JP3355078B2 - Solid oxide fuel cell - Google Patents
Solid oxide fuel cellInfo
- Publication number
- JP3355078B2 JP3355078B2 JP27421295A JP27421295A JP3355078B2 JP 3355078 B2 JP3355078 B2 JP 3355078B2 JP 27421295 A JP27421295 A JP 27421295A JP 27421295 A JP27421295 A JP 27421295A JP 3355078 B2 JP3355078 B2 JP 3355078B2
- Authority
- JP
- Japan
- Prior art keywords
- fuel cell
- solid oxide
- oxide fuel
- sio
- gas separator
- 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 - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
【０００１】[0001]
【発明の属する技術分野】本発明は固体電解質型燃料電
池に係り、特にセパレータ本体がＭｇＯ及びＭｇＡｌ2
Ｏ4 、或いは、ランタンクロマイト系複合酸化物を主成
分とするセラミックスよりなるガスセパレータを備える
固体電解質型燃料電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid oxide fuel cell, and more particularly to a separator having a main body of MgO and MgAl 2.
The present invention relates to a solid oxide fuel cell provided with a gas separator made of ceramics containing O 4 or a lanthanum chromite-based composite oxide as a main component.
【０００２】[0002]
【従来の技術及び先行技術】セラミックス焼結体よりな
るガスセパレータを有した固体電解質型燃料電池の一例
について第１〜３図を参照して説明する。第３図の通
り、この固体電解質型燃料電池１は、集電板２、ガスセ
パレータ３、集電板４、セル５をこの順に多数積層して
なるものである。この固体電解質型燃料電池１の構成部
材のうち、ガスセパレータ３は、第１図の通り、それぞ
れＭｇＯ及びＭｇＡｌ2 Ｏ4 を主成分とするセラミック
ス焼結体よりなるセパレータ本体６、積層用枠体７及び
ガス流通用枠体８と、セパレータ本体６に対し接合され
たランタンクロマイト系複合酸化物製電子流路材９とで
構成されている。2. Description of the Related Art An example of a solid oxide fuel cell having a gas separator made of a ceramic sintered body will be described with reference to FIGS. As shown in FIG. 3, the solid oxide fuel cell 1 is formed by laminating a large number of current collectors 2, gas separators 3, current collectors 4, and cells 5 in this order. As shown in FIG. 1, among the constituent members of the solid oxide fuel cell 1, the gas separator 3 includes a separator main body 6 made of a ceramic sintered body mainly containing MgO and MgAl 2 O 4 , and a frame for lamination. 7 and a gas flow frame 8, and a lanthanum chromite-based composite oxide electron flow path material 9 joined to the separator body 6.
【０００３】積層用枠体７は細帯形状のものである。ガ
ス流通用枠体８は、細帯形状部８ａに対し円盤形状部８
ｂを接合したものである。[0003] The laminating frame 7 has a narrow band shape. The gas distribution frame 8 is formed in the disc-shaped portion 8 with respect to the narrow band-shaped portion 8a.
b.
【０００４】従来、枠体７，８をセパレータ本体６に接
合するには、例えば、特開平６−６４９７４号公報記載
の方法に従って、ＭｇＯ粉末及びＡｌ2 Ｏ3 粉末の混合
物を水と混合してスラリーとし、このスラリーを被接合
面に塗付し、第２図に示す如く、被接合部材同士を重ね
合わせ、乾燥、焼成するようにしている。Conventionally, to join the frames 7, 8 to the separator body 6, a mixture of MgO powder and Al 2 O 3 powder is mixed with water according to the method described in, for example, Japanese Patent Application Laid-Open No. 6-64974. A slurry is applied to the surface to be joined, and the members to be joined are overlapped, dried and fired as shown in FIG.
【０００５】なお、ガス流通用枠体８は、細帯形状部８
ａと円盤形状部８ｂとを別々に焼結体として製作してお
き、両者を上記と同じくＭｇＯ−Ａｌ2 Ｏ3 スラリーを
用いて焼成して結合させることにより製造されている。[0005] The gas flow frame 8 has a narrow band-shaped portion 8.
Leave manufactured and a and disc-shaped portion 8b as separate sintered bodies, and both being prepared by binding by firing using well MgO-Al 2 O 3 slurry as above.
【０００６】また、セル５は、Ｙ2 Ｏ3 安定化ＺｒＯ2
（ＹＳＺ）の板状焼結体よりなる電解質５ａに対し、Ｎ
ｉ−ＹＳＺ系サーメット（燃料極）やランタンマンガナ
イト系複合酸化物（空気極）などよりなる電極５ｂを接
合した構造となっている。The cell 5 is composed of Y 2 O 3 stabilized ZrO 2
(YSZ) electrolyte 5a made of a plate-like sintered body
The electrode 5b is made of an i-YSZ-based cermet (fuel electrode) or a lanthanum manganite-based composite oxide (air electrode).
【０００７】このセル５の電解質５ａは、ガスセパレー
タ３の枠体７，８に対し、上記のＭｇＯ−Ａｌ2 Ｏ3 ス
ラリーの塗付、乾燥及び焼成により接合されている。The electrolyte 5a of the cell 5 is joined to the frames 7 and 8 of the gas separator 3 by applying, drying and firing the above-mentioned MgO-Al 2 O 3 slurry.
【０００８】上記の通り、従来において、ＭｇＯ及びＭ
ｇＡｌ2 Ｏ4 を主体とするガスセパレータ３の製造に際
しては、ＭｇＯ粉末及びＡｌ2 Ｏ3 粉末を含むスラリー
を被接合面に塗付し、被接合物同士を重ね合わせた後、
乾燥、焼成し、接合界面に発生するＭｇＯ−Ａｌ2 Ｏ3
複合酸化物層を介して両者を接合するようにしているの
であるが、このＭｇＯ−Ａｌ2 Ｏ3 複合酸化物は、その
焼結温度が高いために、接合時の温度が１４００℃以上
の高温になる。しかし、このような高温で接合すると、
燃料極や空気極も高温に曝されて劣化し、これにより電
池性能が損なわれるようになるという問題があった。As described above, conventionally, MgO and M
When manufacturing the gas separator 3 mainly composed of gAl 2 O 4 , a slurry containing MgO powder and Al 2 O 3 powder is applied to the surfaces to be joined, and after the objects to be joined are overlapped,
Drying and baking, MgO-Al 2 O 3 generated at the bonding interface
Although the two are joined via the composite oxide layer, the MgO-Al 2 O 3 composite oxide has a high sintering temperature, and thus the joining temperature is 1400 ° C. or higher. become. However, when joining at such high temperatures,
There has been a problem that the fuel electrode and the air electrode are also exposed to high temperatures and deteriorated, thereby impairing the cell performance.
【０００９】本出願人は、上記従来の問題点を解決し、
製作時の接合温度を従来よりも低下させることができる
ものとしてＭｇＯとＳｉＯ2 とをＭｇＯ：ＳｉＯ2 ＝
１：０．５〜５（重量比）の割合で含む接合材を用いた
固体電解質型燃料電池を先に提案した（特願平７−３８
２６２号。以下「先願」という。）。The present applicant has solved the above-mentioned conventional problems,
MgO and MgO and SiO 2 the junction temperature at the time of production as it can lower than the conventional: SiO 2 =
A solid oxide fuel cell using a bonding material containing 1: 0.5 to 5 (weight ratio) was previously proposed (Japanese Patent Application No. 7-38).
No. 262. Hereinafter, it is referred to as “first application”. ).
【００１０】上記先願に係る接合材によれば、１２００
〜１３００℃程度で接合を行うことができる。According to the joining material according to the above-mentioned prior application, 1200
The bonding can be performed at about 1300 ° C.
【００１１】なお、固体電解質型燃料電池には、セパレ
ータ材料としてランタンクロマイト系複合酸化物を主成
分とするセラミックス焼結体を用いたものもあり、この
ような固体電解質型燃料電池１０は、一般に第４図に示
す如く、インターコネクターを兼ねたガスセパレータ１
１と、燃料極１２、電解質１３及び空気極１４を積層し
てなるセル１５とを交互に積層して構成されている。第
５図はこの固体電解質型燃料電池１０の積層構造の詳細
を示す部分拡大断面図であり、図示の如く、ガスセパレ
ータ１１同士は、電解質１３を介して接合されている
（図中、Ａは接合部分）。Some solid oxide fuel cells use a ceramic sintered body mainly composed of a lanthanum chromite-based composite oxide as a separator material. Such a solid oxide fuel cell 10 is generally used as a separator. As shown in FIG. 4, a gas separator 1 also serving as an interconnector
1 and a cell 15 in which a fuel electrode 12, an electrolyte 13 and an air electrode 14 are stacked alternately. FIG. 5 is a partially enlarged cross-sectional view showing the details of the layered structure of the solid oxide fuel cell 10, and as shown, the gas separators 11 are joined via an electrolyte 13 (A in the figure). Joint).
【００１２】[0012]
【発明が解決しようとする課題】しかしながら、先願に
係る接合材は、接合材自体の熱膨張率が小さく、ヒート
サイクルをかけた場合、接合部分で割れ、剥離を生じる
という問題があった。However, the joining material according to the prior application has a problem that the joining material itself has a small coefficient of thermal expansion and, when subjected to a heat cycle, cracks or peels off at the joining portion.
【００１３】本発明の目的は、上記先願の問題点を解決
し、固体電解質型燃料電池のセルの性能低下を起こさな
い温度での接合を可能にし、且つヒートサイクルをかけ
ても剥離、割れを起こさない接合材を用いた固体電解質
型燃料電池を提供することにある。An object of the present invention is to solve the above-mentioned problems of the prior application, to enable bonding at a temperature at which the performance of a cell of a solid oxide fuel cell does not deteriorate, and to separate and crack even when subjected to a heat cycle. It is an object of the present invention to provide a solid oxide fuel cell using a bonding material that does not cause the problem.
【００１４】[0014]
【課題を解決するための手段】本発明の固体電解質型燃
料電池は、セラミックス焼結体よりなるガスセパレータ
を持つ固体電解質型燃料電池であって、ガスセパレータ
材料同士、及び／又は、ガスセパレータ材料とセル材料
とが、接合材を介して焼成することにより結晶性接合相
を生成させて接合されてなる固体電解質型燃料電池にお
いて、該接合材がＳｉＯ2 とＣａＯとを含み、ＳｉＯ2
とＣａＯとの割合がＳｉＯ2 ：ＣａＯ＝１：０．５〜２
（モル比）であることを特徴とする。SUMMARY OF THE INVENTION A solid oxide fuel cell according to the present invention is a solid oxide fuel cell having a gas separator made of a ceramic sintered body, wherein the gas separator materials and / or the gas separator material are used. and the cell material, in a solid electrolyte fuel cell formed by joined to produce a crystalline bonding phase by firing by means of a bonding material, the bonding material comprises SiO 2 and CaO, SiO 2
And the ratio of CaO is SiO 2 : CaO = 1: 0.5 to 2
(Molar ratio).
【００１５】本発明によれば、主成分としてＳｉＯ2 及
びＣａＯで構成される混合粉末をスラリー化して被接合
面に塗布し、各部材を張り合わせて、１３００℃以下の
温度で焼成することにより容易に接合することができ
る。According to the present invention, a mixed powder mainly composed of SiO 2 and CaO is slurried and applied to a surface to be joined, and each member is bonded and fired at a temperature of 1300 ° C. or less. Can be joined.
【００１６】本発明では、ガスセパレータ材料の主成分
と接合材であるＳｉＯ2 −ＣａＯ系とが１３００℃以下
という焼成温度で液相焼結する反応を利用して、接合層
に複合酸化物を生成させる。これによって、各部材間は
化学的に強固に接合されることになる。In the present invention, a composite oxide is formed in the bonding layer by utilizing a reaction in which the main component of the gas separator material and the SiO 2 —CaO-based bonding material are liquid phase sintered at a firing temperature of 1300 ° C. or less. Generate. As a result, the members are chemically bonded strongly.
【００１７】このような接合材は、特にセルがＹＳＺ或
はその近似物で構成され、ガスセパレータがＭｇＯ及び
ＭｇＡｌ2 Ｏ4 を主成分とする場合、或いは、ランタン
クロマイト系複合酸化物（Ｌａ（Ｍ）ＣｒＯ3 （ＭはＭ
ｇ，Ｃａ等））を主成分とする場合に有効である。Such a bonding material is particularly used when the cell is composed of YSZ or an approximation thereof, and when the gas separator contains MgO and MgAl 2 O 4 as main components, or a lanthanum chromite-based composite oxide (La ( M) CrO 3 (M is M
g, Ca, etc.)) as the main component.
【００１８】この場合、ガスセパレータ材料であるＭｇ
Ｏ／ＭｇＡｌ2 Ｏ4 又はＬａ（Ｍ）ＣｒＯ3 （Ｍ；Ｍ
ｇ，Ｃａ等）と接合材であるＣａＯ／ＳｉＯ2 とが液相
焼結する反応を用い、接合層にＡｌ−Ｓｉ−Ｃａ系複合
酸化物又はＭ−Ｓｉ系複合酸化物（Ｍ：Ｍｇ，Ｃａ等）
の結晶性接合相を生成させる。また、電解質材料である
ＹＳＺ（またこの近似物）と接合材であるＣａＯ／Ｓｉ
Ｏ2 とはＺｒ−Ｓｉ系複合酸化物の結晶性接合相を生成
させる。この２つの反応による結晶相を持つことによっ
て、ガスセパレータ／ガスセパレータ間又はガスセパレ
ータ／セル間は強固に結合されることになる。In this case, the gas separator material Mg
O / MgAl 2 O 4 or La (M) CrO 3 (M; M
g, Ca, etc.) and a bonding material CaO / SiO 2 are subjected to liquid phase sintering, and the Al—Si—Ca-based composite oxide or the M-Si-based composite oxide (M: Mg, Ca etc.)
To form a crystalline bonding phase. Further, YSZ (also an approximation thereof) as an electrolyte material and CaO / Si as a bonding material are used.
O 2 forms a crystalline bonding phase of a Zr—Si-based composite oxide. By having a crystal phase due to these two reactions, the gas separator / gas separator or the gas separator / cell is firmly bonded.
【００１９】また、本発明に係るＣａＯ／ＳｉＯ2 組成
を用いることによってガスセパレータ材料であるＭｇＯ
／ＭｇＡｌ2 Ｏ4 又はＬａ（Ｍ）ＣｒＯ3 （Ｍ；Ｃａ，
Ｍｇ等）やセル材料のＹＳＺと熱膨張率をほぼ同じにす
ることが可能となり、ヒートサイクルをかけた場合でも
剥離や割れを起こすことなく接合することが可能とな
る。Further, by using the CaO / SiO 2 composition according to the present invention, MgO which is a gas separator material is used.
/ MgAl 2 O 4 or La (M) CrO 3 (M; Ca,
Mg or the like and the YSZ of the cell material can be made to have substantially the same coefficient of thermal expansion, and even if a heat cycle is applied, bonding can be performed without causing peeling or cracking.
【００２０】[0020]
【発明の実施の形態】以下に本発明を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
【００２１】本発明においては、第２図に示すようなＭ
ｇＯ及びＭｇＡｌ2 Ｏ4 を主成分とするスピネル系セラ
ミックス焼結体製のガスセパレータ３のセパレータ本体
６と枠体７，８との接合、或いは、この枠体７，８とセ
ル５のＹＳＺ焼結体製電解質５ａとの接合、或いは、第
４，５図に示すようなランタンクロマイト系複合酸化物
を主成分とするガスセパレータ１１とセル１５のＹＳＺ
焼結体製電解質１３の接合に当り、ＳｉＯ2 とＣａＯと
を含み、ＳｉＯ2 とＣａＯとの割合がＳｉＯ2：ＣａＯ
＝１：０．５〜２（モル比）である接合材を用いる。In the present invention, M as shown in FIG.
Bonding of the separator body 6 of the gas separator 3 made of a spinel ceramic sintered body mainly composed of gO and MgAl 2 O 4 to the frames 7 and 8 or YSZ firing of the frames 7 and 8 and the cell 5 Bonding with the electrolyte 5a made of the sintered body, or the YSZ of the gas separator 11 and the cell 15 mainly containing a lanthanum chromite-based composite oxide as shown in FIGS.
Per the bonding of the sintered body made of the electrolyte 13, and a SiO 2 and CaO, the ratio between the SiO 2 and CaO is SiO 2: CaO
= 1: 0.5 to 2 (molar ratio) is used.
【００２２】即ち、具体的には、ＳｉＯ2 粉末及びＣａ
Ｏ粉末を上記割合で混合してなる混合粉末に、必要に応
じてポリビニルブチラール等の結合剤、ジブチルフタレ
ート等の可塑剤、ノニオン系界面活性剤等の分散剤等を
添加して下記配合のスラリーとしたものを被接合面にス
プレー等により乾燥後の塗布量で０．２〜０．５ｇ／ｃ
ｍ2 となるように塗布して乾燥し、その後、被接合面同
志を当接し、０．３〜０．５ｋｇ／ｃｍ2 程度の荷重を
かけて、１３００℃以下、好ましくは１２００〜１３０
０℃の温度で焼成して接合を行う。That is, specifically, SiO 2 powder and Ca
Add a binder such as polyvinyl butyral, a plasticizer such as dibutyl phthalate, a dispersant such as a nonionic surfactant, etc. to a mixed powder obtained by mixing the O powder in the above ratio, if necessary. 0.2 to 0.5 g / c in the coating amount after drying by spraying on the surface to be joined
m 2, and then dried. Then, the surfaces to be joined are brought into contact with each other, and a load of about 0.3 to 0.5 kg / cm 2 is applied thereto, and 1300 ° C. or less, preferably 1200 to 130 ° C.
The bonding is performed by firing at a temperature of 0 ° C.
【００２３】接合用スラリー配合 ＳｉＯ2 −ＣａＯ混合粉末：１００ｇ 結合剤：１８ｇ 可塑剤：１６ｇ 分散剤：２ｇ 溶 媒（エタノール等）：１５０ｍｌ 本発明において、接合材のＳｉＯ2 とＣａＯとの割合が
上記範囲からはずれてＳｉＯ2 が少なくなると、焼結性
が悪く接合できない。また、ＳｉＯ2 が多くなると接合
層自体の強度が小さく、また熱膨張率が電解質に比べて
大幅に小さくなるためにヒートサイクルをかけた場合に
割れ、剥離が生じる。 Slurry for bonding SiO 2 -CaO mixed powder: 100 g Binder: 18 g Plasticizer: 16 g Dispersant: 2 g Solvent (ethanol etc.): 150 ml In the present invention, the ratio of SiO 2 to CaO in the bonding material is If the amount of SiO 2 is less than the above range, the sinterability is poor and the joining cannot be performed. In addition, when the amount of SiO 2 increases, the strength of the bonding layer itself becomes small, and the coefficient of thermal expansion becomes much smaller than that of the electrolyte.
【００２４】なお、本発明において、接合されるガスセ
パレータのセパレータ本体や枠体としては、ＭｇＯ及び
ＭｇＡｌ2 Ｏ4 を主成分とするセラミックス焼結体、又
は、ランタンクロマイト系複合酸化物を主成分とするセ
ラミックス焼結体よりなるものが挙げられるが、具体的
なセラミックス組成は次の通りである。In the present invention, the separator body or frame of the gas separator to be joined is preferably made of a ceramic sintered body mainly composed of MgO and MgAl 2 O 4 or a lanthanum chromite-based composite oxide. The specific ceramic composition is as follows.
【００２５】スピネル系セラミックス焼結体組成（重量
％） ＭｇＯ：４２ ＭｇＡｌ2 Ｏ4 ：５８ランタンクロマイト系セラミックス焼結体組成（重量
％） Ｌａ0.7 Ｃａ0.3 ＣｒＯ3 ：１００ また、セルの電解質を構成するＹ2 Ｏ3 安定化ＺｒＯ2
としては、次のような組成が主に採用される。[0025]Spinel ceramic sintered body composition (weight
%) MgO: 42 MgAlTwo OFour : 58Lanthanum chromite ceramic composition (weight
%) La0.7 Ca0.3 CrOThree : 100 Y constituting the electrolyte of the cellTwo OThree Stabilized ZrOTwo
For example, the following composition is mainly employed.
【００２６】ＹＳＺ焼結体組成（モル％） ＺｒＯ2 ：９２〜９０ Ｙ2 Ｏ3 ：８〜１０ YSZ sintered body composition (mol%) ZrO 2 : 92 to 90 Y 2 O 3 : 8 to 10
【００２７】[0027]
【実施例】以下に実施例を挙げて本発明をより具体的に
説明する。The present invention will be described more specifically with reference to the following examples.
【００２８】実施例１ ＳｉＯ2 粉末とＣａＯ粉末とを表１に示す重量比で混合
し、得られたＳｉＯ2−ＣａＯ混合粉末を用いて、下記
配合で接合用スラリーを調製した。Example 1 A SiO 2 powder and a CaO powder were mixed at a weight ratio shown in Table 1, and a joining slurry was prepared with the following composition using the obtained SiO 2 -CaO mixed powder.
【００２９】接合用スラリー配合 ＳｉＯ2 −ＣａＯ混合粉末：１００ｇ 結合剤（ポリビニルブチラール）：１８ｇ 可塑剤（ジブチルフタレート）：１６ｇ 分散剤（ノニオン系界面活性剤）：２ｇ 溶 媒（エタノール）：１５０ｍｌ このスラリーを、ＭｇＯ−ＭｇＡｌ2 Ｏ4 系セラミック
ス焼結体製ガスセパレータ（組成：ＭｇＯ：４２重量
％，ＭｇＡｌ2 Ｏ4 ：５８重量％）の接合を必要とする
面にスプレー塗布し（乾燥後の塗布量０．１ｇ／ｃｍ
2 ）、部材同士を貼り合せ、乾燥後、０．３ｋｇ／ｃｍ
2 の面圧荷重下、表１に表す温度で焼成して接合を行っ
た。 Slurry for bonding SiO 2 -CaO mixed powder: 100 g Binder (polyvinyl butyral): 18 g Plasticizer (dibutyl phthalate): 16 g Dispersant (nonionic surfactant): 2 g Solvent (ethanol): 150 ml the slurry, MgO-MgAl 2 O 4 based ceramic sintered body made of a gas separator (composition: MgO: 42 wt%, MgAl 2 O 4: 58 wt%) spray applied to the surface in need of bonding (after drying 0.1 g / cm
2 ) After bonding the members together and drying, 0.3kg / cm
Under the surface pressure load of No. 2 , sintering was performed at the temperature shown in Table 1 to perform bonding.
【００３０】得られた接合体を接合部を含むように切断
して４点曲げ試験を行って、接合部の強度を調べたとこ
ろ、本発明のＳｉＯ2 −ＣａＯ組成範囲内のものは、い
ずれも表１に示す如く、１２０ＭＰａ以上の高い接合強
度が得られたことが確認された。[0030] The resulting conjugate by performing the cut four-point bending test to include a joint portion, were examined strength of the joint, as in the SiO 2 -CaO composition range of the present invention, any As shown in Table 1, it was confirmed that a high bonding strength of 120 MPa or more was obtained.
【００３１】また、各接合部のガスシール性能を調べた
ところ、表１に示す如く、本発明のＳｉＯ2 −ＣａＯ組
成範囲内のものは、実用上十分な性能が得られた。Further, when the gas sealing performance of each joint was examined, as shown in Table 1, those having a composition within the range of SiO 2 —CaO of the present invention showed sufficient performance for practical use.
【００３２】また、本発明のＳｉＯ2 −ＣａＯ組成範囲
内のものについて、固体電解質型燃料電池の発電温度で
ヒートサイクル試験を行ったところ、割れ、剥離等は認
められず、ガスシール試験においても顕著な変化はみら
れず、実用上充分な性能を示した。Further, when a heat cycle test was performed on the SiO 2 —CaO composition of the present invention at the power generation temperature of the solid oxide fuel cell, no cracking or peeling was observed. No remarkable change was observed, and the performance was sufficient for practical use.
【００３３】[0033]
【表１】 [Table 1]
【００３４】実施例２ 実施例１で調製した各スラリーを用いて、実施例１と同
様の接合条件で、ＭｇＯ−ＭｇＡｌ2 Ｏ4 系セラミック
ス焼結体製枠体とセルのＹＳＺ焼結体製電解質（組成：
ＺｒＯ2 ＝９２ｍｏｌ％，Ｙ2 Ｏ3 ＝８ｍｏｌ％）との
接合を行い、同様に強度及び空気透過率を調べ、結果を
表２に示した。Example 2 Using the respective slurries prepared in Example 1, under the same joining conditions as in Example 1, a frame made of a MgO—MgAl 2 O 4 ceramic sintered body and a cell made of a YSZ sintered body were produced. Electrolyte (composition:
(ZrO 2 = 92 mol%, Y 2 O 3 = 8 mol%), and the strength and air permeability were similarly examined. The results are shown in Table 2.
【００３５】表２より、本発明のＳｉＯ2 −ＣａＯ組成
範囲であれば、強度、ガスシール性能共に、良好な結果
が得られることが明らかである。From Table 2, it is clear that within the SiO 2 -CaO composition range of the present invention, good results can be obtained in both strength and gas sealing performance.
【００３６】また、本実施例においても、実施例１と同
様に、本発明のＳｉＯ2 −ＣａＯ組成範囲内のものにつ
いて、固体電解質型燃料電池の発電温度でヒートサイク
ル試験を行ったところ、割れ、剥離等は認められず、ガ
スシール試験においても顕著な変化は見られず、実用上
充分な性能を示した。Also, in this embodiment, as in the case of the first embodiment, a heat cycle test was performed on the material within the SiO 2 —CaO composition range of the present invention at the power generation temperature of the solid oxide fuel cell. No peeling or the like was observed, and no remarkable change was observed in the gas seal test, showing sufficient performance for practical use.
【００３７】[0037]
【表２】 [Table 2]
【００３８】実施例３ 実施例１で調製した各スラリーを用いて、実施例１と同
様の接合条件で、ランタンクロマイト系複合酸化物系セ
ラミックス焼結体製ガスセパレータ（組成：Ｌａ0.7 Ｃ
ａ0.3 ＣｒＯ3 ）とセルのＹＳＺ焼結体製電解質（組
成：ＺｒＯ2 ＝９２ｍｏｌ％，Ｙ2 Ｏ3 ＝８ｍｏｌ％）
との接合を行い、同様に強度及び空気透過率を調べ、結
果を表３に示した。Example 3 A gas separator (composition: La 0.7 C) made of a lanthanum chromite-based composite oxide-based ceramics sintered body under the same joining conditions as in Example 1 using the respective slurries prepared in Example 1.
a 0.3 CrO 3 ) and electrolyte made of YSZ sintered body of cell (composition: ZrO 2 = 92 mol%, Y 2 O 3 = 8 mol%)
And the strength and air permeability were similarly examined. The results are shown in Table 3.
【００３９】表３より、本発明のＳｉＯ2 −ＣａＯ組成
範囲であれば、強度、ガスシール性能共に、良好な結果
が得られることが明らかである。From Table 3, it is clear that within the SiO 2 -CaO composition range of the present invention, good results can be obtained in both strength and gas sealing performance.
【００４０】また、本実施例においても、実施例１と同
様に、本発明のＳｉＯ2 −ＣａＯ組成範囲内のものにつ
いて、固体電解質型燃料電池の発電温度でヒートサイク
ル試験を行ったところ、割れ、剥離等は認められず、ガ
スシール試験においても顕著な変化は見られず、実用上
充分な性能を示した。In this example, as in Example 1, a heat cycle test was carried out at a power generation temperature of a solid oxide fuel cell for the SiO 2 -CaO composition range of the present invention. No peeling or the like was observed, and no remarkable change was observed in the gas seal test, showing sufficient performance for practical use.
【００４１】[0041]
【表３】 [Table 3]
【００４２】[0042]
【発明の効果】以上詳述した通り、本発明の固体電解質
型燃料電池によれば、セラミックス焼結体製ガスセパレ
ータ同士、或いは、セパレータとセルとの接合に際し、
接合温度を低くすることができるため、セル性能に悪影
響を及ばすことがない。また、接合材自体の熱膨張率
が、ガスセパレータの熱膨張率やセルの熱膨張率とほぼ
同じであるため、ヒートサイクルをかけても剥離、割れ
等を生じることがない。このため、高性能で耐久性に優
れ、信頼性の高い固体電解質型燃料電池の製造が可能と
なる。As described above in detail, according to the solid oxide fuel cell of the present invention, when the gas separators made of ceramic sintered bodies are joined to each other or when the separators and the cells are joined,
Since the junction temperature can be lowered, the cell performance is not adversely affected. Further, since the thermal expansion coefficient of the bonding material itself is almost the same as the thermal expansion coefficient of the gas separator and the thermal expansion coefficient of the cell, there is no occurrence of peeling, cracking or the like even when subjected to a heat cycle. Therefore, it is possible to manufacture a solid oxide fuel cell having high performance, excellent durability, and high reliability.
【図１】ガスセパレータとセルの構成を示す分解斜視図
である。FIG. 1 is an exploded perspective view showing a configuration of a gas separator and a cell.
【図２】ガスセパレータの構成を示す分解斜視図であ
る。FIG. 2 is an exploded perspective view showing a configuration of a gas separator.
【図３】固体電解質型燃料電池の一実施例を示す分解斜
視図である。FIG. 3 is an exploded perspective view showing one embodiment of a solid oxide fuel cell.
【図４】固体電解質型燃料電池の他の実施例を示す分解
斜視図である。FIG. 4 is an exploded perspective view showing another embodiment of the solid oxide fuel cell.
【図５】図４に示す固体電解質型燃料電池の部分拡大断
面図である。5 is a partially enlarged cross-sectional view of the solid oxide fuel cell shown in FIG.
１，１０ 固体電解質型燃料電池 ２，４ 集電板 ３，１１ ガスセパレータ ５，１５ セル ６ セパレータ本体 ７ 積層用枠体 ８ ガス流通用枠体 ９ 電子流路材 １２ 燃料極 １３ 電解質 １４ 空気極 DESCRIPTION OF SYMBOLS 1,10 Solid electrolyte type fuel cell 2,4 Current collector plate 3,11 Gas separator 5,15 Cell 6 Separator main body 7 Stacking frame 8 Gas distribution frame 9 Electronic channel material 12 Fuel electrode 13 Electrolyte 14 Air electrode
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 8/02 H01M 8/12 C04B 37/00 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) H01M 8/02 H01M 8/12 C04B 37/00
Claims (4)
ータを持つ固体電解質型燃料電池であって、ガスセパレ
ータ材料同士、及び／又は、ガスセパレータ材料とセル
材料とが、接合材を介して焼成することにより結晶性接
合相を生成させて接合されてなる固体電解質型燃料電池
において、 該接合材がＳｉＯ2 とＣａＯとを含み、ＳｉＯ2 とＣａ
Ｏとの割合がＳｉＯ2：ＣａＯ＝１：０．５〜２（モル
比）であることを特徴とする固体電解質型燃料電池。1. A solid oxide fuel cell having a gas separator made of a ceramic sintered body, wherein the gas separator materials and / or the gas separator material and the cell material are fired via a bonding material. in the solid electrolyte fuel cell formed by joined to produce a crystalline bonding phase by including the bonding material and SiO 2 and CaO, SiO 2 and Ca
A solid oxide fuel cell, wherein the ratio of O to SiO 2 : CaO = 1: 0.5 to 2 (molar ratio).
て、ガスセパレータ材料がＭｇＯ及びＭｇＡｌ2 Ｏ4 を
主成分とすることを特徴とする固体電解質型燃料電池。2. The solid oxide fuel cell according to claim 1, wherein the gas separator material is mainly composed of MgO and MgAl 2 O 4 .
て、ガスセパレータ材料がランタンクロマイト系複合酸
化物を主成分とすることを特徴とする固体電解質型燃料
電池。3. The solid oxide fuel cell according to claim 1, wherein the gas separator material is mainly composed of a lanthanum chromite-based composite oxide.
電解質型燃料電池において、セル材料がＹ2 Ｏ3 安定化
ＺｒＯ2 系セラミックス材料であることを特徴とする固
体電解質型燃料電池。4. The solid oxide fuel cell according to claim 1, wherein the cell material is a Y 2 O 3 stabilized ZrO 2 ceramic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27421295A JP3355078B2 (en) | 1995-10-23 | 1995-10-23 | Solid oxide fuel cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27421295A JP3355078B2 (en) | 1995-10-23 | 1995-10-23 | Solid oxide fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09115536A JPH09115536A (en) | 1997-05-02 |
| JP3355078B2 true JP3355078B2 (en) | 2002-12-09 |
Family
ID=17538602
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|---|---|---|---|
| JP27421295A Expired - Lifetime JP3355078B2 (en) | 1995-10-23 | 1995-10-23 | Solid oxide fuel cell |
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| Country | Link |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007329018A (en) * | 2006-06-08 | 2007-12-20 | Nippon Telegr & Teleph Corp <Ntt> | Insulation part for solid oxide fuel cell and solid oxide fuel cell |
| JP4420139B2 (en) * | 2008-04-04 | 2010-02-24 | 株式会社村田製作所 | Solid electrolyte fuel cell and manufacturing method thereof |
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- 1995-10-23 JP JP27421295A patent/JP3355078B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
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