JPH10106596A - Solid electrolyte fuel cell - Google Patents
Solid electrolyte fuel cellInfo
- Publication number
- JPH10106596A JPH10106596A JP8261875A JP26187596A JPH10106596A JP H10106596 A JPH10106596 A JP H10106596A JP 8261875 A JP8261875 A JP 8261875A JP 26187596 A JP26187596 A JP 26187596A JP H10106596 A JPH10106596 A JP H10106596A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- separator
- bonding agent
- fuel cell
- mgo
- 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.)
- Granted
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
Landscapes
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、固体電解質膜とセ
パレータのガスシール部が接合剤で接合された固体電解
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 electrolyte fuel cell in which a solid electrolyte membrane and a gas seal of a separator are joined with a joining agent.
【０００２】[0002]
【従来の技術】平板型の固体電解質型燃料電池は、図１
に示すように、電池の最小単位としてのセル１が、三層
膜２ａとそれを両側から挟むセパレータ３ａ，３ｂによ
り構成されている。三層膜２ａは、燃料極４、固体電解
質膜５及び空気極６の各層からなり、外部から供給され
る燃料ガス（水素）及び酸化ガス（空気）と反応を起こ
し、電気を発生する。この固体電解質膜５の材料には、
一般にイットリア安定化ジルコニア（ＹＳＺ）が用いら
れる。2. Description of the Related Art A flat solid electrolyte fuel cell is shown in FIG.
As shown in (1), the cell 1 as the minimum unit of the battery includes a three-layer film 2a and separators 3a and 3b sandwiching the three-layer film 2a from both sides. The three-layer film 2a is composed of layers of a fuel electrode 4, a solid electrolyte membrane 5, and an air electrode 6, and reacts with a fuel gas (hydrogen) and an oxidizing gas (air) supplied from the outside to generate electricity. Materials for the solid electrolyte membrane 5 include:
Generally, yttria-stabilized zirconia (YSZ) is used.
【０００３】三層膜２ａ，２ｂは、直列に接続、積層さ
れて大きな電圧を得るが、セパレータ３ａ，３ｂが電子
伝導体として三層膜２ａと三層膜２ｂを仕切り、また、
燃料極４に入る燃料ガス（水素）と空気極６に入る酸化
ガス（空気）とが混じるのを防いでいる。このようなセ
パレータの材料には、一般にランタンクロマイト（Ｌａ
ＣｒＯ3 ）系セラミックが用いられる。The three-layer films 2a and 2b are connected and laminated in series to obtain a large voltage, but the separators 3a and 3b partition the three-layer film 2a and the three-layer film 2b as an electron conductor.
The fuel gas (hydrogen) entering the fuel electrode 4 and the oxidizing gas (air) entering the air electrode 6 are prevented from being mixed. The material of such a separator is generally lanthanum chromite (La
A CrO 3 ) -based ceramic is used.
【０００４】セパレータ３ａ，３ｂの両面には、それぞ
れ面に沿って互いに直角方向に一連の溝７ａ，７ｂ，７
ｃ，７ｄが設けられ、燃料極４側は燃料ガス（水素）
が、また、空気極６側は酸化ガス（空気）が通る流路に
なっている。A series of grooves 7a, 7b, 7 are formed on both surfaces of the separators 3a, 3b at right angles to each other along the respective surfaces.
c, 7d are provided, and the fuel electrode 4 side is a fuel gas (hydrogen).
However, the air electrode 6 side is a flow path through which the oxidizing gas (air) passes.
【０００５】そして、セパレータ３ａの溝７ｂに平行な
端縁部８ａ，８ｂ、及びセパレータ３ｂの溝７ｃに平行
な端縁部８ｃ，８ｄが、三層膜２ａを構成する固体電解
質膜５の端縁部９ａ，９ｂ及び９ｄ，９ｃとそれぞれ接
合される部分については、燃料ガス（水素）と酸化ガス
（空気）を隔離して、ガスが混じるのを防ぐ必要があ
る。The edges 8a, 8b parallel to the grooves 7b of the separator 3a and the edges 8c, 8d parallel to the grooves 7c of the separator 3b are formed by the edge of the solid electrolyte membrane 5 constituting the three-layer film 2a. It is necessary to prevent fuel gas (hydrogen) and oxidizing gas (air) from being mixed with each other at portions joined to the edges 9a, 9b and 9d, 9c, respectively.
【０００６】すなわち、このセパレ−タと固体電解質膜
の接合部に、接合のために中間層を配する場合、その部
材に必要とされる特性は、緻密でガスを通さないこ
と、酸化と還元のいずれの雰囲気においても安定であ
ること、熱膨張係数が被接合部の材料と近いこと、等
が挙げられる。That is, when an intermediate layer is provided at the junction between the separator and the solid electrolyte membrane for bonding, the characteristics required for the member are that it be dense and impervious to gas, oxidation and reduction. And that the coefficient of thermal expansion is close to the material of the portion to be joined.
【０００７】このため、従来は、イットリア安定化ジル
コニア（ＹＳＺ）からなる固体電解質膜と、ランタンク
ロマイト（ＬａＣｒＯ3 ）系セラミックからなるセパレ
ータを、それぞれ別個に焼結させた後、両者の接合部に
ガスシール用ガラス系酸化物接合剤（ペースト）を中間
層として介在させ接合していた。For this reason, conventionally, a solid electrolyte membrane made of yttria-stabilized zirconia (YSZ) and a separator made of lanthanum chromite (LaCrO 3 ) -based ceramic are separately sintered, and then joined to the joint between the two. A glass-based oxide bonding agent (paste) for gas sealing was used as an intermediate layer for bonding.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、このガ
スシール用ガラス系酸化物接合剤に通常含まれているＳ
ｉは、セパレータのランタンクロマイト（ＬａＣｒ
Ｏ3 ）系セラミックの劣化を促進させるという問題があ
った。However, the glass-based oxide bonding agent for a gas seal usually contains S
i is the separator lanthanum chromite (LaCr)
There is a problem that the deterioration of the O 3 ) -based ceramic is accelerated.
【０００９】一般に、ランタンクロマイト（ＬａＣｒＯ
3 ）の焼結には１８００℃の高温を必要とするため、こ
れにＣａまたはＳｒの酸化物を添加して、焼結温度を１
６００℃以下に低下させている。その際、添加したＣａ
またはＳｒの酸化物はＬａＣｒＯ3 と反応し、ＣａＣｒ
Ｏ4 またはＳｒＣｒＯ4 が生じている。Generally, lanthanum chromite (LaCrO)
3 ) Since the sintering requires a high temperature of 1800 ° C., an oxide of Ca or Sr is added thereto and the sintering temperature is set to 1
The temperature is lowered to 600 ° C. or less. At that time, the added Ca
Alternatively, the oxide of Sr reacts with LaCrO 3 to produce CaCr.
O 4 or SrCrO 4 is generated.
【００１０】ところが、ガラス系酸化物の接合剤を用い
て固体電解質とセパレータを接合する場合、ガラス中に
含まれているＳｉＯ2 は、例えば前記ＣａＣｒＯ4 と反
応して、機械的に脆いＣａ2 ＳｉＯ4 が生成し、これが
ランタンクロマイト（ＬａＣｒＯ3 ）焼結体を劣化させ
る原因になっていた。However, when the solid electrolyte and the separator are joined using a joining agent of a glass-based oxide, SiO 2 contained in the glass reacts with, for example, the above-mentioned CaCrO 4 to form mechanically brittle Ca 2 O. SiO 4 was generated, which had caused deterioration of the lanthanum chromite (LaCrO 3 ) sintered body.
【００１１】一方、これとは別に、セパレータ本体に
は、ＭｇＡｌ2 Ｏ4 （スピネル）とＭｇＯとを混合して
緻密焼結した電気絶縁性の焼結体を用い、また、セパレ
ータの電子流路にはランタンクロマイト（ＬａＣｒ
Ｏ3 ）系焼結体を用いてこれらを組み合わせ、セパレー
タを構成する方法がある（特開平５−７４４７０号公
報）。この方法は、ＭｇＡｌ2 Ｏ4 とＭｇＯの混合割合
を制御することによって、熱膨張係数を容易に調整で
き、また、ＭｇＡｌ2 Ｏ4 とＭｇＯとの混合物は、ラン
タンクロマイト（ＬａＣｒＯ3 ）系セラミックを大きく
劣化させることがない。On the other hand, separately from this, an electrically insulating sintered body obtained by densely sintering a mixture of MgAl 2 O 4 (spinel) and MgO is used for the separator body. Lantern chromite (LaCr)
There is a method of combining these using an O 3 ) -based sintered body to form a separator (Japanese Patent Laid-Open No. Hei 5-74470). This method, by controlling the mixing ratio of MgAl 2 O 4 and MgO, the thermal expansion coefficient can be easily adjusted, also, a mixture of MgAl 2 O 4 and MgO is lanthanum chromite (LaCrO 3) ceramic There is no significant deterioration.
【００１２】この場合、ＭｇＡｌ2 Ｏ4 ／ＭｇＯ焼結体
は、固体電解質膜とランタンクロマイト系（ＬａＣｒＯ
3 ）セラミックの接合において、その中間層として働い
ていると考えられる。しかしながら、この方法は、あら
かじめ焼結されたＭｇＡｌ2Ｏ4 ／ＭｇＯセラミックを
用いるので、接合形状に制約がある。In this case, the MgAl 2 O 4 / MgO sintered body is composed of a solid electrolyte membrane and a lanthanum chromite (LaCrO 2).
3 ) It is thought that it works as an intermediate layer in ceramic bonding. However, since this method uses a MgAl 2 O 4 / MgO ceramic which has been sintered in advance, there is a restriction on the joining shape.
【００１３】そこで、本発明の目的は、イットリア安定
化ジルコニア（ＹＳＺ）やランタンクロマイト（ＬａＣ
ｒＯ3 ）系セラミックを劣化させることなく、固体電解
質膜とセパレータが良好に接合される固体電解質型燃料
電池を提供することにある。Accordingly, an object of the present invention is to provide yttria-stabilized zirconia (YSZ) or lanthanum chromite (LaC
An object of the present invention is to provide a solid oxide fuel cell in which a solid electrolyte membrane and a separator are satisfactorily joined without deteriorating an rO 3 ) -based ceramic.
【００１４】[0014]
【課題を解決するための手段】本発明は、請求項１にお
いて、固体電解質型燃料電池は、固体電解質膜とセパレ
ータが非ガラス系の無機酸化物接合剤で接合されている
ことを特徴とする。According to the present invention, there is provided a solid electrolyte fuel cell according to claim 1, wherein the solid electrolyte membrane and the separator are joined with a non-glass inorganic oxide joining agent. .
【００１５】また、請求項２において、固体電解質型燃
料電池は、前記非ガラス系の無機酸化物接合剤が、Ｍｇ
Ａｌ2 Ｏ4 、ＭｇＯ及びＣｒ2 Ｏ3 からなることを特徴
とする。According to a second aspect of the present invention, in the solid oxide fuel cell, the non-glass inorganic oxide bonding agent is made of Mg.
It is characterized by being made of Al 2 O 4 , MgO and Cr 2 O 3 .
【００１６】また、請求項３において、固体電解質型燃
料電池は、前記非ガラス系の無機酸化物接合剤が、Ｍｇ
Ａｌ2 Ｏ4 、ＭｇＯ及びＣｒ2 Ｏ3 が、５／９５≦Ｃｒ
2 Ｏ3 ／（ＭｇＡｌ2 Ｏ4 ＋ＭｇＯ）≦２０／８０の重
量比で構成されていることを特徴とする。According to a third aspect of the present invention, in the solid oxide fuel cell, the non-glass-based inorganic oxide binder is Mg
Al 2 O 4 , MgO and Cr 2 O 3 are 5/95 ≦ Cr
It is characterized by a weight ratio of 2 O 3 / (MgAl 2 O 4 + MgO) ≦ 20/80.
【００１７】このように、本発明は、固体電解質膜とセ
パレータを、Ｓｉを含まない非ガラス系の無機酸化物接
合剤、例えば、ＭｇＡｌ2 Ｏ4 ／ＭｇＯの混合物からな
る接合剤を用いて焼結接合するため、Ｓｉによるセパレ
ータのランタンクロマイト系セラミックへの影響がな
く、セラミックの劣化がない。As described above, according to the present invention, the solid electrolyte membrane and the separator are sintered using a non-glass-based inorganic oxide bonding agent containing no Si, for example, a bonding agent made of a mixture of MgAl 2 O 4 / MgO. Since the bonding is performed, Si does not affect the lanthanum chromite ceramic of the separator, and there is no deterioration of the ceramic.
【００１８】さらに、接合剤中にＣｒを一定の比率で存
在させることにより、接合剤の焼結性が向上し、より緻
密な接合を行うことができる。Further, by allowing Cr to be present in the bonding agent at a fixed ratio, the sinterability of the bonding agent is improved, and a more precise bonding can be performed.
【００１９】[0019]
【発明の実施の形態】次に、本発明の実施の形態を実施
例に基づき説明する。Next, embodiments of the present invention will be described based on examples.
【００２０】始めに、イットリア安定化ジルコニア（Ｙ
ＳＺ）の粉末に、バインダー（ブチラール系樹脂）及び
溶剤（トルエン及びエタノール）を所定量加え、これを
混合してスラリーとした。そして、このスラリーからド
クターブレード法で厚み約５０μｍの固体電解質膜用セ
ラミックグリーンシートを作製した。First, yttria-stabilized zirconia (Y
A predetermined amount of a binder (butyral-based resin) and a solvent (toluene and ethanol) were added to the powder of SZ), and these were mixed to form a slurry. Then, a ceramic green sheet for a solid electrolyte membrane having a thickness of about 50 μm was prepared from this slurry by a doctor blade method.
【００２１】次に、燃料極を作製するため、酸化ニッケ
ル（ＮｉＯ）とイットリア安定化ジルコニア（ＹＳＺ）
の粉末を重量比６：４で混合したものに、バインダー
（ブチラール系樹脂）と溶剤（トルエン及びエタノー
ル）を所定量加えて混合し、スラリー化した。そして、
このスラリーからドクターブレード法により、厚み約５
０μｍの燃料極用セラミックグリーンシートを作製し
た。Next, in order to produce a fuel electrode, nickel oxide (NiO) and yttria-stabilized zirconia (YSZ) are used.
A predetermined amount of a binder (butyral-based resin) and a solvent (toluene and ethanol) were added to a mixture of the powders at a weight ratio of 6: 4, and mixed to form a slurry. And
From the slurry, a doctor blade method was used to obtain a thickness of about 5
A 0 μm ceramic green sheet for fuel electrode was prepared.
【００２２】また、空気極を作製するため、Ｓｒを添加
したランタンマンガナイト（（Ｌａ，Ｓｒ）ＭｎＯ3 ）
の粉末に、バインダー（ブチラール系樹脂）と溶剤（ト
ルエン及びエタノール）を所定量加えて混合し、スラリ
ー化した。そして、このスラリーからドクターブレード
法により、厚さ約５０μｍの空気極用セラミックグリー
ンシートを得た。In order to produce an air electrode, lanthanum manganite ((La, Sr) MnO 3 ) to which Sr is added.
A predetermined amount of a binder (butyral-based resin) and a solvent (toluene and ethanol) were added to the powder and mixed to form a slurry. Then, a ceramic green sheet for an air electrode having a thickness of about 50 μm was obtained from the slurry by a doctor blade method.
【００２３】そして、固体電解質膜用セラミックグリ−
ンシートを数枚重ねたものの表裏面に、セパレータと接
合される部分を残して、空気極用及び燃料極用のセラミ
ックグリーンシート各１枚を配置して熱圧着し、空気
極、燃料極及び固体電解質膜からなる三層膜のセラミッ
クグリーンシート圧着体とした。And a ceramic grease for a solid electrolyte membrane.
The ceramic green sheets for the air electrode and the fuel electrode are placed on the front and back sides of the stack of several sheets, leaving the part to be joined to the separator, and thermocompression bonded. A three-layer ceramic green sheet crimped body made of an electrolyte membrane was obtained.
【００２４】続いて、この圧着体を１３００℃の温度で
２時間焼成し、三層膜のセラミック焼結体を得た。Subsequently, the pressed body was fired at a temperature of 1300 ° C. for 2 hours to obtain a three-layer ceramic sintered body.
【００２５】一方、セパレータは、Ｃａを添加したラン
タンクロマイト（（Ｌａ，Ｃａ）ＣｒＯ3 ）粉末を用い
て鋳込み成形法で成形し、これを焼成して相対密度９５
％以上の焼結体として得た。なお、相対密度とは、理論
密度を１００としたときの実際密度をパーセントで表し
たものである。On the other hand, the separator is molded by a casting method using lanthanum chromite ((La, Ca) CrO 3 ) powder to which Ca is added, and is fired to have a relative density of 95%.
% As a sintered body. The relative density is a percentage of the actual density when the theoretical density is 100.
【００２６】次に、接合剤を作製するために、まず、ス
ピネル（ＭｇＡｌ2 Ｏ4 ）と酸化マグネシウム（Ｍｇ
Ｏ）の重量比が５５／４５の混合粉末を準備した。Next, spinel (MgAl 2 O 4 ) and magnesium oxide (Mg
A mixed powder having a weight ratio of O) of 55/45 was prepared.
【００２７】そして、酸化クロム（Ｃｒ2 Ｏ3 ）と先に
準備したスピネルと酸化マグネシウムの混合物（ＭｇＡ
ｌ2 Ｏ4 ＋ＭｇＯ）を、表１に示す割合（重量比：０／
１００〜２５／７５）で混合したものに、ワニスを添加
してペースト状の接合剤を作製した。Then, a mixture of chromium oxide (Cr 2 O 3 ) and the previously prepared spinel and magnesium oxide (MgA
l 2 O 4 + MgO) in the proportions (weight ratio: 0 /
100 to 25/75), and a varnish was added to the mixture to prepare a paste-like bonding agent.
【００２８】[0028]
【表１】 [Table 1]
【００２９】次に、一対の前記ランタンクロマイト系焼
結体のセパレータと前記三層膜の固体電解質膜とを、両
者の接合部に前記接合剤を介して圧着した。Next, a pair of the lanthanum chromite-based sintered body separator and the three-layered solid electrolyte membrane were pressure-bonded to the joint between the two via the bonding agent.
【００３０】このようにして構成した三層膜のセラミッ
ク積層体とセパレータからなる圧着体を、１３００℃で
２時間焼成した。The pressed body composed of the three-layer ceramic laminate and the separator thus constituted was fired at 1300 ° C. for 2 hours.
【００３１】また、比較のため、ガラス系酸化物の接合
剤を作成するため、ＳｉＯ2 系ガラスを準備し、これに
ワニスを添加してペースト状のガラス系酸化物接合剤を
作製した。For comparison, a glass-based oxide bonding agent was prepared by preparing an SiO 2 -based glass and adding a varnish thereto to prepare a glass-based bonding agent.
【００３２】そして、一対の前記ランタンクロマイト系
焼結体のセパレータと前記三層膜の固体電解質膜とを、
両者の接合部にガラス系酸化物接合剤（ＳｉＯ2 系ガラ
ス接合剤）を介して圧着し、この圧着体を、１２００℃
で２時間焼成してセルを得た。Then, a pair of the lanthanum chromite-based sintered body separator and the three-layered solid electrolyte membrane are
The two bonded parts were pressed together via a glass-based oxide bonding agent (SiO 2 -based glass bonding agent), and the pressed body was 1200 ° C.
For 2 hours to obtain a cell.
【００３３】図２はこのようにして得られたセルの側面
図であり、（ａ）は燃料ガス（水素）が供給される側か
ら、また、（ｂ）は酸化ガス（空気）が供給される側か
らみた、セルの側面図である。同図において、３ａ，３
ｂはセパレータ、４は燃料極、５は固体電解質膜、６は
空気極、１１ａ，１１ｂ，１２ｃ，１２ｄは接合剤を示
している。FIGS. 2A and 2B are side views of the cell obtained in this manner. FIG. 2A shows the side from which the fuel gas (hydrogen) is supplied, and FIG. 2B shows the side where the oxidizing gas (air) is supplied. FIG. 4 is a side view of the cell as viewed from the side of the cell. In the figure, 3a, 3
b denotes a separator, 4 denotes a fuel electrode, 5 denotes a solid electrolyte membrane, 6 denotes an air electrode, and 11a, 11b, 12c and 12d denote bonding agents.
【００３４】以上、得られたセルについて、イットリア
安定化ジルコニア（ＹＳＺ）からなる固体電解質膜とラ
ンタンクロマイト（ＬａＣｒＯ3 ）系セラミックからな
るセパレータとの接合部を観察し、ガスシール部の接合
剤の焼結性及び固体電解質膜とセパレータとの接合状態
を確認した。From the above cell, the joint between the solid electrolyte membrane made of yttria-stabilized zirconia (YSZ) and the separator made of lanthanum chromite (LaCrO 3 ) ceramic was observed. The sinterability and the bonding state between the solid electrolyte membrane and the separator were confirmed.
【００３５】また、このときの接合剤の相対密度を求め
るために次のようにした。すなわち、Ｃｒ2 Ｏ3 と（Ｍ
ｇＡｌ2 Ｏ4 ＋ＭｇＯ）を、表１に示す割合（重量比：
０／１００〜２５／７５）で混合したものに、バインダ
ー（ブチラール系樹脂）と溶剤（トルエン及びエタノー
ル）を加えてスラリーとし、ドクターブレード法でセラ
ミックグリーンシートに成形した。そして、このセラミ
ックグリーンシートを数枚重ねた成形体を、前述の固体
電解質膜とセパレータを接合剤を介して焼成した同じ温
度条件、時間で焼成し、得られた焼結体の密度を測定
し、相対密度を求めた。In order to determine the relative density of the bonding agent at this time, the following was performed. That is, Cr 2 O 3 and (M
gAl 2 O 4 + MgO) in the ratio (weight ratio:
(0/100 to 25/75), a binder (butyral-based resin) and a solvent (toluene and ethanol) were added to form a slurry, which was formed into a ceramic green sheet by a doctor blade method. Then, the formed body obtained by stacking several ceramic green sheets was fired at the same temperature condition and time when the above-mentioned solid electrolyte membrane and separator were fired via a bonding agent, and the density of the obtained sintered body was measured. And the relative density.
【００３６】さらに、接合後のセパレータのランタンク
ロマイト（ＬａＣｒＯ3 ）系セラミックの劣化につい
て、接合した３層膜とＬａＣｒＯ3 焼結体との複合体を
還元雰囲気中で熱処理し、Ｃａ2 ＳｉＯ4 が生成してひ
び割れが発生したかどうかを確認して劣化のありなしを
評価した。Further, with respect to the deterioration of the lanthanum chromite (LaCrO 3 ) -based ceramic of the joined separator, the composite of the joined three-layer film and the LaCrO 3 sintered body was subjected to a heat treatment in a reducing atmosphere to reduce the Ca 2 SiO 4. It was confirmed whether or not cracks were generated and generated, and the presence or absence of deterioration was evaluated.
【００３７】以上の評価結果を表１に示す。Table 1 shows the above evaluation results.
【００３８】表１からわかるように、試料Ｎｏ．１ない
し試料Ｎｏ．６に用いた接合剤は、Ｓｉを含まないＭｇ
Ａｌ2 Ｏ4 ＋ＭｇＯやＭｇＡｌ2 Ｏ4 ＋ＭｇＯ＋Ｃｒ2
Ｏ3の非ガラス系無機酸化物からなり、この接合剤を用
いた場合、ランタンクロマイト（ＬａＣｒＯ3 ）系セラ
ミックに劣化が見られなかった。As can be seen from Table 1, Sample No. 1 to Sample No. The bonding agent used for No. 6 was Mg containing no Si.
Al 2 O 4 + MgO or MgAl 2 O 4 + MgO + Cr 2
It was made of a non-glass inorganic oxide of O 3 , and when this bonding agent was used, no deterioration was observed in the lanthanum chromite (LaCrO 3 ) ceramic.
【００３９】また、前記非ガラス系無機酸化物の接合剤
にＣｒを添加したものは、Ｃｒ2 Ｏ3 と（ＭｇＡｌ2 Ｏ
4 ＋ＭｇＯ）の比率が、５／９５≦Ｃｒ2 Ｏ3 ／（Ｍｇ
Ａｌ2 Ｏ4 ＋ＭｇＯ）≦２０／８０の範囲において、接
合剤の相対密度が高く、接合剤の焼結性、固体電解質膜
とセパレータとの接合状態とも良好であった。In addition, those obtained by adding Cr to the non-glass based inorganic oxide bonding agent include Cr 2 O 3 and (MgAl 2 O).
4 + MgO) is 5/95 ≦ Cr 2 O 3 / (Mg
In the range of (Al 2 O 4 + MgO) ≦ 20/80, the relative density of the bonding agent was high, and the sintering property of the bonding agent and the bonding state between the solid electrolyte membrane and the separator were good.
【００４０】なお、本実施例では、接合剤にペースト状
のものを用いたが、Ｃｒ2 Ｏ3 と（ＭｇＡｌ2 Ｏ4 ＋Ｍ
ｇＯ）との混合物に、バインダー（ブチラール系樹脂）
と溶剤（トルエン及びエタノール）を加えてスラリーと
し、ドクターブレード法でセラミックグリーンシートに
成形したものを用いても同様の効果が得られる。In this embodiment, the paste was used as the bonding agent, but the bonding agent was made of Cr 2 O 3 and (MgAl 2 O 4 + M
gO) and a binder (butyral resin)
A similar effect can be obtained by using a slurry obtained by adding a solvent and a solvent (toluene and ethanol) to form a slurry, and forming the slurry into a ceramic green sheet by a doctor blade method.
【００４１】また、上記実施例では無機酸化物接合剤が
ＭｇＡｌ2 Ｏ4 ＋ＭｇＯ＋Ｃｒ2 Ｏ3 である場合につい
て説明したが、本発明はこれに限定されるものではな
く、例えばＣａＴｉＯ3 やＳｒＴｉＯ3 等の非ガラス系
無機酸化物を接合剤に用いても同様の効果を得ることが
できる。In the above embodiment, the case where the inorganic oxide bonding agent is MgAl 2 O 4 + MgO + Cr 2 O 3 has been described. However, the present invention is not limited to this, and for example, CaTiO 3 , SrTiO 3, etc. The same effect can be obtained by using the non-glass-based inorganic oxide as a bonding agent.
【００４２】[0042]
【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、三層膜の固体電解質膜とセパレータの接合にお
いて、接合剤を緻密に焼結させることができるため、固
体電解質膜とセパレータとの接合がより強固なものとな
る。As is apparent from the above description, according to the present invention, the bonding agent can be densely sintered in joining the three-layered solid electrolyte membrane and the separator. Bonding with the separator becomes stronger.
【００４３】また、この接合剤は従来のガラス系接合剤
と異なり、セパレータに用いるランタンクロマイト系セ
ラミックの劣化を促進させない。Also, unlike the conventional glass-based bonding agent, this bonding agent does not promote deterioration of the lanthanum chromite-based ceramic used for the separator.
【００４４】したがって、固体電解質膜のイットリア安
定化ジルコニア（ＹＳＺ）とセパレータのランタンクロ
マイト（ＬａＣｒＯ3 ）系セラミックの接合部のガスシ
ール性がより向上し、燃料電池の運転時の気密性、温度
の対する信頼性及び耐久性に優れた固体電解質型燃料電
池を提供することができる。Therefore, the gas-sealing property of the joint between the yttria-stabilized zirconia (YSZ) of the solid electrolyte membrane and the lanthanum chromite (LaCrO 3 ) -based ceramic of the separator is further improved, and the airtightness and the temperature during operation of the fuel cell are improved. It is possible to provide a solid oxide fuel cell having excellent reliability and durability.
【図１】本発明に係る固体電解質型燃料電池のセル構造
を示す分解斜視図である。FIG. 1 is an exploded perspective view showing a cell structure of a solid oxide fuel cell according to the present invention.
【図２】（ａ）本発明に係る固体電解質型燃料電池のセ
ルのガスシール部の構造を示す燃料ガス（水素）の供給
側から見た側面図である。 （ｂ）本発明に係る固体電解質型燃料電池のセルのガス
シール部の構造を示す酸化ガス（空気）の供給側から見
た側面図である。FIG. 2A is a side view showing a structure of a gas seal portion of a cell of a solid oxide fuel cell according to the present invention, as viewed from a fuel gas (hydrogen) supply side. (B) It is the side view seen from the supply side of oxidizing gas (air) which shows the structure of the gas seal part of the cell of the solid oxide fuel cell concerning the present invention.
１ セル ２ａ，２ｂ ３層膜 ３ａ，３ｂ セパレータ ４ 燃料極 ５ 固体電解質膜 ６ 空気極 ７ａ，７ｂ，７ｃ，７ｄ 溝 ８ａ，８ｂ，８ｃ，８ｄ セパレータの端縁部 ９ａ，９ｂ，９ｃ，９ｄ 固体電解質膜の端縁部 １１ａ，１１ｂ，１２ｃ，１２ｄ 接合剤 DESCRIPTION OF SYMBOLS 1 Cell 2a, 2b Three-layer membrane 3a, 3b Separator 4 Fuel electrode 5 Solid electrolyte membrane 6 Air electrode 7a, 7b, 7c, 7d Groove 8a, 8b, 8c, 8d Separator edge 9a, 9b, 9c, 9d Solid Edge of electrolyte membrane 11a, 11b, 12c, 12d Bonding agent
Claims (3)
系の無機酸化物接合剤で接合されていることを特徴とす
る固体電解質型燃料電池。1. A solid oxide fuel cell, wherein the solid electrolyte membrane and the separator are joined with a non-glass inorganic oxide joining agent.
4 、ＭｇＯ及びＣｒ2 Ｏ3 からなることを特徴とする請
求項１記載の固体電解質型燃料電池。2. The non-glass based bonding agent is MgAl 2 O.
4, MgO and the solid electrolyte type fuel cell according to claim 1, characterized in that it consists of Cr 2 O 3.
ＭｇＡｌ2 Ｏ4 、ＭｇＯ及びＣｒ2 Ｏ3 が次の重量比で
構成されていることを特徴とする請求項１または２記載
の固体電解質型燃料電池。 ５／９５≦Ｃｒ2 Ｏ3 ／（ＭｇＡｌ2 Ｏ4 ＋ＭｇＯ）≦
２０／８０3. The non-glass based inorganic oxide bonding agent,
3. The solid oxide fuel cell according to claim 1, wherein MgAl 2 O 4 , MgO and Cr 2 O 3 are constituted in the following weight ratio. 5/95 ≦ Cr 2 O 3 / (MgAl 2 O 4 + MgO) ≦
20/80
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26187596A JP3707155B2 (en) | 1996-10-02 | 1996-10-02 | Solid oxide fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26187596A JP3707155B2 (en) | 1996-10-02 | 1996-10-02 | Solid oxide fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10106596A true JPH10106596A (en) | 1998-04-24 |
| JP3707155B2 JP3707155B2 (en) | 2005-10-19 |
Family
ID=17367981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26187596A Expired - Fee Related JP3707155B2 (en) | 1996-10-02 | 1996-10-02 | Solid oxide fuel cell |
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| Country | Link |
|---|---|
| JP (1) | JP3707155B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004207170A (en) * | 2002-12-26 | 2004-07-22 | Ngk Spark Plug Co Ltd | Stacked body and solid electrolyte fuel cell |
| JP2009135051A (en) * | 2007-11-30 | 2009-06-18 | Korea Advanced Inst Of Sci Technol | Joining structure between end cell and separator of solid oxide fuel cell |
| JP2013258157A (en) * | 2013-08-26 | 2013-12-26 | Mitsubishi Heavy Ind Ltd | Solid electrolyte fuel cell |
-
1996
- 1996-10-02 JP JP26187596A patent/JP3707155B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004207170A (en) * | 2002-12-26 | 2004-07-22 | Ngk Spark Plug Co Ltd | Stacked body and solid electrolyte fuel cell |
| JP2009135051A (en) * | 2007-11-30 | 2009-06-18 | Korea Advanced Inst Of Sci Technol | Joining structure between end cell and separator of solid oxide fuel cell |
| JP2013258157A (en) * | 2013-08-26 | 2013-12-26 | Mitsubishi Heavy Ind Ltd | Solid electrolyte fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3707155B2 (en) | 2005-10-19 |
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