JP5364291B2 - Bonding material, bonding member, bonding method, solid oxide fuel cell, and bonding material for solid oxide fuel cell - Google Patents
Bonding material, bonding member, bonding method, solid oxide fuel cell, and bonding material for solid oxide fuel cell Download PDFInfo
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Description
本発明は、固体電解質型燃料電池（以下、「ＳＯＦＣ」と記載する。）や水蒸気電解セル等の電極と他の構造部材を電気的に接合する場合に用いられる接合材、これを用いた接合部材および接合方法、ならびにこの接合部材を有するＳＯＦＣに関する。 The present invention relates to a bonding material used when an electrode such as a solid oxide fuel cell (hereinafter referred to as “SOFC”) or a steam electrolysis cell and other structural members are electrically bonded, and bonding using the same. The present invention relates to a member, a joining method, and an SOFC having the joining member.
ＳＯＦＣの要部の一般的な構成として、図１に示すものが知られている。発電膜２は、イットリア安定化ジルコニアの固体電解質膜４と、その両面に形成された燃料側電極３と空気側電極５とから構成され、ディンプル状の形状をしている。発電膜２の燃料側電極３の側には、燃料側電極３と電気的に接続されたインターコネクタ７が設けられ、発電膜２の空気側電極５の側には、空気側電極５と電気的に接続されたインターコネクタ７が設けられている。こうした構成のＳＯＦＣにおいては、インターコネクタ７と燃料側電極３との間、インターコネクタ７と空気側電極５との間に一般的に導電性接合部材１１、１２が用いられている。
As a general configuration of the main part of the SOFC, the one shown in FIG. 1 is known. The
導電性接合部材１１、１２はペースト状の接合材を焼結して形成することができる。燃料側の導電性接合部材１１を形成する接合材としては、例えば、酸化ニッケル（ＮｉＯ）、酸化鉄（Ｆｅ２Ｏ３）および酸化チタン（ＴｉＯ２）をベース材料として含む接合材が、良好な導電性、接合性を有する接合部材を形成する材料として提案されている（例えば、特許文献１参照。）。
上記ＮｉＯ、Ｆｅ２Ｏ３およびＴｉＯ２をベース材料として含む接合材を用いてＳＯＦＣを構成した場合、ＳＯＦＣの運転中にＮｉＯおよびＦｅ２Ｏ３がそれぞれＮｉおよびＦｅに還元されることで、燃料側導電性接合部材１１の導電性を確保している。
しかし、ＮｉＯおよびＦｅ２Ｏ３が還元される際に体積収縮を伴うため、接合部材がやや多孔質になり、酸化雰囲気で製造したときと比べて、還元処理後の接合強度が低下するという問題がある。
When the SOFC is configured using the bonding material including NiO, Fe 2 O 3 and TiO 2 as the base material, the fuel is obtained by reducing NiO and Fe 2 O 3 to Ni and Fe, respectively, during the operation of the SOFC. The conductivity of the side
However, when NiO and Fe 2 O 3 are reduced, the shrinkage of the volume is accompanied, so that the joining member becomes slightly porous and the joining strength after the reduction treatment is reduced as compared with the case where the joining member is manufactured in an oxidizing atmosphere. There is.
本発明は、このような事情に鑑みてなされたものであって、還元処理後も接合強度の低下のないあるいは接合強度の低下が少ない接合部材を形成する接合材を提供することを目的とする。
また本発明は、前記接合材より形成され、ＳＯＦＣの運転等において還元雰囲気で使用しても接合強度が低下しにくい接合部材を提供することを目的とする。
また本発明は、前記接合材を用いて、ＳＯＦＣにおける燃料側電極とインターコネクタ等の他の部材とのあいだ等に、運転等において還元雰囲気で使用しても接合強度が低下しにくい接合部を形成する接合方法を提供することを目的とする。
また本発明は、燃料側電極とインターコネクタ等の他の部材とのあいだ等において、運転等において還元雰囲気で使用しても接合強度が低下しにくい接合部を有し、信頼性が向上したＳＯＦＣを提供することを目的とする。
This invention is made | formed in view of such a situation, Comprising: It aims at providing the bonding | jointing material which forms the joining member which does not have the fall of joining strength after a reduction process, or there is little decline in joining strength. .
It is another object of the present invention to provide a joining member which is formed from the joining material and whose joining strength is not easily lowered even when used in a reducing atmosphere in SOFC operation or the like.
Further, the present invention uses the above-mentioned bonding material to provide a bonding portion in which the bonding strength is not easily lowered even when used in a reducing atmosphere during operation or the like between the fuel-side electrode in SOFC and another member such as an interconnector. An object is to provide a bonding method to be formed.
In addition, the present invention provides a SOFC having improved reliability, including a joint portion between the fuel side electrode and another member such as an interconnector, in which the joint strength is not easily lowered even when used in a reducing atmosphere in operation or the like. The purpose is to provide.
上記課題を解決するために、本発明は、以下の手段を採用する。
本発明の接合材は、酸化ニッケル（ＮｉＯ）と、酸化マンガン（ＭｎＯ２）とを、合計１００重量部含有するベース材料を含み、前記酸化マンガンの量を２０重量部以上３０重量部以下とした。
上記本発明の接合材は、ベース材料に酸化マンガンを用いることにより、ＳＯＦＣの燃料側導電性接合部材に用いても、還元処理後の収縮が小さくなり、還元処理後の強度低下を抑えることができる。
In order to solve the above problems, the present invention employs the following means.
The bonding material of the present invention includes a base material containing a total of 100 parts by weight of nickel oxide (NiO) and manganese oxide (MnO 2 ), and the amount of the manganese oxide is 20 parts by weight or more and 30 parts by weight or less. .
By using manganese oxide as a base material, the bonding material of the present invention reduces shrinkage after reduction treatment and suppresses strength reduction after reduction treatment even when used as a fuel-side conductive joining member for SOFC. it can.
本発明に係る接合部材は、複数の部材の間に配置された前記本発明の接合材を焼結して得られる。
従って、本発明の接合部材は、上述の通り、ＳＯＦＣの燃料側に用いた場合に、還元処理後の収縮が小さくなり、還元処理後の強度低下を抑えることができる。
The joining member according to the present invention is obtained by sintering the joining material of the present invention disposed between a plurality of members.
Therefore, as described above, when the joining member of the present invention is used on the fuel side of SOFC, the shrinkage after the reduction treatment is reduced, and the strength reduction after the reduction treatment can be suppressed.
本発明に係る接合方法は、前記本発明の接合材を複数の部材の間に配置し、該接合材を焼結する方法である。
従って、本発明の接合方法によれば、ＳＯＦＣにおける燃料側電極とインターコネクタ等の部材間に、接合強度に優れた接合部を形成することができる。
The bonding method according to the present invention is a method in which the bonding material of the present invention is disposed between a plurality of members and the bonding material is sintered.
Therefore, according to the bonding method of the present invention, it is possible to form a bonded portion having excellent bonding strength between the fuel-side electrode and the interconnector and the like in the SOFC.
本発明に係るＳＯＦＣは、複数の部材と、該複数の部材の間を接合する前記本発明の接合部材とを有する。
従って、本発明のＳＯＦＣは、燃料側電極とインターコネクタ等の部材間の接合部の接合強度を高めることができるので、信頼性に優れる。
The SOFC according to the present invention includes a plurality of members and the joining member of the present invention that joins between the plurality of members.
Therefore, the SOFC of the present invention is excellent in reliability because it can increase the bonding strength of the bonding portion between the fuel side electrode and the interconnector.
本発明によれば、還元処理後も接合強度の低下のないあるいは接合強度の低下が少ない接合部材を形成する接合材を提供することができる。
また本発明によれば、ＳＯＦＣの運転等において還元雰囲気で使用しても接合強度が低下しにくい接合部材を提供することができる。
また本発明によれば、ＳＯＦＣにおける燃料側電極とインターコネクタ等の他の部材とのあいだ等に、運転等において還元雰囲気で使用しても接合強度が低下しにくい接合部を形成する接合方法を提供することができる。
また本発明によれば、燃料側電極とインターコネクタ等の他の部材とのあいだ等において、運転等において還元雰囲気で使用しても接合強度が低下しにくい接合部を有し、信頼性が向上したＳＯＦＣを提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the joining material which forms the joining member which does not show the fall of joining strength after a reduction process or there is little decline in joining strength can be provided.
Further, according to the present invention, it is possible to provide a joining member in which the joining strength is not easily lowered even when used in a reducing atmosphere in SOFC operation or the like.
Further, according to the present invention, there is provided a joining method for forming a joint portion in which the joining strength is not easily lowered even when used in a reducing atmosphere in operation or the like between the fuel side electrode in SOFC and another member such as an interconnector. Can be provided.
In addition, according to the present invention, there is a joint between the fuel side electrode and another member such as an interconnector, etc., and the joint strength is not easily lowered even when used in a reducing atmosphere in operation, etc., and reliability is improved. SOFC can be provided.
以下、本発明の実施形態について説明する。
本発明の第１の実施形態は、酸化ニッケル（ＮｉＯ）と、酸化マンガン（ＭｎＯ２）とを、合計１００重量部含有するベース材料を含み、前記酸化マンガンの量が２０重量部以上３０重量部以下（酸化ニッケルの量を８０重量部以下７０重量部以上）である接合材である。
Hereinafter, embodiments of the present invention will be described.
The first embodiment of the present invention includes a base material containing a total of 100 parts by weight of nickel oxide (NiO) and manganese oxide (MnO 2 ), and the amount of the manganese oxide is 20 parts by weight or more and 30 parts by weight. The bonding material is below (the amount of nickel oxide is 80 parts by weight or less and 70 parts by weight or more).
酸化マンガンは還元処理後の接合部材の収縮を低減し、還元処理後の強度低下を抑えるために添加される。酸化マンガンが２０重量部未満では所望の還元収縮低減効果が得られず、還元処理後の接合強度が低下するので好ましくない。また、酸化マンガンが３０重量部を超えた場合は、還元処理後の接合部材が膨張することがあり、この場合も還元処理後の接合強度が低下するので好ましくない。 Manganese oxide is added to reduce the shrinkage of the joint member after the reduction treatment and to suppress the strength reduction after the reduction treatment. If manganese oxide is less than 20 parts by weight, the desired reduction shrinkage reduction effect cannot be obtained, and the bonding strength after the reduction treatment is lowered, which is not preferable. Moreover, when manganese oxide exceeds 30 weight part, the joining member after a reduction process may expand | swell, and since the joining strength after a reduction process also falls in this case, it is unpreferable.
酸化ニッケルの粒径は、０．３μｍ以上５μｍ以下が好ましい。酸化ニッケルの粒径が０．３μｍ未満では、接合部材の収縮率が大きくなり、大気熱処理時にひび割れが発生して接合強度が低下するので好ましくない。酸化ニッケルの粒径が５μｍを超えると、接合部材の焼結性が低下し、接合部材の接合強度が低下するので好ましくない。酸化ニッケルの粒径は、０．５μｍ以上１．５μｍ以下がより好ましい。 The particle diameter of nickel oxide is preferably 0.3 μm or more and 5 μm or less. When the particle diameter of nickel oxide is less than 0.3 μm, the shrinkage rate of the joining member increases, and cracks are generated during heat treatment in the atmosphere, resulting in a decrease in joining strength. When the particle size of nickel oxide exceeds 5 μm, the sinterability of the joining member is lowered, and the joining strength of the joining member is lowered. The particle diameter of nickel oxide is more preferably 0.5 μm or more and 1.5 μm or less.
酸化マンガンの粒径は、０．５μｍ以上５μｍ以下が好ましい。酸化マンガンの粒径が０．５μｍ未満では、接合部材の収縮率が大きくなり、大気熱処理時にひび割れが発生して接合強度が低下するので好ましくない。酸化マンガンの粒径が５μｍを超えると、接合部材の焼結性が低下し、接合部材の接合強度が低下するので好ましくない。酸化マンガンの粒径は、０．８μｍ以上２μｍ以下がより好ましい。 The particle size of manganese oxide is preferably 0.5 μm or more and 5 μm or less. If the particle size of manganese oxide is less than 0.5 μm, the shrinkage rate of the joining member increases, cracking occurs during the air heat treatment, and the joining strength decreases, which is not preferable. When the particle size of manganese oxide exceeds 5 μm, the sinterability of the joining member is lowered, and the joining strength of the joining member is lowered, which is not preferable. The particle size of manganese oxide is more preferably 0.8 μm or more and 2 μm or less.
前記ベース材料は、その１００重量部に対し、熱膨張調整材を１０重量部以上２０重量部以下含有してもよい。
一般に、接合部材は還元される際に体積収縮を伴うため、やや多孔質になり、酸化雰囲気で製造したときと比べて、還元処理後の接合強度が低下するという問題がある。このような還元収縮を防止する目的で、前記熱膨張調整材が添加される。
前記熱膨張調整材の含有量が１０重量部未満では、還元収縮防止の効果が小さく不充分となる場合があり好ましくない。また、前記熱膨張調整材の含有量が２０重量部を超えると導電性の低下を生ずる場合があるので好ましくない。
The base material may contain 10 parts by weight or more and 20 parts by weight or less of a thermal expansion adjusting material with respect to 100 parts by weight of the base material.
Generally, since the joining member is accompanied by volume shrinkage when being reduced, the joining member becomes slightly porous, and there is a problem that the joining strength after the reduction treatment is reduced as compared with the case where the joining member is manufactured in an oxidizing atmosphere. In order to prevent such reduction shrinkage, the thermal expansion adjusting material is added.
When the content of the thermal expansion adjusting material is less than 10 parts by weight, the effect of preventing reduction shrinkage may be small and insufficient, which is not preferable. In addition, if the content of the thermal expansion adjusting material exceeds 20 parts by weight, the conductivity may be lowered, which is not preferable.
前記熱膨張調整材は、アルミナ、窒化ケイ素、炭化ケイ素およびコージェライトからなる群より選ばれる少なくとも一種の材料を含むことが好ましい。
これら材料の熱膨張係数は、アルミナが約８×１０−６／℃、窒化ケイ素が約４×１０−６／℃、炭化ケイ素が約５×１０−６／℃、コージェライトが約２×１０−６／℃であり、いずれの材料も本発明の接合材において良好な還元収縮防止効果を有する熱膨張調整材として機能する。
The thermal expansion adjusting material preferably contains at least one material selected from the group consisting of alumina, silicon nitride, silicon carbide, and cordierite.
The thermal expansion coefficients of these materials are about 8 × 10 −6 / ° C. for alumina, about 4 × 10 −6 / ° C. for silicon nitride, about 5 × 10 −6 / ° C. for silicon carbide, and about 2 × 10 6 for cordierite. The temperature is −6 / ° C., and any material functions as a thermal expansion adjusting material having a good reduction shrinkage preventing effect in the bonding material of the present invention.
前記熱膨張調整材は、平均粒径５μｍ以上１５μｍ以下の粒子状の熱膨張調整材であることが好ましい。
前記熱膨張調整材の平均粒径が５μｍより小さいと、接合部材の収縮率が大きくなり、大気熱処理時にひび割れが発生して接合強度が低下するので好ましくない。また、熱膨張調整材の平均粒径が１５μｍより大きいと、接合部材の焼結性が低下し、接合部材の接合強度が低下するので好ましくない。
The thermal expansion adjusting material is preferably a particulate thermal expansion adjusting material having an average particle diameter of 5 μm to 15 μm.
When the average particle diameter of the thermal expansion adjusting material is smaller than 5 μm, the shrinkage rate of the joining member is increased, cracks are generated during the atmospheric heat treatment, and the joining strength is lowered. Moreover, when the average particle diameter of the thermal expansion adjusting material is larger than 15 μm, the sinterability of the joining member is lowered, and the joining strength of the joining member is lowered, which is not preferable.
前記接合材は前記ベース材料に加えてビヒクルを含むものが望ましい。
ビヒクルは、接合材を焼結する際に蒸発し、焼結後の接合部材中には残留しない原料であるが、ビヒクルを用いることにより接合材のベース材料をペースト状にし、取り扱いを容易にすることができる。
ビヒクルは、粉体を分散できるものであれば特に限定されないが、好ましくは、ブチルカルビトール、テレピン油、ブタノール等が挙げられ、特に好ましくはブチルカルビトールである。ビヒクルの添加量は、ビヒクルの種類によって異なるが、ベース材料を１００重量部とすると、３０重量部以上５０重量部以下添加することが好ましい。
The bonding material preferably includes a vehicle in addition to the base material.
The vehicle is a raw material that evaporates when the bonding material is sintered and does not remain in the sintered bonding member. By using the vehicle, the base material of the bonding material is made into a paste to facilitate handling. be able to.
The vehicle is not particularly limited as long as it can disperse the powder, but preferably includes butyl carbitol, turpentine oil, butanol and the like, and particularly preferably butyl carbitol. The addition amount of the vehicle varies depending on the type of the vehicle, but when the base material is 100 parts by weight, it is preferable to add 30 parts by weight or more and 50 parts by weight or less.
本発明の第２の実施形態は、前記第１の実施形態による接合材を複数の部材の間に配置し、該接合材を焼結する接合方法ならびにこの接合方法により前記接合材から得られた接合部材である。 In the second embodiment of the present invention, the bonding material according to the first embodiment is disposed between a plurality of members, and the bonding material is sintered from the bonding material, and the bonding material is obtained from the bonding material by the bonding method. It is a joining member.
接合の対象となる前記複数の部材としては、ＳＯＦＣの構成部材が挙げられ、ＳＯＦＣの運転時に還元雰囲気となる燃料側部材が、還元時の接合強度の低下を抑制できるという本発明の接合材の効果が発揮できるので好適である。従って、本実施形態の接合方法は、ＳＯＦＣの燃料側電極と他の燃料側部材（例えばインターコネクタ）との接合に好適に適用できる。 Examples of the plurality of members to be joined include SOFC constituent members, and the fuel-side member that is in a reducing atmosphere during operation of the SOFC can suppress a reduction in joining strength during reduction. This is preferable because the effect can be exhibited. Therefore, the joining method of the present embodiment can be suitably applied to joining of the SOFC fuel-side electrode and another fuel-side member (for example, an interconnector).
本実施形態の接合方法においては、公知の塗布方法が採用され、例えばスクリーンプリント法を採用することができる。例えば、インターコネクタとディンプル状の固体電解質上に製膜された燃料側電極とをスクリーンプリント法で接合する場合には、まずペースト状の接合材を、スクリーンにあいた穴から印刷するスクリーンプリントの方法により、インターコネクタの平板上に１００〜２００μｍの厚さに均一に塗布し、発電膜を載せて、空気中で熱処理を行う。熱処理では、２００℃までにビヒクルを蒸発させ、その後さらにＳＯＦＣの作業温度を考慮して１０００℃以上、好ましくは１０００〜１２５０℃で処理して焼結させる。この熱処理は、特に好ましくは１２５０℃で４時間の処理である。この熱処理により前記接合材が焼結し、本実施形態の接合部材となる。 In the bonding method of the present embodiment, a known coating method is employed, for example, a screen printing method can be employed. For example, when joining an interconnector and a fuel-side electrode formed on a dimple-like solid electrolyte by a screen printing method, first a screen printing method of printing a paste-like joining material from a hole in the screen Thus, the film is uniformly applied to a thickness of 100 to 200 μm on the flat plate of the interconnector, the power generation film is placed, and heat treatment is performed in air. In the heat treatment, the vehicle is evaporated up to 200 ° C., and is further processed and sintered at 1000 ° C. or higher, preferably 1000 to 1250 ° C. in consideration of the working temperature of SOFC. This heat treatment is particularly preferably a treatment at 1250 ° C. for 4 hours. By this heat treatment, the bonding material is sintered and becomes the bonding member of this embodiment.
本発明の第３の実施形態は、複数の部材と、該複数の部材の間を接合する前記第２の実施形態による接合部材とを有するＳＯＦＣである。
前記複数の部材としては、ＳＯＦＣの運転時に還元雰囲気となる燃料側部材が、還元時の接合強度の低下を抑制できるという本発明の接合材の効果が発揮できるので好適である。従って、本実施形態のＳＯＦＣとしては、ＳＯＦＣの燃料側電極と他の燃料側部材（例えばインターコネクタ）とが前記第２の実施形態による接合部材で接合されたＳＯＦＣが挙げられる。
The third embodiment of the present invention is an SOFC having a plurality of members and the joining member according to the second embodiment that joins the plurality of members.
As the plurality of members, the fuel-side member that is in a reducing atmosphere during the operation of the SOFC is preferable because the effect of the bonding material of the present invention that can suppress a decrease in bonding strength during reduction can be achieved. Therefore, the SOFC of this embodiment includes an SOFC in which a fuel-side electrode of the SOFC and another fuel-side member (for example, an interconnector) are joined by the joining member according to the second embodiment.
本実施形態のＳＯＦＣは、燃料側で用いられる接合部材を前記第２の実施形態による接合部材に代えた以外は、従来のＳＯＦＣと同様の構成とすることができる。従って、以下、前述の図１を参照して本実施形態のＳＯＦＣの構成例を説明する。前述の構成要素と同様の機能を有する構成要素については、同じ符号を用いて説明する。なお、本発明のＳＯＦＣは、以下の構成例に限定されない。 The SOFC of this embodiment can have the same configuration as that of a conventional SOFC except that the joining member used on the fuel side is replaced with the joining member according to the second embodiment. Therefore, a configuration example of the SOFC of this embodiment will be described below with reference to FIG. Components having functions similar to those of the above-described components will be described using the same reference numerals. The SOFC of the present invention is not limited to the following configuration example.
図１に示すように、発電膜２は、イットリア安定化ジルコニアの固体電解質膜４と、その両面に形成された燃料側電極３と空気側電極５とから構成され、ディンプル状の形状をしている。発電膜２の燃料側電極３の側には、燃料側電極３と電気的に接続されたインターコネクタ７が設けられ、発電膜２の空気側電極５の側には、空気側電極５と電気的に接続されたインターコネクタ７が設けられている。インターコネクタ７と空気側電極５との間には、この部位の使用環境に適合した導電性接合部材１２が用いられている。またインターコネクタ７と燃料側電極３との間には、前記第２の実施形態による接合部材１１が用いられている。
As shown in FIG. 1, the
次に、本発明を実験例に基づき説明するが、本発明はこれら実験例に限定されるものではない。 Next, the present invention will be described based on experimental examples, but the present invention is not limited to these experimental examples.
実験例１
表１に示した分量の酸化ニッケル粉末と酸化マンガン粉末に、ビヒクル（混合溶媒）としてブチルカルビトールを加えて、アルミナ製３本ロールミルを用いて混練し、ペースト状として、実施例１および２ならびに比較例１および２の接合材ペーストのサンプルを得た。
また、上記酸化ニッケル粉末と酸化マンガン粉末の混合粉末に代えて酸化ニッケル粉末と酸化鉄粉末を重量比７０：３０で含む混合粉末を用いた以外は上記と同様にして、比較例３の接合材ペーストのサンプルを得た。
Experimental example 1
To the nickel oxide powder and manganese oxide powder of the amount shown in Table 1, butyl carbitol was added as a vehicle (mixed solvent) and kneaded using a three-roll mill made of alumina. Samples of the bonding material pastes of Comparative Examples 1 and 2 were obtained.
The bonding material of Comparative Example 3 was the same as above except that a mixed powder containing nickel oxide powder and iron oxide powder in a weight ratio of 70:30 was used instead of the mixed powder of nickel oxide powder and manganese oxide powder. A sample of paste was obtained.
これら接合材ペーストのサンプルを用いて、図２に示す発電膜とインターコネクタの接合サンプルを作製し、以下に説明する方法で接合部の接合強度を測定した。
まず、接合材ペーストを３０ｍｍ角のインターコネクタ２２の片面に１００〜２００μｍの厚さに均一に塗布し、この塗布部分に、３０ｍｍ角の発電膜２３の燃料側電極側を接着した。次に接合材ペーストを大気中１２５０℃で４時間にわたって焼付処理をしたのち炉冷し、導電性接合部材２１の大気焼成後サンプルとした。また、さらに１０００℃で４％Ｈ２−Ｎ２バランス雰囲気で還元処理を施したものを、導電性接合部材２１の還元処理後サンプルとした。
Using the samples of the bonding material paste, a bonding sample of the power generation film and the interconnector shown in FIG. 2 was prepared, and the bonding strength of the bonding portion was measured by the method described below.
First, the bonding material paste was uniformly applied to one side of a 30 mm square interconnector 22 to a thickness of 100 to 200 μm, and the fuel side electrode side of the 30 mm square power generation film 23 was adhered to this applied portion. Next, the bonding material paste was baked at 1250 ° C. in the atmosphere for 4 hours and then cooled in the furnace to obtain a sample of the
上記大気焼成後サンプルおよび還元処理後サンプルのそれぞれについて、インターコネクタ２２と、固体電解質膜４の両面に燃料極電極１３及び空気側電極１５を形成してなる発電膜２３の燃料側電極１３側との接合強度を測定するために、インターコネクタ２２を接着剤でアクリル板２５に接着し、発電膜２３の空気側電極１５側には重しを入れられるような容器２７を取り付けた。この容器に重しを入れていき、インターコネクタ２２と発電膜２３の燃料側電極側とがはがれる重量を測定し、導電性接合部材２１の接合強度を評価した。測定結果を表１に示す。
For each of the air-fired sample and the reduction-treated sample, the interconnector 22 and the fuel-
また、上記接合材ペーストのサンプルを大気中で焼成して棒状の焼結体を作製して長さを測定した。この焼結体をさらに１０００℃で４％Ｈ２−Ｎ２バランス雰囲気で還元処理し、再び長さを測定した。大気焼成後の焼結体の長さと還元処理後の焼結体の長さから、各サンプルの還元収縮率を求めた。結果を表１に示す。 Moreover, the sample of the said joining material paste was baked in air | atmosphere, the rod-shaped sintered compact was produced, and the length was measured. This sintered body was further reduced at 1000 ° C. in a 4% H 2 —N 2 balance atmosphere, and the length was measured again. From the length of the sintered body after firing in the air and the length of the sintered body after the reduction treatment, the reduction shrinkage rate of each sample was determined. The results are shown in Table 1.
表１に示した結果から、酸化ニッケルと、酸化マンガンとを、合計１００重量部含有するベース材料を含み、前記酸化マンガンの量が２０重量部以上３０重量部以下である接合材でＳＯＦＣの燃料側接合部材を形成することにより、還元処理後の収縮が小さくなり、還元処理後の強度低下が抑えられることが分かる。
酸化マンガンが２０重量部未満では所望の還元収縮低減効果が得られず、還元処理後の接合強度が低下することがわかる。また、酸化マンガンが３０重量部を超えた場合は、還元処理後の接合部材が膨張することがあり、この場合も還元処理後の接合強度が低下することがわかる。
From the results shown in Table 1, the fuel of SOFC is a joining material including a base material containing 100 parts by weight of nickel oxide and manganese oxide in a total amount of 20 parts by weight or more and 30 parts by weight or less. It can be seen that by forming the side joining member, the shrinkage after the reduction treatment is reduced, and the strength reduction after the reduction treatment is suppressed.
It can be seen that if the manganese oxide is less than 20 parts by weight, the desired reduction shrinkage reduction effect cannot be obtained, and the bonding strength after the reduction treatment is lowered. Moreover, when manganese oxide exceeds 30 weight part, it turns out that the joining member after a reduction process may expand | swell, and also in this case, the joint strength after a reduction process falls.
実験例２
重量比７０：３０の酸化ニッケル粉末（粒径１μｍ）および酸化マンガン粉末（粒径１μｍ）を合計８５重量部とし、これに表２に示す熱膨張調整用粉末を１５重量部加えて、実施例３〜８ならびに比較例４および５のベース材料とした。また従来例として、酸化ニッケル（ＮｉＯ）粉末、酸化鉄（Ｆｅ２Ｏ３）粉末および酸化チタン（ＴｉＯ２）粉末を重量比４０：４０：２０で混合したものを比較例６のベース材料とした。これらベース材料にビヒクル（混合溶媒）としてブチルカルビトールを加えて、アルミナ製３本ロールミルを用いて混練し、ペースト状として、接合材ペーストの各サンプルを得た。
Experimental example 2
A total of 85 parts by weight of 70:30 nickel oxide powder (particle diameter 1 μm) and manganese oxide powder (particle diameter 1 μm) in a weight ratio of 70:30, and 15 parts by weight of the thermal expansion adjusting powder shown in Table 2 were added thereto. The base materials of 3 to 8 and Comparative Examples 4 and 5 were used. Further, as a conventional example, a mixture of nickel oxide (NiO) powder, iron oxide (Fe 2 O 3 ) powder and titanium oxide (TiO 2 ) powder in a weight ratio of 40:40:20 was used as the base material of Comparative Example 6. . Butyl carbitol was added as a vehicle (mixed solvent) to these base materials and kneaded using a three-roll mill made of alumina to obtain each sample of the bonding material paste as a paste.
これら接合材ペーストのサンプルを用いて、実験例１と同様の方法で接合部の接合強度を測定した。測定結果を表２に示す。 Using these bonding material paste samples, the bonding strength of the bonding portion was measured in the same manner as in Experimental Example 1. The measurement results are shown in Table 2.
表２に示した結果から、酸化ニッケル、酸化マンガンおよび粒径５μｍ以上１５μｍ以下の熱膨張調整材を含有するベース材料を含む接合材を用いて形成された接合部材は、還元処理後の接合強度が従来の接合部材より高いということが分かる。 From the results shown in Table 2, the joining member formed using a joining material including nickel oxide, manganese oxide and a base material containing a thermal expansion adjusting material having a particle size of 5 μm or more and 15 μm or less has a bonding strength after reduction treatment. It can be seen that is higher than the conventional joining member.
熱膨張調整材（アルミナ）の粒径が５μｍ未満の比較例４では、接合部材の収縮率が大きくなるので、大気焼成後サンプルではひび割れが発生し、接合強度が低下することが分かる。従って、熱膨張調整材の粒径が５μｍ未満では好ましくないことが分かる。
また、熱膨張調整材（アルミナ）の粒径が１５μｍより大きい比較例５では、接合材の焼結性が低下するので、接合強度が低下することが分かる。従って、熱膨張調整材の粒径が１５μｍより大きいと好ましくないことが分かる。
In Comparative Example 4 in which the particle size of the thermal expansion adjusting material (alumina) is less than 5 μm, the shrinkage rate of the joining member is increased, so that it can be seen that cracking occurs in the sample after air firing, and the joining strength is reduced. Therefore, it can be seen that the particle size of the thermal expansion adjusting material is less than 5 μm.
Further, in Comparative Example 5 in which the particle size of the thermal expansion adjusting material (alumina) is larger than 15 μm, it can be seen that the bonding strength decreases because the sintering property of the bonding material decreases. Therefore, it is understood that it is not preferable that the particle size of the thermal expansion adjusting material is larger than 15 μm.
また、実施例６〜８より、熱膨張係数が約８×１０−６／℃のアルミナだけでなく、約４×１０−６／℃の窒化ケイ素、約５×１０−６／℃の炭化ケイ素、約２×１０−６／℃のコージェライト等も良好な還元収縮防止効果を有する熱膨張調整材として機能することがわかる。 Further, from Examples 6 to 8, not only alumina having a thermal expansion coefficient of about 8 × 10 −6 / ° C., but also silicon nitride of about 4 × 10 −6 / ° C., silicon carbide of about 5 × 10 −6 / ° C. It can be seen that cordierite of about 2 × 10 −6 / ° C. functions as a thermal expansion adjusting material having a good effect of preventing reduction shrinkage.
実験例３
酸化ニッケル粉末および酸化マンガン粉末の粒径を表３に示すとおりに変え、アルミナ粉末の粒径を全て１０μｍとした以外は実験例２と同様の方法により、実施例９〜１１ならびに比較例７および８の接合材ペーストのサンプルを作製し、これを用いて、実験例１と同様の方法で接合部の接合強度を測定した。測定結果を表３に示す。
Experimental example 3
Examples 9 to 11 and Comparative Examples 7 and 7 were made in the same manner as in Experimental Example 2 except that the particle sizes of the nickel oxide powder and the manganese oxide powder were changed as shown in Table 3 and the particle size of the alumina powder was all 10 μm. A sample of 8 bonding material paste was prepared, and using this, the bonding strength of the bonded portion was measured in the same manner as in Experimental Example 1. Table 3 shows the measurement results.
酸化ニッケルの粒径が０．３μｍ未満の比較例７では、接合部材の収縮率が大きくなるので、大気焼成後サンプルではひび割れが発生し、接合強度が低下することが分かる。従って、酸化ニッケルの粒径が０．３μｍ未満では好ましくないことが分かる。
酸化ニッケルの粒径が５μｍより大きい比較例８では、接合材の焼結性が低下するので、接合強度が低下することが分かる。従って、酸化ニッケルの粒径が５μｍより大きいと好ましくないことが分かる。
In Comparative Example 7 in which the particle size of nickel oxide is less than 0.3 μm, the shrinkage rate of the joining member is increased, so that it can be seen that cracking occurs in the sample after air firing, and the joining strength is reduced. Therefore, it can be seen that the nickel oxide particle size is less than 0.3 μm.
In Comparative Example 8 in which the particle size of nickel oxide is larger than 5 μm, it can be seen that the bonding strength decreases because the sinterability of the bonding material decreases. Therefore, it is understood that it is not preferable that the particle diameter of nickel oxide is larger than 5 μm.
また、酸化マンガンの粒径が０．５μｍ未満の比較例７では、接合部材の収縮率が大きくなるので、大気焼成後サンプルではひび割れが発生し、接合強度が低下することが分かる。従って、酸化マンガンの粒径が０．５μｍ未満では好ましくないことが分かる。
酸化マンガンの粒径が５μｍより大きい比較例８では、接合材の焼結性が低下するので、接合強度が低下することが分かる。従って、酸化マンガンの粒径が５μｍより大きいと好ましくないことが分かる。
Further, in Comparative Example 7 in which the particle size of manganese oxide is less than 0.5 μm, the shrinkage rate of the joining member is increased, so that it can be seen that cracking occurs in the sample after air firing, and the joining strength is reduced. Therefore, it can be seen that the manganese oxide particle size is less than 0.5 μm.
In Comparative Example 8 in which the particle size of manganese oxide is larger than 5 μm, it can be seen that the bonding strength decreases because the sinterability of the bonding material decreases. Therefore, it is understood that it is not preferable that the particle size of manganese oxide is larger than 5 μm.
１１，１２，２１ 導電性接合部材
２，２３ 発電膜
３，１３ 燃料側電極
４，１４ 固体電解質膜
５，１５ 空気側電極
７，２２ インターコネクタ
11, 12, 21
Claims (13)
酸化ニッケルと、
酸化マンガンと
を、合計１００重量部含有するベース材料を含み、
前記酸化マンガンの量が２０重量部以上３０重量部以下である接合材。 It is a bonding material used in a reducing atmosphere,
Nickel oxide,
Including a base material containing a total of 100 parts by weight of manganese oxide;
A bonding material in which the amount of the manganese oxide is 20 parts by weight or more and 30 parts by weight or less.
該接合材を焼結する接合方法。 The bonding material according to any one of claims 1 to 5 is disposed between a plurality of members,
A joining method for sintering the joining material.
該複数の部材の間を接合する請求項６に記載の接合部材と
を有する固体電解質型燃料電池。 A plurality of members;
A solid oxide fuel cell comprising: a joining member according to claim 6 that joins the plurality of members.
酸化マンガンと With manganese oxide
を、合計１００重量部含有するベース材料を含み、A base material containing a total of 100 parts by weight,
前記酸化マンガンの量が２０重量部以上３０重量部以下である固体電解質型燃料電池用接合材。 A solid oxide fuel cell bonding material, wherein the amount of manganese oxide is 20 parts by weight or more and 30 parts by weight or less.
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