JP3180402B2 - Bonded structure of yttrium stabilized zirconia and lanthanum chromite - Google Patents
Bonded structure of yttrium stabilized zirconia and lanthanum chromiteInfo
- Publication number
- JP3180402B2 JP3180402B2 JP00139392A JP139392A JP3180402B2 JP 3180402 B2 JP3180402 B2 JP 3180402B2 JP 00139392 A JP00139392 A JP 00139392A JP 139392 A JP139392 A JP 139392A JP 3180402 B2 JP3180402 B2 JP 3180402B2
- Authority
- JP
- Japan
- Prior art keywords
- stabilized zirconia
- yttrium
- lanthanum chromite
- bonding agent
- lanthanum
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
- H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
- H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
- H01M8/0219—Chromium complex oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
- Ceramic Products (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、イットリウム安定化ジ
ルコニアとランタンクロマイトの接合構造に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a joint structure between yttrium-stabilized zirconia and lanthanum chromite.
【０００２】[0002]
【従来の技術と課題】例えば、固体電解質型燃料電池に
おいては、イットリウム安定化ジルコニアからなるスペ
ーサとランタンクロマイトからなるインターコネクタと
を接合する必要がある。従来はスペーサ及びインターコ
ネクタをそれぞれ単独で焼結した後、シール用ガラス等
の接合剤を介して接合していた。しかしながら、この接
合では、使用するガス（燃料ガス、空気）に対する機密
性や稼働時の温度の昇降に対する信頼性、耐久性に問題
があった。2. Description of the Related Art For example, in a solid oxide fuel cell, it is necessary to join a spacer made of yttrium stabilized zirconia and an interconnector made of lanthanum chromite. Conventionally, after sintering the spacer and the interconnector independently, they have been bonded via a bonding agent such as sealing glass. However, in this joining, there are problems in confidentiality with respect to a gas (fuel gas, air) to be used, reliability with respect to temperature rise and fall during operation, and durability.
【０００３】これとは別に、接合剤としてイットリウム
安定化ジルコニアをペースト状にしたものを用いて焼成
接合するものが考えられるが、インターコネクタ中のＣ
ｒが接合剤に拡散するため、接合剤の焼結性が変わり、
インターコネクタとの界面部が焼結しないという問題が
ある。そこで、本発明の課題は、気密性や稼働時の温度
の昇降に対する信頼性、耐久性に優れたイットリウム安
定化ジルコニアとランタンクロマイトの接合構造を提供
することにある。[0003] Separately, it is conceivable to use a paste made of yttrium-stabilized zirconia as a bonding agent and to perform sintering bonding.
Since r diffuses into the bonding agent, the sinterability of the bonding agent changes,
There is a problem that the interface with the interconnector does not sinter. Therefore, an object of the present invention is to provide a joint structure of yttrium-stabilized zirconia and lanthanum chromite that is excellent in airtightness, reliability against temperature rise and fall during operation, and excellent durability.
【０００４】[0004]
【課題を解決するための手段と作用】以上の課題を解決
するため、本発明に係るイットリウム安定化ジルコニア
とランタンクロマイトの接合構造は、イットリウム安定
化ジルコニアとランタンマンガナイトの重量比が０．１
〜１０．０の範囲の混合物を接合剤として用いて共焼結
されていることを特徴とする。In order to solve the above problems, the joint structure of yttrium-stabilized zirconia and lanthanum chromite according to the present invention has a weight ratio of yttrium-stabilized zirconia to lanthanum manganite of 0.1.
It is characterized by being co-sintered using a mixture in the range of ~ 10.0 as a bonding agent.
【０００５】以上の構成において、イットリウム安定化
ジルコニアにランタンマンガナイトを適量添加した接合
剤を用いて共焼結したため、イットリウム安定化ジルコ
ニアとランタンクロマイトの共焼結の際にランタンクロ
マイトから接合剤へＣｒが拡散しなくなり、Ｃｒ拡散に
よる接合剤の焼結性の変化が防止される。そして、接合
剤中のイットリウム安定化ジルコニアは被接合部材であ
るイットリウム安定化ジルコニアと焼結し、接合剤中の
ランタンマンガナイトは被接合部材であるランタンクロ
マイトと焼結する。また、接合剤中のランタンマンガナ
イトは被接合部材であるイットリウム安定化ジルコニア
の焼結性を妨げることはない。[0005] In the above configuration, since the co-sintering was performed using a bonding agent obtained by adding an appropriate amount of lanthanum manganite to yttrium-stabilized zirconia, the co-sintering of yttrium-stabilized zirconia and lanthanum chromite changed from lanthanum chromite to the bonding agent. Cr is no longer diffused, and a change in the sinterability of the bonding agent due to the diffusion of Cr is prevented. Then, yttrium-stabilized zirconia in the bonding agent sinters with yttrium-stabilized zirconia as a member to be bonded, and lanthanum manganite in the bonding agent sinters with lanthanum chromite as a member to be bonded. In addition, lanthanum manganite in the bonding agent does not hinder the sinterability of yttrium-stabilized zirconia as a member to be bonded.
【０００６】[0006]
【実施例】以下、本発明に係るイットリウム安定化ジル
コニアとランタンクロマイトの接合構造の実施例を説明
する。本実施例では固体電解質型燃料電池を例にして説
明する。図１は固体電解質型燃料電池の分解斜視図であ
る。固体電解質１は矩形状をしており、その材料として
はイットリウム安定化ジルコニア（以下、ＹＳＺとい
う）の粉末とバインダー剤のブチラール系樹脂、溶剤
（トルエン／エタノール）を混合してドクターブレード
法でグリーンシート状にしたものを用いる。空気極２及
び燃料極３はそれぞれ固体電解質１の上面、下面に設け
られる。燃料極３の材料としては、ＮｉＯとＹＳＺを重
量比６：４で混合した粉末とブチラール系樹脂、溶剤
（トルエン／エタノール）を混合してグリーンシート状
にしたものを用いる。空気極２の材料としては、Ｓｒ添
加ランタンマンガナイトの粉末とブチラール系樹脂、溶
剤（トルエン／エタノール）を混合してグリーンシート
状にしたものを用いる。グリーンシート状にされた固体
電解質１の上下面にそれぞれグリーンシート状にされた
空気極２、燃料極３が熱圧着される。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a joint structure between yttrium-stabilized zirconia and lanthanum chromite according to the present invention will be described below. In the present embodiment, a solid oxide fuel cell will be described as an example. FIG. 1 is an exploded perspective view of a solid oxide fuel cell. The solid electrolyte 1 has a rectangular shape and is made of a mixture of a powder of yttrium-stabilized zirconia (hereinafter referred to as YSZ), a butyral-based resin as a binder agent, and a solvent (toluene / ethanol). Use a sheet. The air electrode 2 and the fuel electrode 3 are provided on the upper surface and the lower surface of the solid electrolyte 1, respectively. The material of the fuel electrode 3 is a green sheet formed by mixing a powder obtained by mixing NiO and YSZ at a weight ratio of 6: 4, a butyral resin, and a solvent (toluene / ethanol). As a material of the air electrode 2, a green sheet is prepared by mixing Sr-added lanthanum manganite powder, a butyral resin, and a solvent (toluene / ethanol). The green sheet-shaped air electrode 2 and the fuel electrode 3 are thermocompression-bonded to the upper and lower surfaces of the green sheet-shaped solid electrolyte 1 respectively.
【０００７】ディストリビュータ５，６は空気極２や燃
料極３の表面に設けられ、空気極２や燃料極３に均等に
燃料ガスや空気がゆきわたるように、またそれぞれの電
極２，３と後述のインターコネクタ１０，１１を電気的
に接続するために電極材料と同じ材料にて形成される。
すなわち、ディストリビュータ６は、ＮｉＯとＹＳＺを
重量比１：１で混合した粉末と溶剤等を混合してグリー
ンシート状にしたものを用いる。同様にして、ディスト
リビュータ５は、Ｓｒ添加ランタンマンガナイトの粉末
と溶剤等を混合してグリーンシート状にしたものを用い
る。このグリーンシートを複数枚重ねて厚みのある長尺
状のディストリビュータ５，６を成型し、それぞれ空気
極２及び燃料極３の表面に整列させて配設する。The distributors 5 and 6 are provided on the surfaces of the air electrode 2 and the fuel electrode 3 so that the fuel gas and the air are evenly distributed to the air electrode 2 and the fuel electrode 3. It is formed of the same material as the electrode material for electrically connecting the interconnectors 10 and 11.
That is, the distributor 6 uses a powder obtained by mixing NiO and YSZ at a weight ratio of 1: 1 with a solvent or the like to form a green sheet. Similarly, the distributor 5 uses a mixture of Sr-added lanthanum manganite powder and a solvent to form a green sheet. A plurality of the green sheets are stacked to form long and thick distributors 5 and 6, which are arranged on the surfaces of the air electrode 2 and the fuel electrode 3, respectively.
【０００８】スペーサ７，８は、それぞれ整列されたデ
ィストリビュータ５，６の両側に配置され、空気や燃料
ガスを外気から遮断する。スペーサ７，８の材料として
は、ＹＳＺの粉末とブチラール系樹脂、溶剤（トルエン
／エタノール）を混合してグリーンシート状にしたもの
を用いる。このグリーンシートを複数枚重ねて厚みのあ
る長尺状のスペーサ７，８を成型する。成型されたスペ
ーサ７，８は、それぞれ空気極２、燃料極３の表面に接
着される。The spacers 7 and 8 are arranged on both sides of the aligned distributors 5 and 6, respectively, and block air and fuel gas from outside air. As a material for the spacers 7 and 8, a material obtained by mixing YSZ powder, a butyral-based resin, and a solvent (toluene / ethanol) to form a green sheet is used. A plurality of these green sheets are stacked to form thick elongated spacers 7 and 8. The molded spacers 7 and 8 are bonded to the surfaces of the air electrode 2 and the fuel electrode 3, respectively.
【０００９】さらに、インターコネクタ１０，１１が上
下に配置される。インターコネクタ１０，１１の材料と
しては、ランタンクロマイトの粉末と溶剤等を混合して
グリーンシート状にしたものを用いる。インターコネク
タ１０，１１は接合剤を介してスペーサ７，８に圧着さ
れる。接合剤の材料としては、ＹＳＺの粉末に対してＳ
ｒ添加ランタンマンガナイトを重量比で０．０５〜２
０．０加えて混合し、ワニスを混合してペースト状にし
たもの（表１のＬＯＴ Ｎｏ．１〜７参照）を用いる。Further, interconnectors 10, 11 are arranged vertically. As a material for the interconnectors 10 and 11, a material obtained by mixing lanthanum chromite powder, a solvent, and the like to form a green sheet is used. The interconnectors 10, 11 are pressed against the spacers 7, 8 via a bonding agent. As the material of the bonding agent, S
r-added lanthanum manganite in a weight ratio of 0.05 to 2
0.0 was added and mixed, and a varnish was mixed to form a paste (see LOT Nos. 1 to 7 in Table 1).
【００１０】こうして組み合わされた固体電解質型燃料
電池を、１３００℃の温度まで昇温し、この温度で２時
間共焼結した。焼結後、スペーサ７，８とインターコネ
クタ１０，１１の接合状態を評価した。その評価結果を
表１に示す。The solid oxide fuel cell thus combined was heated to a temperature of 1300 ° C. and co-sintered at this temperature for 2 hours. After sintering, the bonding state between the spacers 7, 8 and the interconnectors 10, 11 was evaluated. Table 1 shows the evaluation results.
【００１１】[0011]
【表１】 [Table 1]
【００１２】表１においては、ランタンマンガナイトの
対ＹＳＺ重量比が０．１〜１０．０の範囲の接合剤で、
スペーサ７，８とインターコネクタ１０，１１が良好に
接合することが示されている。すなわち、この範囲で、
インターコネクタ１０，１１から接合剤へＣｒが拡散し
なくなる。ランタンマンガナイトの対ＹＳＺ重量比が
０．１〜１０．０の範囲から外れる接合剤では、スペー
サ７，８とインターコネクタ１０，１１は接合しなかっ
た。In Table 1, the lanthanum manganite to YSZ weight ratio ranges from 0.1 to 10.0.
It is shown that the spacers 7, 8 and the interconnectors 10, 11 are well joined. That is, in this range,
Cr does not diffuse from the interconnectors 10 and 11 to the bonding agent. When the weight ratio of lanthanum manganite to YSZ was out of the range of 0.1 to 10.0, the spacers 7, 8 and the interconnectors 10, 11 were not bonded.
【００１３】なお、本発明に係るイットリウム安定化ジ
ルコニアとランタンクロマイトの接合構造は前記実施例
に限定するものではなく、その要旨の範囲内で種々に変
形することができる。The joining structure of yttrium-stabilized zirconia and lanthanum chromite according to the present invention is not limited to the above embodiment, but can be variously modified within the scope of the invention.
【００１４】[0014]
【発明の効果】以上の説明で明らかなように、本発明に
よれば、ランタンマンガナイトをイットリウム安定化ジ
ルコニアに対して重量比０．１〜１０．０の範囲で添加
した接合剤を用いて、イットリウム安定化ジルコニアと
ランタンクロマイトを焼成接合したので、ランタンクロ
マイトに含まれているＣｒの一部が接合剤に拡散するの
を防止でき、Ｃｒ拡散による接合剤の焼結性の変化を防
止できる。従って、気密性や稼働時の温度の昇降に対す
る信頼性、耐久性に優れたイットリウム安定化ジルコニ
アとランタンクロマイトの接合構造を得ることができ
る。As is apparent from the above description, according to the present invention, a bonding agent in which lanthanum manganite is added to yttrium-stabilized zirconia in a weight ratio of 0.1 to 10.0 is used. Since lanthanum chromite and yttrium-stabilized zirconia are fired and joined, it is possible to prevent a part of Cr contained in the lanthanum chromite from diffusing into the bonding agent and prevent a change in sinterability of the bonding agent due to Cr diffusion. . Therefore, it is possible to obtain a joint structure of yttrium-stabilized zirconia and lanthanum chromite, which is excellent in airtightness, reliability against temperature rise and fall during operation, and durability.
【００１５】この結果、固体電解質型燃料電池等に備わ
っているスペーサとインターコネクタの接合を共焼結に
よって形成することが可能になる。As a result, the joint between the spacer and the interconnector provided in the solid oxide fuel cell or the like can be formed by co-sintering.
【図１】本発明に係るイットリウム安定化ジルコニアと
ランタンクロマイトの接合構造の実施例を示す斜視図。FIG. 1 is a perspective view showing an embodiment of a joint structure of yttrium-stabilized zirconia and lanthanum chromite according to the present invention.
７，８…スペーサ（イットリウム安定化ジルコニア） １０，１１…インターコネクタ（ランタンクロマイト） 7, 8 ... spacer (yttrium-stabilized zirconia) 10, 11 ... interconnector (lanthanum chromite)
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−304870（ＪＰ，Ａ) 特開 平３−285268（ＪＰ，Ａ) 特開 平３−219563（ＪＰ，Ａ) 特開 平３−88273（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 37/02 H01M 8/12 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-304870 (JP, A) JP-A-3-285268 (JP, A) JP-A-3-219563 (JP, A) JP-A-3-304 88273 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) C04B 37/02 H01M 8/12
Claims (1)
ンマンガナイトの重量比が０．１〜１０．０の範囲の混
合物を接合剤として用いて共焼結されていることを特徴
とするイットリウム安定化ジルコニアとランタンクロマ
イトの接合構造。1. A yttrium-stabilized zirconia characterized by being co-sintered using a mixture of yttrium-stabilized zirconia and lanthanum manganite in a weight ratio of 0.1 to 10.0 as a bonding agent. Lantern chromite joint structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00139392A JP3180402B2 (en) | 1992-01-08 | 1992-01-08 | Bonded structure of yttrium stabilized zirconia and lanthanum chromite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00139392A JP3180402B2 (en) | 1992-01-08 | 1992-01-08 | Bonded structure of yttrium stabilized zirconia and lanthanum chromite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05186277A JPH05186277A (en) | 1993-07-27 |
| JP3180402B2 true JP3180402B2 (en) | 2001-06-25 |
Family
ID=11500252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00139392A Expired - Fee Related JP3180402B2 (en) | 1992-01-08 | 1992-01-08 | Bonded structure of yttrium stabilized zirconia and lanthanum chromite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3180402B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2377189B1 (en) | 2008-12-18 | 2018-05-02 | Saint-Gobain Ceramics & Plastics Inc. | Highly sinterable lanthanum strontium titanate interconnects through doping |
| CN102265440B (en) * | 2008-12-31 | 2014-09-03 | 圣戈本陶瓷及塑料股份有限公司 | Thermal shock-tolerant solid oxide fuel cell stack |
| WO2013096756A1 (en) | 2011-12-22 | 2013-06-27 | Saint-Gobain Ceramics & Plastics, Inc. | Solid oxide fuel cell interconnects including a ceramic interconnect material and partially stabilized zirconia |
-
1992
- 1992-01-08 JP JP00139392A patent/JP3180402B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05186277A (en) | 1993-07-27 |
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