JP2009009802A5 - - Google Patents
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- JP2009009802A5 JP2009009802A5 JP2007169472A JP2007169472A JP2009009802A5 JP 2009009802 A5 JP2009009802 A5 JP 2009009802A5 JP 2007169472 A JP2007169472 A JP 2007169472A JP 2007169472 A JP2007169472 A JP 2007169472A JP 2009009802 A5 JP2009009802 A5 JP 2009009802A5
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- metal member
- brazing material
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これに対して、ロウ付けは、強度が高く温度サイクルにも強く、理想的な接合方法である。このロウ付け法のうち、固体酸化物形燃料電池を対象とした技術が開示されている（特許文献１参照）。 On the other hand, brazing is an ideal joining method because it is strong and resistant to temperature cycles. Among the brazing method, is shown technology is opened intended for solid oxide fuel cell (see Patent Document 1).
また、酸素分圧を１０-5〜１０-20ａｔｍとした雰囲気で、金属酸化物を還元し、メタライズ処理した後に接合する技術が開示されている（特許文献２参照）。
更に、ロウ材として、Ａｇ−ＣｕＯ、Ａｇ−Ｖ2Ｏ5、Ｐｔ−Ｎｂ2Ｏ5などを用い、セルとＡｌ酸化被膜を形成した耐熱合金とを、大気雰囲気にて接合する技術が開示されている（特許文献３参照）。
In addition, a technique is disclosed in which a metal oxide is reduced and metallized in an atmosphere with an oxygen partial pressure of 10 −5 to 10 −20 atm (see Patent Document 2).
Furthermore, a technique is disclosed in which Ag—CuO, Ag—V 2 O 5 , Pt—Nb 2 O 5 or the like is used as a brazing material, and a cell and a heat-resistant alloy formed with an Al oxide film are joined in an air atmosphere. (See Patent Document 3).
しかしながら、前記特許文献１及び特許文献２の技術では、ペロブスカイト型酸化物である空気極が分解し、性能が劣化するという問題があった。 However, in the technique of Patent Document 1 and Patent Document 2, and the air electrode degradation is perovskite-type oxide, there is a problem that the performance is degraded.
また、特許文献３の技術では、大気雰囲気で接合を行っているものの、Ａｌ酸化皮膜を形成する合金とセルとの接合は、Ａｌ酸化被膜と合金との密着性が悪く、十分な接合強度が得られないという問題があった。更に、報告されているＣｕＯを添加したＡｇロウ材では、Ｃｒ酸化被膜を形成する合金を接合した場合、合金表面に形成されたＣｒ酸化被膜と添加物であるＣｕＯとによって、低融点の化合物を生成するため、その合金（金属部材）が腐食するという問題があった。 Further, in the technique of Patent Document 3, although bonding is performed in an air atmosphere, the bonding between the alloy forming the Al oxide film and the cell has poor adhesion between the Al oxide film and the alloy, and sufficient bonding strength is obtained. There was a problem that it could not be obtained. Furthermore, in the reported Ag brazing material to which CuO is added, when an alloy forming a Cr oxide film is joined, a compound having a low melting point is formed by the Cr oxide film formed on the alloy surface and the additive CuO. As a result, the alloy (metal member) corroded.
（１）請求項１の発明は、金属部材とセラミックス体とを、又は前記金属部材同士を、主としてＡｇ（銀）ロウ材からなる接合部にて接合した固体電解質形燃料電池において、前記金属部材の前記接合部側の表面に、Ｃｒ酸化物被膜又はＡｌ酸化物被膜が形成されており、前記接合部のＡｇロウ材中に、Ｎｉ、Ｃｏ、Ｃｒ、Ｔｉ、Ｃｅ、Ｓｒ、Ｍｎ、Ｌａ、Ｓｍ、及びＹの各元素の酸化物のうち、少なくとも１種を含むことを特徴とする。 (1) The invention according to claim 1, and a metal member and the ceramic member, or the metal members to each other, mainly in the Ag (silver) hand contact combined solid oxide fuel cell to the junction comprising a brazing material, the metal A Cr oxide film or an Al oxide film is formed on the surface of the member on the joint portion side , and Ni, Co, Cr, Ti, Ce, Sr, Mn, La are formed in the Ag brazing material of the joint portion. It contains at least 1 sort (s) among the oxides of each element of S, Sm, and Y.
高い強度を得るためには、前記特許文献１、２の技術による接合は有効であるが、空気極の性能劣化が生じるため、固体電解質形燃料電池の接合方法としては、不適切であったが、本発明のように、特定の酸化物を含んだＡｇロウ材を用いることで、大気雰囲気でロウ付けを行った場合でも、金属部材の腐蝕も生じず、高い接合強度を得ることができる。
つまり、本発明では、特定の酸化物を含んだＡｇロウ材を用いることにより、大気雰囲気でロウ付けを行った場合でも、空気極の性能が劣化するといった金属部材の腐蝕も生じず、高い接合強度を得ることができる。
In order to obtain a high strength, but joining by techniques of the Patent Documents 1 and 2 is effective, since the sexual performance degradation of the air electrode occurs, as a joining method of a solid electrolyte fuel cell was inadequate but, as in the present invention, by using the Ag brazing material containing an oxide of a specific, even when a brazing in the atmosphere, does not occur even corrosion of the metal member, it is possible to obtain a high bonding strength it can.
That is, in the present invention, by using the Ag brazing material containing an oxide of a specific, even when a brazed in an air atmosphere, also not occur corrosion of metal members such as the performance of the air electrode is deteriorated, high Bonding strength can be obtained.
なお、Ａｇロウ材とは、Ａｇを主成分とするロウ材である。
しかも、本発明では、金属部材の表面にＣｒ酸化物被膜が形成される場合でも、効果的に金属部材の腐食を防止できる。また、金属部材の表面にＡｌ酸化物被膜が形成される場合でも、高い接合強度を確保できる。
（２）請求項２の発明は、前記金属部材は、Ｃｒ又はＡｌを含む合金であることを特徴とする。
本発明では、ロウ付けされる金属部材を例示している。
（３）請求項３の発明では、前記接合部のＡｇロウ材中に存在する前記酸化物の体積比が、全Ａｇロウ材中の２０％以下であることを特徴とする。
The Ag brazing material is a brazing material mainly composed of Ag.
Moreover, in the present invention, even when a Cr oxide film is formed on the surface of the metal member, corrosion of the metal member can be effectively prevented. Moreover, even when an Al oxide film is formed on the surface of the metal member, high bonding strength can be ensured.
(2) The invention of claim 2 is characterized in that the metal member is an alloy containing Cr or Al.
In the present invention, the metal member to be brazed is illustrated.
( 3 ) The invention of claim 3 is characterized in that the volume ratio of the oxide present in the Ag brazing material of the joint is 20% or less of the total Ag brazing material.
（４）請求項４の発明は、前記請求項１〜３のいずれか１項に記載の固体電解質形燃料電池の製造方法であって、Ｃｒ又はＡｌを含有する前記金属部材を用意する工程と、大気雰囲気中で、前記金属部材の前記接合部側の表面にＣｒ酸化物被膜又はＡｌ酸化物被膜を生成すると共に、前記Ａｇロウ材を用いて前記金属部材と前記セラミックス体とを、又は前記金属部材同士を接合する工程と、を有することを特徴とする。 (4) The invention according to claim 4, a method for producing a solid electrolyte fuel cell according to any one of the claims 1-3, comprising the steps of preparing the metal member containing Cr or Al In addition, in the air atmosphere , a Cr oxide film or an Al oxide film is formed on the surface of the metal member on the joint portion side, and the metal member and the ceramic body are formed using the Ag brazing material, or A step of joining metal members to each other .
そして、このように組み付けた構成を、大気中で加熱した後に冷却して、ロウ付け接合により一体化し、固体電解質形燃料電池スタック１を完成した。
従って、本実施形態では、特定の酸化物を含んだＡｇロウ材を用いることで、大気雰囲気でロウ付けを行った場合でも、金属部材の腐蝕も生じず、高い接合強度を得ることができる。
The assembled structure was heated in the air and then cooled and integrated by brazing to complete the solid oxide fuel cell stack 1.
Therefore , in this embodiment, by using an Ag brazing material containing a specific oxide, even when brazing is performed in an air atmosphere, the metal member is not corroded, and high bonding strength can be obtained.
それに対して、比較例２では、Ａｇロウ内に、本発明の酸化物を含まないので、接合面の剥離荷重が小さく、接合強度が低いので好ましくない。
つまり、全ての実施例おいて、Ａｇロウ材のみの無添加品に対して、接合強度の向上が見られた。また、その中でも、特に、Ｎｉ、Ｃｒ、Ｔｉ、Ｃｏの各酸化物を添加することにより、より接合強度を高くすることができる。更に、酸化物の添加量は、２０体積％以下の場合には、接合強度が高く好適である。しかも、金属部材として、Ｃｒ酸化物形成合金を用いると、接合強度が高まることが分かる。
On the other hand, in Comparative Example 2 , since the oxide of the present invention is not included in the Ag brazing, the peeling load on the bonding surface is small and the bonding strength is low, which is not preferable.
That is, in all of the examples, an improvement in bonding strength was observed with respect to the additive-free product containing only the Ag brazing material. Among these, in particular, the addition of Ni, Cr, Ti, and Co oxides can further increase the bonding strength. Furthermore, when the addition amount of the oxide is 20% by volume or less, it is preferable because the bonding strength is high. Moreover, it can be seen that when a Cr oxide-forming alloy is used as the metal member, the bonding strength is increased.
具体的には、テストピースを図６の上下方向に切断し、その接合部分における切断面をＳＥＭにて観察した。また、ＥＤＳにて、その切断面に露出したロウ材の表面の界面層の組成の分析を行った。これによって、金属部材の腐食の有無を調べた。その結果を、前記表１及び表２に示す。 Specifically, the test piece was cut in the vertical direction of FIG. 6, and the cut surface at the joint was observed with an SEM. Further, the composition of the interface layer on the surface of the brazing material exposed on the cut surface was analyzed by EDS. Thereby, the presence or absence of corrosion of the metal member was examined. The results are shown in Table 1 and Table 2.
Claims (4)
前記金属部材の前記接合部側の表面に、Ｃｒ酸化物被膜又はＡｌ酸化物被膜が形成されており、
前記接合部のＡｇロウ材中に、Ｎｉ、Ｃｏ、Ｃｒ、Ｔｉ、Ｃｅ、Ｓｒ、Ｍｎ、Ｌａ、Ｓｍ、及びＹの各元素の酸化物のうち、少なくとも１種を含むことを特徴とする固体電解質形燃料電池。 A metal member and the ceramic member, or the metal members to each other, in the hand against combined solid oxide fuel cell to the junction mainly composed of Ag brazing material,
A Cr oxide film or an Al oxide film is formed on the surface of the metal member on the joint portion side,
A solid material characterized in that the Ag brazing material of the joint contains at least one of oxides of each element of Ni, Co, Cr, Ti, Ce, Sr, Mn, La, Sm, and Y. Electrolytic fuel cell.
Ｃｒ又はＡｌを含有する前記金属部材を用意する工程と、
大気雰囲気中で、前記金属部材の前記接合部側の表面にＣｒ酸化物被膜又はＡｌ酸化物被膜を生成すると共に、前記Ａｇロウ材を用いて前記金属部材と前記セラミックス体とを、又は前記金属部材同士を接合する工程と、
を有することを特徴とする固体電解質形燃料電池の製造方法。 The method of manufacturing a solid electrolyte fuel cell according to any one of claims 1 to 3,
Preparing the metal member containing Cr or Al;
In the air atmosphere , a Cr oxide film or an Al oxide film is formed on the surface of the metal member on the joint portion side, and the metal member and the ceramic body are formed using the Ag brazing material, or the metal A step of joining members together;
A method for producing a solid oxide fuel cell, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007169472A JP5242952B2 (en) | 2007-06-27 | 2007-06-27 | Solid electrolyte fuel cell and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2007169472A JP5242952B2 (en) | 2007-06-27 | 2007-06-27 | Solid electrolyte fuel cell and manufacturing method thereof |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2011254154A Division JP5432231B2 (en) | 2011-11-21 | 2011-11-21 | Joining member for solid oxide fuel cell |
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| Publication Number | Publication Date |
|---|---|
| JP2009009802A JP2009009802A (en) | 2009-01-15 |
| JP2009009802A5 true JP2009009802A5 (en) | 2012-01-12 |
| JP5242952B2 JP5242952B2 (en) | 2013-07-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2007169472A Expired - Fee Related JP5242952B2 (en) | 2007-06-27 | 2007-06-27 | Solid electrolyte fuel cell and manufacturing method thereof |
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Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008013281A1 (en) * | 2008-03-08 | 2009-09-17 | Forschungszentrum Jülich GmbH | Sealing arrangement for high temperature fuel cell stacks |
| JP5268717B2 (en) * | 2009-03-10 | 2013-08-21 | 日本発條株式会社 | Brazing material and bonded body for air bonding |
| JP5405200B2 (en) * | 2009-06-11 | 2014-02-05 | 日本電信電話株式会社 | Solid oxide fuel cell and method for producing the same |
| JP2012532022A (en) * | 2009-07-10 | 2012-12-13 | セラミック・フューエル・セルズ・リミテッド | Brazing method |
| JP5483714B2 (en) * | 2009-08-26 | 2014-05-07 | 日本碍子株式会社 | Bonding agent |
| JP5591743B2 (en) * | 2011-03-11 | 2014-09-17 | 日本特殊陶業株式会社 | Solid oxide fuel cell |
| JP5897552B2 (en) * | 2011-03-25 | 2016-03-30 | 日本碍子株式会社 | Tungsten carbide-based cemented carbide joined body and manufacturing method thereof |
| JP5705636B2 (en) * | 2011-04-26 | 2015-04-22 | 日本特殊陶業株式会社 | Solid oxide fuel cell |
| JP5727428B2 (en) * | 2012-08-31 | 2015-06-03 | 日本特殊陶業株式会社 | Fuel cell with separator and fuel cell |
| JP5727429B2 (en) * | 2012-08-31 | 2015-06-03 | 日本特殊陶業株式会社 | Fuel cell with separator and fuel cell |
| US10122023B2 (en) | 2012-08-31 | 2018-11-06 | Ngk Spark Plug Co., Ltd. | Fuel cell with separator, method for manufacturing same, and fuel cell stack |
| JP5727431B2 (en) * | 2012-08-31 | 2015-06-03 | 日本特殊陶業株式会社 | Fuel cell with separator and fuel cell |
| JP5727432B2 (en) * | 2012-08-31 | 2015-06-03 | 日本特殊陶業株式会社 | Fuel cell with separator, method for manufacturing the same, and fuel cell stack |
| JP5727430B2 (en) * | 2012-08-31 | 2015-06-03 | 日本特殊陶業株式会社 | Fuel cell with separator and fuel cell |
| JP6013304B2 (en) * | 2013-10-29 | 2016-10-25 | 日本特殊陶業株式会社 | Fuel cell single cell with separator and fuel cell stack |
| JP6118230B2 (en) * | 2013-10-30 | 2017-04-19 | 日本特殊陶業株式会社 | Fuel cell stack |
| JP6231388B2 (en) * | 2014-01-07 | 2017-11-15 | 日本特殊陶業株式会社 | Fuel cell cassette and fuel cell stack |
| CA2936662C (en) | 2014-01-15 | 2018-06-26 | Ngk Spark Plug Co., Ltd. | Fuel cell cassette and fuel cell stack |
| JP6100291B2 (en) | 2014-01-23 | 2017-03-22 | 日本特殊陶業株式会社 | FUEL CELL CASSETTE, ITS MANUFACTURING METHOD, FUEL CELL STACK |
| KR101670800B1 (en) * | 2014-08-27 | 2016-10-31 | 한국에너지기술연구원 | Unit cell for solid oxide fuel cell and manufacturing method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63154290A (en) * | 1986-08-29 | 1988-06-27 | Mitsubishi Steel Mfg Co Ltd | Low melting silver brazing filler metal |
| JPH01313198A (en) * | 1988-06-10 | 1989-12-18 | Mitsubishi Steel Mfg Co Ltd | Low melting low silver brazing filler metal |
| JPH06172989A (en) * | 1992-12-09 | 1994-06-21 | Canon Inc | Metal oxide film forming method |
| JP2006172989A (en) * | 2004-12-17 | 2006-06-29 | Ngk Spark Plug Co Ltd | Solid electrolyte fuel battery cell and solid electrolyte fuel battery using it and its manufacturing method |
| JP5204958B2 (en) * | 2006-06-19 | 2013-06-05 | 日本発條株式会社 | Zygote |
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