およびアル
カリ土類金属から選択される少なくとも一種とZrとを
含有する複合酸化物からなる厚み0.05〜100μm
の中間層が形成されていることを特徴とする円筒型燃料
電池セル。1. A fuel cell having a fuel electrode formed on one surface of a cylindrical solid electrolyte and an air electrode formed on the other surface, and a fuel electrode or an air electrode formed on an inner surface of the solid electrolyte. A current collector for electrical connection is provided, and at least the solid electrolyte and the cylindrical fuel cell obtained by simultaneously firing the current collector are provided with cutouts in a part of the solid electrolyte. A part of the fuel electrode or the air electrode formed on the inner surface of the solid electrolyte is exposed, and the exposed surface and the end face of the solid electrolyte near the notch are covered with the current collector, and Between a solid electrolyte and the current collector, a thickness of a composite oxide containing at least one selected from the group consisting of Y, a rare earth element and an alkaline earth metal and Zr and a thickness of 0.05 to 100 μm
Wherein the intermediate layer is formed.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25343595A JP3339998B2 (en) | 1995-09-29 | 1995-09-29 | Cylindrical fuel cell |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25343595A JP3339998B2 (en) | 1995-09-29 | 1995-09-29 | Cylindrical fuel cell |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0997621A JPH0997621A (en) | 1997-04-08 |
JP3339998B2 true JP3339998B2 (en) | 2002-10-28 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP25343595A Expired - Fee Related JP3339998B2 (en) | 1995-09-29 | 1995-09-29 | Cylindrical fuel cell |
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JP (1) | JP3339998B2 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4544872B2 (en) * | 2003-01-27 | 2010-09-15 | 京セラ株式会社 | Fuel cell and fuel cell |
JP4511122B2 (en) * | 2003-02-28 | 2010-07-28 | 京セラ株式会社 | Fuel cell |
EP2168192A1 (en) * | 2007-07-05 | 2010-03-31 | Corning Incorporated | Insulation for sofc systems |
JP5181600B2 (en) * | 2007-09-28 | 2013-04-10 | 大日本印刷株式会社 | Solid oxide fuel cell, stack structure of solid oxide fuel cell, and manufacturing method of solid oxide fuel cell |
JP5363888B2 (en) * | 2009-01-28 | 2013-12-11 | 京セラ株式会社 | SOLID OXIDE FUEL CELL AND METHOD FOR PRODUCING THE SAME, FUEL CELL STACK DEVICE, FUEL CELL MODULE, FUEL CELL DEVICE |
JP4872027B1 (en) * | 2010-11-01 | 2012-02-08 | 日本碍子株式会社 | Solid oxide fuel cell |
-
1995
- 1995-09-29 JP JP25343595A patent/JP3339998B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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JPH0997621A (en) | 1997-04-08 |
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