JPH1021934A - Electrode for fuel cell - Google Patents
Electrode for fuel cellInfo
- Publication number
- JPH1021934A JPH1021934A JP8188081A JP18808196A JPH1021934A JP H1021934 A JPH1021934 A JP H1021934A JP 8188081 A JP8188081 A JP 8188081A JP 18808196 A JP18808196 A JP 18808196A JP H1021934 A JPH1021934 A JP H1021934A
- Authority
- JP
- Japan
- Prior art keywords
- ysz
- electrode
- porous layer
- dense
- film
- 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.)
- Withdrawn
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
- Inert Electrodes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は燃料電池用電極に
関し、特に高温固体電解質型水蒸気電解用カソード電極
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell electrode, and more particularly to a cathode electrode for high temperature solid electrolyte type steam electrolysis.
【０００２】[0002]
【従来の技術】周知の如く、高温固体電解質型水蒸気電
解装置（以下、ＳＯＥと呼ぶ）は、主としてイットリア
安定化ジルコニア（以下、ＹＳＺと呼ぶ）緻密膜を固体
電解質として用いる。そして、その固体電解質の片側に
カソード電極（以下、水素電極と呼ぶ）として重量比７
０／３０〜６０／４０のニッケル−ＹＳＺ混合スラリー
を１３００〜１５００℃で焼成してコーティングし、も
う一方に白金ペーストあるいはＬａ1-x Ｓｒx ＭｎＯ3
（ｘ＝０〜１）（以下、ＬＳＭと呼ぶ）等の電子電導性
ペロブスカイト型酸化物スラリーを１１００〜１３００
℃で焼成してアノード電極（以下、酸素電極と呼ぶ）と
し、これを９００〜１０００℃に保持してカソード側に
水蒸気を送り電解することによって水素を得る構成を有
する。2. Description of the Related Art As is well known, a high temperature solid electrolyte type steam electrolyzer (hereinafter referred to as SOE) mainly uses a dense membrane of yttria-stabilized zirconia (hereinafter referred to as YSZ) as a solid electrolyte. Then, one side of the solid electrolyte is used as a cathode electrode (hereinafter referred to as a hydrogen electrode) at a weight ratio of 7%.
A nickel / YSZ mixed slurry of 0 / 30-60 / 40 is fired and coated at 1300-1500 ° C., and platinum paste or La 1-x Sr x MnO 3 is coated on the other.
(X = 0 to 1) (hereinafter, referred to as LSM) such as 1100 to 1300
The anode electrode (hereinafter, referred to as an oxygen electrode) is fired at a temperature of 900 ° C., which is maintained at 900 to 1000 ° C., and steam is sent to the cathode side to perform electrolysis, thereby obtaining hydrogen.
【０００３】また、得られた水素を用いて電流を取り出
すことにより、燃料電池として機能する。こうした構成
の水蒸気電解装置により、夜間の電力を用いて水素を製
造して昼間の電力ピーク時にその水素を用いて発電する
ことにより、供給電力の平準化を図ることができる。[0003] In addition, a current is taken out using the obtained hydrogen to function as a fuel cell. By using the steam electrolysis apparatus having such a configuration, hydrogen is produced using nighttime electric power, and power is generated using the hydrogen during the daytime electric power peak, thereby making it possible to level the supplied electric power.
【０００４】[0004]
【発明が解決しようとする課題】ところで、水蒸気電解
は吸熱反応であり、燃料電池として発電すると発熱反応
が生じる。本水蒸気電解装置を用いて電解操作と発電操
作の交互運転を繰り返すと、水素電極（電解操作時のカ
ソード電極）で吸熱・発熱が繰り返される。水素電極は
ＮｉとＹＳＺのサーメット（膜厚２０〜６０μｍ）であ
り、ＹＳＺより熱膨脹係数が大きく、水素極の吸熱・発
熱反応に伴い剥離応力が発生し、性能劣化ひいては水素
極／ＹＳＺ緻密膜界面で剥離に到るという問題点があっ
た。Incidentally, steam electrolysis is an endothermic reaction, and an exothermic reaction occurs when power is generated as a fuel cell. When the alternating operation of the electrolysis operation and the power generation operation is repeated using the present steam electrolysis apparatus, heat absorption and heat generation are repeated at the hydrogen electrode (the cathode electrode during the electrolysis operation). The hydrogen electrode is a cermet of Ni and YSZ (film thickness: 20 to 60 μm), has a larger coefficient of thermal expansion than YSZ, generates peeling stress due to endothermic and exothermic reactions of the hydrogen electrode, and deteriorates the performance. This causes a problem of delamination.
【０００５】図４は時間と抵抗との関係を特性図であ
り、３回目の交互運転後に剥離が生じてセル抵抗が上昇
した例を示す。具体的には、図４はＳＯＥ／ＳＯＦＣリ
バーシブル運転（４５０ｍＡｃｍ-2）に伴うセル抵抗の
経時変化を示し、条件は温度：１０００℃、水素流量：
１５０ｃｃ／ｍｉｎ、酸素流量：７５ｃ／ｍｉｎ、水蒸
気流量：０．１３ｇ／ｍｉｎである。FIG. 4 is a characteristic diagram showing the relationship between time and resistance, and shows an example in which peeling has occurred after the third alternate operation and the cell resistance has increased. Specifically, FIG. 4 shows a change with time of the cell resistance due to the SOE / SOFC reversible operation (450 mAcm −2 ).
150 cc / min, oxygen flow rate: 75 c / min, steam flow rate: 0.13 g / min.
【０００６】従来のＮｉ／ＹＳＺサーメットは、ＮｉＯ
とＹＳＺの原料粉末を重量比にしてＮｉＯ／ＹＳＺ＝５
／５以上７／３以下で混ぜ合わせたスラリーを焼成した
ものであり、Ｎｉが骨格を形成している。このため、Ｙ
ＳＺと熱膨脹率が大きく異なり、ＮｉＯ／ＹＳＺの重量
比を５／５未満にすると電子導電性が失なわれる為、そ
の一致化は不可能であった。A conventional Ni / YSZ cermet is NiO
And the raw material powder of YSZ is expressed by a weight ratio of NiO / YSZ = 5.
This is obtained by firing a slurry mixed at a ratio of / 5 or more to 7/3 or less, and Ni forms a skeleton. For this reason, Y
Since the thermal expansion coefficient is significantly different from that of SZ, and if the weight ratio of NiO / YSZ is less than 5/5, the electronic conductivity is lost, and it is impossible to make the same.
【０００７】また、ＮｉＯ／ＹＳＺが７／３を越える
と、高温（９００〜１０００℃）水素雰囲気でＮｉの凝
集が生じて性能劣化を生じるため、横流れ導電率の上限
は約２０００Ｓｃｍ-1（at１０００℃）であった。On the other hand, if NiO / YSZ exceeds 7/3, the agglomeration of Ni occurs in a high-temperature (900 to 1000 ° C.) hydrogen atmosphere to deteriorate the performance. Therefore, the upper limit of the lateral flow conductivity is about 2000 Scm −1 (at 1000 ° C).
【０００８】この発明はこうした事情を考慮してなされ
たもので、ＹＳＺからなる多孔質層からＹＳＺ緻密膜に
向ってＮｉ／ＹＳＺ比が減少する傾斜構造とすることに
より、電解操作と発電操作を繰り返しても、水素極／Ｙ
ＳＺ緻密膜界面で剥離の生じない燃料電池用電極を提供
することを目的とする。The present invention has been made in view of such circumstances, and has a gradient structure in which the Ni / YSZ ratio decreases from a porous layer made of YSZ toward a dense YSZ film, so that the electrolytic operation and the power generation operation can be performed. Even if repeated, hydrogen electrode / Y
An object of the present invention is to provide an electrode for a fuel cell in which peeling does not occur at the interface of the SZ dense film.
【０００９】[0009]
【課題を解決するための手段】この発明は、イットリア
安定化ジルコニア緻密膜とこの緻密膜上にイットリア安
定化ジルコニアスラリーの塗布，焼成によって形成され
た多孔質層からなり、Ｎｉが前記緻密膜及び多孔質層に
含浸析出され、前記多孔質層から緻密膜に向かってＮｉ
／イットリア安定化ジルコニア比が減少する傾斜構造を
有することを特徴とする燃料電池用電極である。SUMMARY OF THE INVENTION The present invention provides a dense yttria-stabilized zirconia film and a porous layer formed by applying and firing a yttria-stabilized zirconia slurry on the dense film. The porous layer is impregnated and deposited, and Ni is deposited from the porous layer toward the dense film.
An electrode for a fuel cell, characterized by having an inclined structure in which the ratio of zirconia / yttria stabilized decreases.
【００１０】この発明に係る燃料電池用電極は、次のよ
うにして作られる。即ち、この発明に係る電極は、イッ
トリア安定化ジルコニア（ＹＳＺ）緻密膜上にＹＳＺス
ラリーを塗布し、焼成することによって多孔質層を形成
した後、無電解メッキ法よりＮｉを多孔質層に含浸析出
させることにより、ＹＳＺ緻密膜に向ってＮｉ／ＹＳＺ
が減少する傾斜構造を有するようにすることにより作
る。The electrode for a fuel cell according to the present invention is manufactured as follows. That is, in the electrode according to the present invention, a porous layer is formed by applying a YSZ slurry on a dense yttria-stabilized zirconia (YSZ) film and firing it, and then impregnating the porous layer with Ni by electroless plating. By depositing, Ni / YSZ toward the YSZ dense film
Is made by having a sloped structure that reduces.
【００１１】具体的には、例えば次のようにして作る。
まず、２００〜５００μｍのＹＳＺ緻密膜上に、粒径１
〜１０μｍのＹＳＺを有機樹脂に混合分散させたものを
スクリーンプリントし、１１００〜１４００℃で１〜２
時間焼成して膜厚３０〜５０μｍのＹＳＺ多孔体をコー
ティングする。その後、ＳｎＣｌ2 溶液に数分間、Ｐｄ
Ｃｌ2 溶液に数分間つけて触媒化した後、メッキ浴（下
記Ａ液とＢ液を混合したもの）に、９５℃で１０〜２０
分間メッキ処理を行ない、ＹＳＺ多孔体中にＮｉを拡散
析出させる。Specifically, for example, it is made as follows.
First, on a YSZ dense film of 200 to 500 μm, a particle size of 1
YSZ of 10 to 10 μm mixed and dispersed in an organic resin is screen-printed, and is printed at 1100 to 1400 ° C. for 1 to 2
After baking for a time, a YSZ porous body having a thickness of 30 to 50 μm is coated. Then, Pd was added to the SnCl 2 solution for several minutes.
After catalyzing by dipping in a Cl 2 solution for several minutes, the solution was placed in a plating bath (a mixture of the following solutions A and B) at 95 ° C. for 10 to 20 minutes.
Then, Ni is diffused and deposited in the YSZ porous body.
【００１２】Ａ液：ＨＯＣＨ2 ＣＯＯＨ５ｇ，ＮＨ2 Ｎ
Ｈ2 ・Ｈ2 Ｏ１００ｇを水に溶かし１リットルの水溶液
にしたものに８：２の割合でアンモニアを混合したも
の。Solution A: HOCH 2 COOH 5 g, NH 2 N
A solution obtained by dissolving 100 g of H 2 · H 2 O in water to make a 1 liter aqueous solution and mixing ammonia at a ratio of 8: 2.
【００１３】Ｂ液：ＮｉＳＯ4 ・６Ｈ2 Ｏ６０ｇ／リッ
トルの水溶液に８：２の割合でアンモニアを混合したも
の（２がアンモニア）。Solution B: NiSO 4 .6H 2 O 60 g / liter aqueous solution mixed with ammonia at a ratio of 8: 2 (2 is ammonia).
【００１４】この発明によれば、本電極の骨格はＹＳＺ
で形成されているため、電極／ＹＳＺ緻密膜の接着強度
が大きく、熱膨脹係数の差が小さい。また、Ｎｉの含有
量がＹＳＺ緻密膜に向かってなだらかに減少しているた
め、熱膨脹係数の違いによる剥離応力が電極／ＹＳＺ緻
密膜界面に集中することなく、Ｎｉ粒子のＹＳＺ骨格中
の微細構造の変化として応力が緩和される効果がある。
更に、電極最上部のＮｉの含有量は１００％であるた
め、横流れ導電率も従来電極以上になる。これにより、
水蒸気電解装置を用いて電解操作と発電操作を繰り返し
ても、剥離の生じない水素電極とすることが可能とな
る。According to the present invention, the skeleton of the present electrode is YSZ
, The adhesive strength of the electrode / YSZ dense film is high, and the difference in thermal expansion coefficient is small. Further, since the Ni content decreases gradually toward the YSZ dense film, the peeling stress due to the difference in thermal expansion coefficient does not concentrate on the interface between the electrode and the YSZ dense film, and the fine structure in the YSZ skeleton of the Ni particles is reduced. Has the effect of reducing stress.
Further, since the Ni content at the top of the electrode is 100%, the lateral flow conductivity is also higher than that of the conventional electrode. This allows
Even if the electrolysis operation and the power generation operation are repeated using a steam electrolysis apparatus, a hydrogen electrode free from peeling can be obtained.
【００１５】[0015]
【発明の実施の形態】以下、この発明の一実施例に係る
燃料電池用カソード電極（水素電極）を製造方法を並記
して説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for manufacturing a cathode electrode (hydrogen electrode) for a fuel cell according to an embodiment of the present invention will be described in parallel.
【００１６】まず、５００μｍｔ，２３ｍｍφのＹＳＺ
緻密膜の片面中央に、０．３μｍのＹＳＺ粉末を有機樹
脂に混合分散させたものを、１０ｍｍφにスクリーンプ
リントした後、１４００℃，空気中で２Ｈｒ焼成して膜
厚５０μｍのＹＳＺ多孔体をコーティングした。つづい
て、アセトン中で超音波洗浄により７分間脱脂し、４７
％ＨＦ中で７分間エッチングし、水洗した。多孔体面以
外の部分をシリコンラバーでマスキングし、ＳｎＣｌ2
水溶液（ＳｎＣｌ2 ・２Ｈ2 Ｏ ０．０３ｇ／５０ｍ
ｌ）に１分間つけた後水洗し、再びＰｄＣｌ2 水溶液
（ＰｄＣｌ2 ０．０２５ｇ／５０ｍｌ）に１分間つけ
た後水洗し、触媒化処理を行なった。最後に、メッキ浴
（前記Ａ液４０ｍｌ，前記Ｂ液３０ｍｌを混合したも
の）に９５℃ウォーターバス上で１５分間つけて、ＹＳ
Ｚ多孔体中にＮｉを拡散析出させて本発明カソード電極
を作成した。First, a YSZ of 500 μmt, 23 mmφ
In the center of one side of the dense film, 0.3μm YSZ powder mixed and dispersed in an organic resin is screen-printed to 10mmφ, then fired at 1400 ° C in air for 2 hours and coated with 50μm thick YSZ porous material. did. Then, degreased by ultrasonic cleaning in acetone for 7 minutes.
Etched in% HF for 7 minutes and washed with water. The portion other than the porous body surface is masked with silicon rubber, and SnCl 2
Aqueous solution (SnCl 2 .2H 2 O 0.03 g / 50 m
then washed with water dipped 1 minute l), then washed with water dipped 1 minute again PdCl 2 solution (PdCl 2 0.025g / 50ml), it was subjected to catalytic treatment. Finally, the plate was immersed in a plating bath (a mixture of 40 ml of the solution A and 30 ml of the solution B) on a 95 ° C. water bath for 15 minutes, and YS
Ni was diffused and deposited in the Z porous body to prepare the cathode electrode of the present invention.
【００１７】このようにして得られた本発明の水素電極
の骨格はＹＳＺで形成されているため、電極／ＹＳＺ緻
密膜の接着強度が大きく、熱膨脹係数の差が小さい。ま
た、Ｎｉの含有量がＹＳＺ緻密膜に向かってなだらかに
減少しているため、熱膨脹係数の違いによる剥離応力が
電極／ＹＳＺ緻密膜界面に集中することなく、Ｎｉ粒子
のＹＳＺ骨格中の微細構造の変化として応力が緩和され
る効果がある。更に、電極最上部のＮｉの含有量は１０
０％であるため、横流れ導電率も従来電極以上になる。
これにより、水蒸気電解装置を用いて電解操作と発電操
作を繰り返しても、剥離の生じない水素電極とすること
が可能となる。Since the skeleton of the hydrogen electrode of the present invention thus obtained is formed of YSZ, the electrode / YSZ dense film has a high adhesive strength and a small difference in thermal expansion coefficient. Further, since the Ni content decreases gradually toward the YSZ dense film, the peeling stress due to the difference in thermal expansion coefficient does not concentrate on the interface between the electrode and the YSZ dense film, and the fine structure in the YSZ skeleton of the Ni particles is reduced. Has the effect of reducing stress. Furthermore, the Ni content at the top of the electrode is 10
Since it is 0%, the lateral flow conductivity is also higher than that of the conventional electrode.
Thereby, even if the electrolysis operation and the power generation operation are repeated using the steam electrolysis apparatus, it is possible to obtain a hydrogen electrode that does not cause peeling.
【００１８】事実、上記実施例に基づき作成した本発明
水素電極の金属組織を表わす断面をＳＥＭ（scanning e
lectron microscope）写真と、ＺｒとＮｉ元素のＥＤＸ
線分析を調べたところ、図１に示す通りとなった。図１
より、Ｎｉの含有量がＹＳＺ緻密膜に向かってなだらか
に減少していることが確認できた。これより、容易に推
定できる効果として、ＹＳＺ緻密膜との熱膨脹係数の違
いによる剥離応力が電極／ＹＳＺ緻密膜界面に集中する
ことがなくなり、熱による応力が緩和されることが期待
される。一方、従来の水素電極についても金属組織を表
わす断面をＳＥＭ（scanning electron microscope）写
真と、ＺｒとＮｉ元素のＥＤＸ線分析を調べたところ、
図５に示す通りである。In fact, a cross section showing the metallographic structure of the hydrogen electrode of the present invention prepared based on the above embodiment is shown by SEM (scanning e
(electron microscope) Photo and EDX of Zr and Ni elements
When the line analysis was examined, it was as shown in FIG. FIG.
From the results, it was confirmed that the Ni content was gradually decreased toward the YSZ dense film. Thus, as an effect that can be easily estimated, it is expected that the peeling stress due to the difference in the thermal expansion coefficient from the YSZ dense film does not concentrate on the electrode / YSZ dense film interface, and the stress due to heat is reduced. On the other hand, a section of the conventional hydrogen electrode showing the metal structure was examined by SEM (scanning electron microscope) photograph and EDX analysis of Zr and Ni elements.
As shown in FIG.
【００１９】上記実施例に基づき作成した本発明カソー
ド電極から図２（Ａ）〜（Ｃ）に示すように加工してリ
ードを取り出し（但し、Ｖは電圧端子，Ｉは電流端
子）、直流４端子法（電圧端子間距離１．６ｍｍ，電極
断面積０．００３３５ｃｍ2 ）により横流れ導電率を測
定した。なお、図２において、符番１は２３φセル、符
番２はＩ，Ｖの端子を示す。測定は４％Ｈ2 （Ｎ2 バラ
ンス），５０ｍｌ／ｍｉｎで流通しながら２００℃／Ｈ
ｒで１０００℃まで昇温し、１００％Ｈ2 を１００ｍｌ
／ｍｉｎで流通して行なった。なお、測定時に電極に流
す電流値は１０ｍＡとした。測定結果を図３に示す。2 (A) to 2 (C), the lead is taken out from the cathode electrode of the present invention prepared based on the above embodiment (V is a voltage terminal, I is a current terminal), and DC 4 The lateral flow conductivity was measured by a terminal method (distance between voltage terminals 1.6 mm, electrode cross-sectional area 0.00335 cm 2 ). In FIG. 2, reference numeral 1 indicates a 23φ cell, and reference numeral 2 indicates I and V terminals. The measurement was performed at 200 ° C./H while flowing at 4% H 2 (N 2 balance) at 50 ml / min.
The temperature was raised to 1000 ° C. with 100% H 2 100 ml
/ Min. The value of the current flowing through the electrode during the measurement was 10 mA. FIG. 3 shows the measurement results.
【００２０】図３の横流れ導電率と通電時間との特性図
より、従来電極が１５００Ｓｃｍ-1程度であるのに対
し、本発明電極は約２４００Ｓｃｍ-1を示した。これ
は、電極最上部のＮｉ含有量が１００％近くなっている
ため、Ｎｉ／ＹＳＺ＝７０／３０サーメット電極以上の
値を示したと考えられる。The transverse flow conductivity of Figure 3 with the characteristic diagram of the conduction time, whereas conventional electrodes is about 1500Scm -1, the invention electrodes was about 2400Scm -1. This is presumably because the Ni content at the uppermost portion of the electrode was close to 100%, so that the Ni / YSZ = 70/30 cermet electrode or higher was exhibited.
【００２１】図４に本発明電極を施工した２３ｍｍφの
ＹＳＺ緻密膜の裏側に１０ｍｍφの酸素極（Ｌａ0.6 Ｓ
ｒ0.4 ＭｎＯ3 ：ＹＳＺ＝６０：４０の多孔質電極）を
１３００℃で焼結させたセルを用いて、４５０ｍＡ／ｃ
ｍ2 で交互運転を行なった時のセル抵抗の経時変化を示
す。従来電極では３サイクル以上で水素極の剥離が生
じ、セル抵抗の上昇が認められたのに対して、本発明電
極では５サイクル交互運転を行なってもセル抵抗の上昇
は認められず、剥離も認められなかった。FIG. 4 shows a 10 mmφ oxygen electrode (La 0.6 S) on the back side of a 23 mmφ YSZ dense film on which the electrode of the present invention is applied.
Using a cell obtained by sintering r 0.4 MnO 3 : YSZ = 60: 40 (porous electrode) at 1300 ° C., 450 mA / c
The change with time of the cell resistance when alternate operation is performed at m 2 is shown. In the conventional electrode, peeling of the hydrogen electrode occurred in 3 cycles or more, and an increase in cell resistance was observed. On the other hand, in the electrode of the present invention, the cell resistance did not increase even after 5 cycles of alternate operation, and peeling was not observed. I was not able to admit.
【００２２】本発明より、電解操作（ＳＯＥ）と発電操
作（ＳＯＦＣ）を繰り返しても、剥離の生じない水素電
極とすることが可能となった。According to the present invention, it has become possible to obtain a hydrogen electrode which does not peel off even if the electrolysis operation (SOE) and the power generation operation (SOFC) are repeated.
【００２３】なお、上記実施例では、カソード電極（水
素電極）に適用した場合について述べたが、これに限定
されず、アノード電極（酸素電極）に適用しても同様な
効果が期待できる。In the above embodiment, the case where the present invention is applied to the cathode electrode (hydrogen electrode) is described. However, the present invention is not limited to this, and the same effect can be expected when applied to the anode electrode (oxygen electrode).
【００２４】[0024]
【発明の効果】以上詳述したように本発明によれば、Ｙ
ＳＺからなる多孔質層からＹＳＺ緻密膜に向ってＮｉ／
ＹＳＺ比が減少する傾斜構造とすることにより、電解操
作と発電操作を繰り返しても、剥離の生じない燃料電池
用電極を提供できる。As described in detail above, according to the present invention, Y
From a porous layer made of SZ to a YSZ dense film, Ni /
By adopting the inclined structure in which the YSZ ratio is reduced, it is possible to provide an electrode for a fuel cell which does not peel off even when the electrolytic operation and the power generation operation are repeated.
【図１】この発明の一実施例に係る水素電極の金属組織
を表わすＳＥＭ写真。FIG. 1 is an SEM photograph showing a metal structure of a hydrogen electrode according to one embodiment of the present invention.
【図２】横流れ導電率測定のための端子取り出しを説明
するための図。FIG. 2 is a diagram for explaining how to take out a terminal for measuring the lateral flow conductivity.
【図３】従来水素電極及び本発明水素電極における横流
れ導電率と通電時間との関係を示す特性図。FIG. 3 is a characteristic diagram showing a relationship between a lateral flow conductivity and a conduction time in a conventional hydrogen electrode and a hydrogen electrode of the present invention.
【図４】従来水素電極及び本発明水素電極におけるＳＯ
Ｅ／ＳＯＦＣリバーシブル運転に伴うセル抵抗の経時変
化を示す特性図。FIG. 4 shows SO in conventional hydrogen electrode and hydrogen electrode of the present invention.
FIG. 4 is a characteristic diagram showing a change with time in cell resistance due to E / SOFC reversible operation.
【図５】従来の水素電極の金属組織を表わすＳＥＭ写
真。FIG. 5 is an SEM photograph showing a metal structure of a conventional hydrogen electrode.
１…セル、 ２…端子。 1 ... cell, 2 ... terminal.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 南條 房幸 兵庫県神戸市兵庫区和田崎町一丁目１番１ 号 三菱重工業株式会社神戸造船所内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Fukuyuki Nanjo 1-1-1 Wadazakicho, Hyogo-ku, Kobe City, Hyogo Prefecture Inside Mitsubishi Heavy Industries, Ltd. Kobe Shipyard
Claims (1)
の緻密膜上にイットリア安定化ジルコニアスラリーの塗
布，焼成によって形成された多孔質層からなり、Ｎｉが
前記緻密膜及び多孔質層に含浸析出され、前記多孔質層
から緻密膜に向かってＮｉ／イットリア安定化ジルコニ
ア比が減少する傾斜構造を有することを特徴とする燃料
電池用電極。1. A dense yttria-stabilized zirconia film and a porous layer formed by applying and firing a yttria-stabilized zirconia slurry on the dense film, and Ni is impregnated and deposited on the dense film and the porous layer. An electrode for a fuel cell, characterized by having a gradient structure in which the ratio of Ni / yttria-stabilized zirconia decreases from the porous layer toward the dense membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8188081A JPH1021934A (en) | 1996-07-01 | 1996-07-01 | Electrode for fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8188081A JPH1021934A (en) | 1996-07-01 | 1996-07-01 | Electrode for fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1021934A true JPH1021934A (en) | 1998-01-23 |
Family
ID=16217377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8188081A Withdrawn JPH1021934A (en) | 1996-07-01 | 1996-07-01 | Electrode for fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1021934A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006092912A1 (en) * | 2005-02-28 | 2006-09-08 | The Tokyo Electric Power Company, Incorporated | Solid oxide type fuel battery cell and process for producing the same |
| JP2010511282A (en) * | 2006-11-29 | 2010-04-08 | コーニング インコーポレイテッド | Activation of solid oxide fuel cell electrode surface |
| JP2010205655A (en) * | 2009-03-05 | 2010-09-16 | Toyota Motor Corp | Method for manufacturing fuel cell, and fuel cell |
| WO2020196236A1 (en) * | 2019-03-27 | 2020-10-01 | 国立大学法人山梨大学 | Solid oxide electrolysis cell, and method and system for operating same |
-
1996
- 1996-07-01 JP JP8188081A patent/JPH1021934A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006092912A1 (en) * | 2005-02-28 | 2006-09-08 | The Tokyo Electric Power Company, Incorporated | Solid oxide type fuel battery cell and process for producing the same |
| JP2010511282A (en) * | 2006-11-29 | 2010-04-08 | コーニング インコーポレイテッド | Activation of solid oxide fuel cell electrode surface |
| JP2010205655A (en) * | 2009-03-05 | 2010-09-16 | Toyota Motor Corp | Method for manufacturing fuel cell, and fuel cell |
| WO2020196236A1 (en) * | 2019-03-27 | 2020-10-01 | 国立大学法人山梨大学 | Solid oxide electrolysis cell, and method and system for operating same |
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