JP3534713B2 - Method for manufacturing ceramic manifold for solid oxide fuel cell - Google Patents
Method for manufacturing ceramic manifold for solid oxide fuel cellInfo
- Publication number
- JP3534713B2 JP3534713B2 JP2001114844A JP2001114844A JP3534713B2 JP 3534713 B2 JP3534713 B2 JP 3534713B2 JP 2001114844 A JP2001114844 A JP 2001114844A JP 2001114844 A JP2001114844 A JP 2001114844A JP 3534713 B2 JP3534713 B2 JP 3534713B2
- Authority
- JP
- Japan
- Prior art keywords
- sol
- manifold
- fuel cell
- mold
- ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000919 ceramic Substances 0.000 title claims description 18
- 239000000446 fuel Substances 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000007787 solid Substances 0.000 title claims description 3
- 238000000034 method Methods 0.000 title description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000002612 dispersion medium Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011819 refractory material Substances 0.000 claims description 3
- 229910021525 ceramic electrolyte Inorganic materials 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5031—Alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5035—Silica
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5042—Zirconium oxides or zirconates; Hafnium oxides or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
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（以下、「ＳＯＦＣ」と記載する。）等に使用でき
るマニホールドに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a manifold that can be used in a solid oxide fuel cell (hereinafter referred to as "SOFC") and the like.
【０００２】[0002]
【従来の技術】ＳＯＦＣに使用するセラミックスマニホ
ールドは、水素ガスや酸素ガスの出入りに用いられるも
のである。従来、このセラミックスマニホールドの製造
方法としては、セラミックス粉体を所定形状に成形した
後、熱処理（焼結）により緻密化する方法が知られてい
る。この場合、収縮により、成形時に比べて線方向の長
さが１０〜２０％小さくなり、変形などの原因となって
いる。2. Description of the Related Art Ceramic manifolds used in SOFCs are used for inflow and outflow of hydrogen gas and oxygen gas. Conventionally, as a method for manufacturing this ceramic manifold, a method is known in which ceramic powder is molded into a predetermined shape and then densified by heat treatment (sintering). In this case, due to the shrinkage, the length in the line direction becomes 10 to 20% smaller than that at the time of molding, which causes deformation and the like.
【０００３】そこで、所定形状に成形した後、１０００
℃以上で軽く熱処理してある程度の強度を発現したさせ
た後、ガスの透過を防止するために、表面にガラス粉末
等のコーティングを行い、表面の穴をつぶしてマニホー
ルドを製造する方法が行われている。この場合、収縮は
全くないか、あっても１％以下である。Therefore, after molding into a predetermined shape, 1000
After lightly heat treating at ℃ or above to develop a certain level of strength, in order to prevent gas permeation, the surface is coated with glass powder, etc. and the holes in the surface are crushed to produce a manifold. ing. In this case, there is no shrinkage or even 1% or less.
【０００４】しかし、ＳＯＦＣを考えた場合には、作動
温度は約１０００℃であり、水素ガス還元雰囲気下で
は、ガスの透過防止に用いられたガラスに含まれる酸化
物が還元されたり、ガラスの成分が蒸発することがあ
り、劣化の問題が生じている。However, in consideration of SOFC, the operating temperature is about 1000 ° C., and in a hydrogen gas reducing atmosphere, oxides contained in the glass used for preventing gas permeation are reduced, and the glass The components may evaporate, causing deterioration problems.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、水素ガス雰
囲気下においても劣化を生じず、ガスの透過を低下させ
たセラミックスマニホールドを提供する。SUMMARY OF THE INVENTION The present invention provides a ceramics manifold which does not deteriorate even in a hydrogen gas atmosphere and has reduced gas permeation.
【０００６】[0006]
【課題を解決するための手段】本発明は、セラミックス
のゾルを用いて表面処理を施したＳＯＦＣ用セラミック
スマニホールド及びこれを用いたＳＯＦＣを提供する。
また、本発明は、キャスタブル耐火物の粉体に分散媒を
添加し分散液を製造するステップと、該分散液を所定形
状の型に流し込んで成形するステップと、該型から取り
出して熱処理するステップと、セラミックスのゾルを用
いて表面処理を施すステップと、乾燥ステップとを含む
固定電解質型燃料電池用セラミックスマニホールドの製
造方法を提供する。The present invention provides a ceramics manifold for SOFC which is surface-treated with a sol of ceramics, and an SOFC using the same.
Further, the present invention provides a step of adding a dispersion medium to the powder of castable refractory to produce a dispersion, a step of casting the dispersion into a mold having a predetermined shape, and a step of taking it out from the mold and subjecting it to heat treatment. And a method of manufacturing a ceramic manifold for a fixed electrolyte fuel cell, which includes a step of performing a surface treatment using a ceramic sol and a drying step.
【０００７】[0007]
【発明の実施の形態】本発明に用いるセラミックスマニ
ホールドは、例えば、キャスタブル耐火物の粉体に、分
散媒を添加することにより流動性を付与し、所定形状の
型に流し込んで固化、成形した後、型から取り出し、強
度付与のため、収縮を生じない程度の温度（１０００℃
以上、好ましくは１０００〜１３００℃）で熱処理した
ものである。即ち、このままでは多孔質である成形体で
ある。キャスタブル耐火物としては、マグネシアとシリ
カとスピネルとアルミナセメントの混合物等が挙げられ
る。分散媒としては、粉体を分散できるものであれば特
に限定しないが、環境面から水が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The ceramics manifold used in the present invention is made, for example, by adding a dispersion medium to powder of a castable refractory material to give fluidity, and then pouring it into a mold of a predetermined shape to solidify and mold it. , Take it out of the mold and give it strength so that it will not shrink (1000 ° C).
Above, it heat-processed at 1000-1300 degreeC preferably. That is, it is a molded body that is porous as it is. Examples of castable refractories include a mixture of magnesia, silica, spinel, and alumina cement. The dispersion medium is not particularly limited as long as it can disperse the powder, but water is preferable from the viewpoint of environment.
【０００８】本発明に用いるセラミックスマニホールド
は、そのままでは数ミクロンから数十ミクロンの孔を有
する多孔質であるため、ゾルを用いて表面の穴をつぶ
し、ガスの透過を防止する。本発明で用いるセラミック
スのゾルとしては、多孔質の成形体の孔をふさぎ、１０
００℃においても劣化しない耐熱性を有するものであれ
ば特に限定しない。多孔質の成形体の孔はミクロンから
数十ミクロンであるため、ゾルは、これより小さい粒子
が分散された液であれば良いが、好ましくは、１００〜
１０００オングストロームの粒子が分散された液であ
る。ゾルとしては、シリカゾル、アルミナゾル、ジルコ
ニアゾル、チタニアゾル等が挙げられるが、入手の容易
さ及びコスト面において、好ましくは、シリカゾル、ア
ルミナゾル又はジルコニアゾルである。ゾルの濃度とし
ては２０〜５０重量％が好ましく、濃度が低すぎると塗
布を繰り返す回数が増加することとなり不都合であり、
濃度が高すぎるとゾルの安定性が低下し、凝集するおそ
れがある。シリカゾル、アルミナゾル、ジルコニアゾル
は、例えば日産化学社から市販されている。Since the ceramics manifold used in the present invention is porous having pores of several microns to several tens of microns as it is, the holes on the surface are crushed by using sol to prevent gas permeation. As the ceramic sol used in the present invention, the pores of a porous molded body are filled with 10
There is no particular limitation as long as it has heat resistance that does not deteriorate even at 00 ° C. Since the pores of the porous molded body are from micron to several tens of microns, the sol may be a liquid in which smaller particles are dispersed, but preferably 100 to
It is a liquid in which 1000 angstrom particles are dispersed. Examples of the sol include silica sol, alumina sol, zirconia sol, titania sol, and the like, and silica sol, alumina sol, or zirconia sol is preferable in terms of availability and cost. The concentration of the sol is preferably 20 to 50% by weight, and if the concentration is too low, the number of times of repeating coating is increased, which is inconvenient.
If the concentration is too high, the stability of the sol may be reduced and there is a risk of aggregation. Silica sol, alumina sol, and zirconia sol are commercially available from Nissan Chemical Co., Ltd., for example.
【０００９】ゾルの塗布方法は、特に限定されないが、
例えばセラミックスマニホールドをゾル中に含浸させる
含浸法が挙げられる。ゾルの塗布後は、自然乾燥や昇温
して乾燥する。セラミックスマニホールドの孔を塞ぐた
めに必要であれば、ゾルの塗布と乾燥を繰り返す。セラ
ミックスマニホールドの多孔度に依存するが、通常は、
乾燥後の膜厚で５〜５０μｍとなるようにすることが好
ましい。The method of applying the sol is not particularly limited,
For example, an impregnation method of impregnating a sol with a ceramics manifold can be mentioned. After application of the sol, it is dried naturally or by raising the temperature. If necessary to close the holes in the ceramics manifold, the application and drying of the sol is repeated. Depending on the porosity of the ceramic manifold,
It is preferable that the film thickness after drying is 5 to 50 μm.
【００１０】ゾルによる表面処理後に、更にガラス粉等
の粉を塗布する表面処理により表面の平滑化及び緻密化
を行ってもよい。マニホールドが水素ガスの出入りに用
いられる場合には、前記のような還元反応による劣化の
問題が生ずるため好ましくないが、酸素ガスの出入りに
用いられる場合には劣化の問題が生じないからである。After the surface treatment with the sol, the surface may be smoothed and densified by further applying a powder such as glass powder. When the manifold is used for inflow and outflow of hydrogen gas, it is not preferable because it causes the deterioration problem due to the reduction reaction as described above, but when it is used for inflow and outflow of oxygen gas, the deterioration problem does not occur.
【００１１】[0011]
【実施例】以下、本発明を実施例に基づき説明するが、
本発明はこれに限定されるものではない。
実施例１
マニホールドを形成するための材料として、熱膨張係数
が１０．２×１０-6／℃に適合し、粒径が３ｍｍ、１ｍ
ｍ、１００μｍ及び１〜１０μｍで構成されている水硬
性キャスタブル材料を用いて、直径３ｃｍ厚さ５ｍｍの
円板を成形した。この円板を１２００℃にて４時間熱処
理した。この材料の平均熱膨張係数は、１０．２×１０
-6／℃で目標と一致していた。また、水銀圧入法による
細孔は、平均細孔径が０．５μｍ、細孔容積が０．１５
ｃｃ／ｇであった。このサンプルを、シリカゾル（粒子
径０．０３μｍ）への浸漬、引き上げた後の乾燥を３回
繰り返し、１０００℃で熱処理した。このときの細孔
は、平均細孔径が０．０５μｍ、細孔容積が０．０３ｃ
ｃ／ｇと処理前に比べ、細孔径が大幅に小さくなると同
時に、細孔容積も大幅に減少した。両者のサンプルで空
気の透過速度を測定したところ、処理前のものが５×１
０0cm3／cm2・cmHgであったのに対し、処理後が３×１０
-4cm3／cm2・cmHgとガス透過速度は1/10000程度と大幅に
低下していた。EXAMPLES The present invention will be described below based on examples.
The present invention is not limited to this. Example 1 As a material for forming a manifold, the coefficient of thermal expansion is 10.2 × 10 −6 / ° C. and the particle size is 3 mm and 1 m.
A disc having a diameter of 3 cm and a thickness of 5 mm was formed by using a hydraulic castable material composed of m, 100 μm, and 1 to 10 μm. This disc was heat-treated at 1200 ° C. for 4 hours. The average coefficient of thermal expansion of this material is 10.2 × 10
It was in agreement with the target at -6 / ℃. The pores obtained by the mercury intrusion method have an average pore diameter of 0.5 μm and a pore volume of 0.15.
It was cc / g. This sample was immersed in silica sol (particle diameter 0.03 μm), pulled up and then dried 3 times, and heat-treated at 1000 ° C. The pores at this time have an average pore diameter of 0.05 μm and a pore volume of 0.03 c.
Compared with c / g, the pore diameter was significantly reduced and the pore volume was also significantly reduced. When the air permeation rate of both samples was measured, it was 5 × 1 before the treatment.
Although it was 0 cm 3 / cm 2 · cmHg, it was 3 × 10 after the treatment.
The gas permeation rate of -4 cm 3 / cm 2 · cmHg was significantly reduced to about 1/10000.
【００１２】[0012]
【発明の効果】ゾルの表面処理を施したＳＯＦＣ用のマ
ニホールドは、ゾルが細孔内でゲル化し細孔内を詰める
ことにより、ガスの透過を低下させることができる。ま
た、水素ガス還元下での劣化の問題も生じない。INDUSTRIAL APPLICABILITY In the SOFC manifold in which the surface treatment of the sol is performed, the sol gels in the pores and fills the pores, whereby the gas permeation can be reduced. Further, the problem of deterioration under hydrogen gas reduction does not occur.
Claims (2)
加し分散液を製造するステップと、該分散液を所定形状
の型に流し込んで成形するステップと、該型から取り出
して熱処理するステップと、セラミックスのゾルを用い
て表面処理を施すステップと、乾燥ステップとを含む固
体電解質型燃料電池用セラミックスマニホールドの製造
方法。1. A dispersion medium is added to powder of castable refractory material.
And a step of producing a dispersion liquid, and forming the dispersion liquid into a predetermined shape.
Pour into the mold to mold and remove from the mold
And heat treatment step, and using ceramic sol
Surface treatment, and a drying step.
Of ceramics manifold for solid electrolyte fuel cell
Way .
とアルミナゾルとジルコニアゾルとからなる一群から選
ばれる請求項１に記載の固体電解質型燃料電池用セラミ
ックスマニホールドの製造方法。2. The ceramic sol is silica sol.
Selected from the group consisting of alumina sol and zirconia sol
A ceramic electrolyte for a solid oxide fuel cell according to claim 1.
Manufacturing method for a x-manifold .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001114844A JP3534713B2 (en) | 2001-04-13 | 2001-04-13 | Method for manufacturing ceramic manifold for solid oxide fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2001114844A JP3534713B2 (en) | 2001-04-13 | 2001-04-13 | Method for manufacturing ceramic manifold for solid oxide fuel cell |
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| Publication Number | Publication Date |
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| JP2002313368A JP2002313368A (en) | 2002-10-25 |
| JP3534713B2 true JP3534713B2 (en) | 2004-06-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001243966A (en) | 2000-02-02 | 2001-09-07 | Haldor Topsoe As | Solid oxide fuel cell |
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| JP2001243966A (en) | 2000-02-02 | 2001-09-07 | Haldor Topsoe As | Solid oxide fuel cell |
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