JP3501409B2 - Self-supporting flat-plate solid electrolyte fuel cell - Google Patents
Self-supporting flat-plate solid electrolyte fuel cellInfo
- Publication number
- JP3501409B2 JP3501409B2 JP17120693A JP17120693A JP3501409B2 JP 3501409 B2 JP3501409 B2 JP 3501409B2 JP 17120693 A JP17120693 A JP 17120693A JP 17120693 A JP17120693 A JP 17120693A JP 3501409 B2 JP3501409 B2 JP 3501409B2
- Authority
- JP
- Japan
- Prior art keywords
- plate
- solid electrolyte
- self
- scandia
- electrolyte
- 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 - Lifetime
Links
- 239000007784 solid electrolyte Substances 0.000 title claims description 38
- 239000000446 fuel Substances 0.000 title claims description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 41
- 241000968352 Scandia <hydrozoan> Species 0.000 claims description 27
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 6
- 239000002737 fuel gas Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 description 48
- 239000006104 solid solution Substances 0.000 description 16
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 16
- 238000002156 mixing Methods 0.000 description 11
- 238000010248 power generation Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007581 slurry coating method Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- IGPAMRAHTMKVDN-UHFFFAOYSA-N strontium dioxido(dioxo)manganese lanthanum(3+) Chemical compound [Sr+2].[La+3].[O-][Mn]([O-])(=O)=O IGPAMRAHTMKVDN-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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)
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は、自立膜平板型固体電解
質型燃料電池に関し、さらに詳しくは自立膜平板型固体
電解質型燃料電池における固体電解質に関するものであ
る。
【０００２】
【従来の技術】燃料電池としては、電解質の種類によっ
てリン酸型、溶融炭酸塩型、固体電解質型などが従来よ
り良く知られている。その中で固体電解質型燃料電池
（以下「ＳＯＦＣ」という。）は、電解質としてリン酸
水溶液や溶融炭酸塩のような液体状材料の代わりにイオ
ン導電性を有する固体材料を用いたものである。
【０００３】そしてこのＳＯＦＣは、リン酸型、溶融炭
酸塩型など他の燃料電池に比べて発電効率が良く、排熱
温度も高いため効率的な利用が可能な発電システムを構
築できるということで近年特に注目を浴びている。とこ
ろでこのＳＯＦＣの形態としては、一般に図６に示した
平板型のものと、図示しないが円筒型のものとに大きく
分類される。またこの図６に示した平板型のものにおい
ても、図７（ａ）に示した外部マニホールドタイプのも
のと、図７（ｂ）に示した内部マニホールドタイプのも
のとが代表的なものとして挙げられる。
【０００４】図６及び図７（ａ）（ｂ）に示したＳＯＦ
Ｃの構造について簡単に説明すると、燃料ガスが接する
燃料極１０と空気が接する酸素極２０との間に固体電解
質板３０を挟み、燃料極１０の外側および酸素極２０の
外側にそれぞれセパレータ４０ａ、４０ｂを設けた構造
の単セルが多数層にわたって積層状に設けられてなる。
そしてこのように構成されたＳＯＦＣにおいては、燃料
極に燃料ガス（水素、一酸化炭素）が接触し、酸素極に
は酸化ガス（空気、もしくは酸素）が接触する。そして
酸素極で生成した酸素イオン（Ｏ２−）が固体電解質内
を移動して燃料極に到達し、燃料極では酸素イオンが水
素（Ｈ２ ）と反応して電子を放出する。これにより電
気が作り出され、電気の流れが生ずるものである。
【０００５】このＳＯＦＣにおいては、用いられる固体
電解質の電気的特性、特に導電率が電池の性能に大きく
影響する。従来この種の固体電解質としては、安定化ジ
ルコニアが用いられてきた。この安定化ジルコニアは、
ジルコニア（ＺｒＯ２ ）が高温度（約１１５０℃付
近）で単斜晶形から正方晶形へ結晶構造が変化すること
に伴ない容積変化が生じることから、この容積変化を防
ぐ手段としてカルシウム（Ｃａ）やイットリウム（Ｙ）
などの酸化物を固溶させて結晶構造の安定化を図ったも
のである。現在ではイットリア安定化ジルコニア（Ｙ２
Ｏ３ StabilizedＺｒＯ２、以下「ＹＳＺ」という。）
が最も多く使用されている。
【０００６】
【発明が解決しようとする課題】しかしながら、このＹ
ＳＺ固体電解質を用いたＳＯＦＣでは、そのＹＳＺ固体
電解質そのものの内部抵抗が高いために導電率が低く、
そのために高い電力密度が得られないという問題があっ
た。
【０００７】例えば、固体電解質板に燃料極や酸素極を
スラリーコーティング法により形成してなる、いわゆる
自立膜平板型のＳＯＦＣにおいては、その構造上、固体
電解質板の板厚を０.２〜０.３ｍｍとせざるを得ず、そ
のためにＹＳＺ固体電解質を用いた場合には１０００℃
における導電率が０.０５〜０.１５Ｓ／ｃｍ程度と低く
なり、電力密度が０.５Ｗ／ｃｍ２程度しか得られない
といった問題があった。
【０００８】このため従来のＳＯＦＣにおいては、以下
のような欠点があった。すなわち、発電セルの大型化
によりシステムの設置面積が増大する。電池の内部抵
抗が高く、発電効率が低くなる。高い電流密度で運転
した場合にセルの寿命が短くなる、等々。
【０００９】本発明は、このような問題点を解決するた
めになされたものであり、その目的とするところは、材
料として内部抵抗の低い、すなわち、導電率の高い固体
電解質材料を探索し、高い導電率特性を備え、発電電力
密度に優れた自立膜平板型固体電解質型燃料電池を提供
することにある。
【００１０】
【課題を解決するための手段】このような目的を達成す
るため本発明者らは、種々の材料特性について実験研究
を重ねた結果、従来のイットリア−ジルコニア系（Ｙ２
Ｏ３−ＺｒＯ２ 系）の固体電解質よりもスカンジア−
ジルコニア系（Ｓｃ２Ｏ３−ＺｒＯ２ 系）の固体電解
質の方が、自立膜平板型固体電解質型燃料電池における
固体電解質として優れていることを見い出した。
【００１１】すなわち、本発明に係る自立膜平板型固体
電解質型燃料電池は、請求項１に記載のように、燃料ガ
スが接する燃料極と空気が接する酸素極との間に、自立
膜平板型の固体電解質を有するセル構造を備え、前記固
体電解質は、ジルコニア中に８〜１１モル％の範囲内で
スカンジアが固溶され、かつ、１０００℃における導電
率が０．３０〜０．３８Ｓ／ｃｍの範囲内にあるスカン
ジア安定化ジルコニアからなるとともに、その板厚は１
００〜３００μｍの範囲内とされていることを要旨とす
るものである。本発明に係る自立膜平板型固体電解質型
燃料電池（以下「自立膜平板型ＳＯＦＣ」という。）
は、セル構造中の自立膜平板型の固体電解質として、ジ
ルコニア中に８〜１１モル％の範囲内でスカンジアが固
溶され、かつ、１０００℃における導電率が０．３０〜
０．３８Ｓ／ｃｍの範囲内にあるスカンジア安定化ジル
コニアからなるとともに、その板厚が１００〜３００μ
ｍの範囲内とされている固体電解質（以下「ＳｃＳＺ固
体電解質」という。）を用いているので、従来より広く
用いられてきたＹＳＺ固体電解質等を用いた自立膜平板
型のＳＯＦＣと比較して、固体電解質自体の内部抵抗が
低い、すなわち、導電率が高い。そのため、固体電解質
の板厚をあえて薄くする等しなくても、高い導電性を備
え、発電電力密度に優れた自立膜平板型ＳＯＦＣとする
ことが可能になる。
【００１２】尚、燃料極及び酸素極は、自立膜平板型の
固体電解質の一方の面及び他方の面にそれぞれスラリー
コーティング法によって設けられていることが好まし
い。その場合の燃料極材料としては、ニッケル−イット
リア安定化ジルコニア（Ｎｉ−ＹＳＺ系）であってもよ
いし、あるいは他の材料であってもよく、特に限定され
るものではない。また、酸素極材料としては、ランタン
ストロンチウムマンガネート（Ｌａ（Ｓｒ）ＭｎＯ３）
が一例として挙げられる。
【００１３】
【実施例】以下に本発明について詳細に説明する。初め
に本発明の一実施例に係る自立膜平板型ＳＯＦＣに供さ
れる固体電解質板の製造工程について、図１に示した製
造工程図に基づいて順に説明する。それによれば、初め
に固体電解質板の主材料であるジルコニア（ＺｒＯ
２ ）の粉末粒子と安定化材料であるスカンジア（Ｓｃ
２Ｏ３）の粉末粒子とを適当な配合比率で混合する。こ
の混合粉末の平均粒径は３μｍ程度である。また、ジル
コニア・スカンジアの混合粉末を調整する方法として、
ゾルゲル法や共沈法などの液相製造プロセスを適用すれ
ば不純物が少なく、均一な混合粉末を得ることができ
る。ＺｒＯ２とＳｃ２Ｏ３の配合比率については、後述
するようにいろいろな条件（Ｓｃ２Ｏ３ の配合比率が
８モル％〜１５モル％）を選択している。
【００１４】次にこの混合粉末を板厚１００〜３００μ
ｍの板（およそ２０ｃｍ角板）に成形する。この成形手
段としては、この実施例では静水圧プレス機（ＣＩＰ）
を用いて１ｔ／ｃｍ２ の押圧力により加圧成形してい
る。ただし、この成形手段に限られるものではなく、従
来一般に用いられているドクターブレード法やカレンダ
ーロール法により薄板を製作するものであってもよい。
そしてしかる後、この成形板を１５００〜１７００℃の
温度で焼成する。これによりスカンジア （Ｓｃ
２Ｏ３）がジルコニア（ＺｒＯ２）中に８〜１５モル％
の範囲内で固溶されたスカンジア安定化ジルコニア（Ｓ
ｃ２Ｏ３ Stabilized ＺｒＯ２）からなる固体電解質板
（以下「ＳｃＳＺ電解質板」という。）が得られる。
【００１５】次にこのＳｃＳＺ電解質板に燃料極あるい
は酸素極を形成するに当たっては、これらの極材料のセ
ラミックス粉末を泥状にしていわゆるスラリーコーティ
ング法によりこのＳｃＳＺ電解質板の片面と反対側の面
とにそれぞれ塗布し、しかる後所定温度で焼成する。燃
料極の場合には、例えばニッケル（Ｎｉ）４０重量％−
ジルコニア（ＺｒＯ２ ）６０重量％のニッケル−ジル
コニアサーメットを５０μｍ程度の厚さでこのＳｃＳＺ
電解質板の片面にコーティングし、１４００〜１５００
℃の温度で焼成する。これによりＳｃＳＺ電解質板の片
面に薄膜状の燃料極が形成されることとなる。
【００１６】また、酸素極の場合には、例えばランタン
ストロンチウムマンガネート（Ｌａ（Ｓｒ）ＭｎＯ
３ ）を５０μｍ程度の厚さでＳｃＳＺ電解質板の前述
の燃料極とは反対側の面にコーティングし、１１５０℃
前後の温度で焼成する。これによりＳｃＳＺ電解質板の
反対側の面に、同じく薄膜状の酸素極が形成されること
となる。尚、酸素極の材料の配合比率としては、ランタ
ンマンガネート９５〜８５モル％に対し、ストロンチウ
ム５〜１５モル％程度とするのが適当である。次にこの
ようにして製作された自立膜平板型ＳＯＦＣとＳｃＳＺ
電解質板について種々の実験を行なったのでこれらにつ
いて説明する。
【００１７】初めに、従来のＹＳＺ電解質板を用いた自
立膜平板型ＳＯＦＣと本発明に係るＳｃＳＺ電解質板を
用いた自立膜平板型ＳＯＦＣについて発電特性の比較を
行なったので、その結果を図２を用いて説明する。ここ
で、供試した固体電解質は、それぞれ、ＹＳＺ電解質板
の場合８モル％Ｙ２Ｏ３−９２モル％ＺｒＯ２、ＳｃＳ
Ｚ電解質板の場合１１モル％Ｓｃ２Ｏ３−８９モル％Ｚ
ｒＯ２のものとしてある。両者は同等の板厚としてい
る。
【００１８】尚、同図中、横軸に電流［ｍＡ］を示し、
縦軸に電圧［ｍＶ］及び電力密度［Ｗ／ｃｍ２］を示
し、電圧特性と電力特性について両者を比較した。その
結果、電圧特性をみた場合に電流値を上げていくにつれ
て電圧値が徐々に低下していくことについては、ＳｃＳ
Ｚ電解質板を用いた場合もＹＳＺ電解質板を用いた場合
も同様であるが、ＳｃＳＺ電解質板を用いた方がＹＳＺ
電解質板を用いた方よりも電圧低下の割合が小さく、お
よそ７００ｍＡあたりから電流値が高い範囲で、同等の
電流［ｍＡ］に対して高い電圧［ｍＶ］を示しているこ
とがわかる。また電流が高いほどその電圧差が大きいこ
ともわかる。
【００１９】一方、電力特性をみた場合もＳｃＳＺ電解
質板を用いた場合には６００〜８００ｍＡで電力密度の
ピーク値を示し、それ以上の電流では徐々に電力密度が
低下するのに対し、ＹＳＺ電解質板を用いた場合には３
００〜５００ｍＡで電力密度のピーク値を示している
が、そのピーク値がＳｃＳＺ電解質板を用いた場合には
およそ１.１ Ｗ／ｃｍ２ であるのに対し、ＹＳＺ電解
質板を用いた場合にはおよそ０.８Ｗ／ｃｍ２と低く、
ＳｃＳＺ電解質板を用いた方がＹＳＺ電解質板を用いた
方よりも高い電力密度のピーク値を示すことがわかる。
また電力密度のピーク値を越してからの電力密度の低下
の割合もＳｃＳＺ電解質板を用いた方がＹＳＺ電解質板
を用いた方よりも小さく、同等の電流［ｍＡ］に対して
常に高い電力密度［Ｗ／ｃｍ２ ］を示している。しか
も電流値が高いほどその電力密度の差が大きいことがわ
かる。そしてこの図２に示した実験結果より、ＳｃＳＺ
電解質板を用いた方が材料としての内部抵抗が低いため
に導電率が高くなり、高い電力密度が得られたものと考
察されるものである。
【００２０】図３は、ＳｃＳＺ電解質板中のスカンジア
（Ｓｃ２Ｏ３）の配合比率を変え、つまりＳｃ２Ｏ３の
固溶量を変えることにより、このＳｃＳＺ電解質板の導
電率特性に対する温度依存性を調べた結果を示してい
る。横軸に温度変数１０００／Ｔ［１／Ｋ］（Ｋ：絶対
温度）を示し、縦軸に導電率変数log σ［Ｓ／ｃｍ］を
示している。ＳｃＳＺ電解質板中のスカンジア（Ｓｃ２
Ｏ３）の配合比率を８〜１５モル％までいろいろ変えて
みたが、その結果８モル％ＳｃＳＺ電解質板が最も導電
率特性に優れることがわかる。そして温度変数１０００
／Ｔ［１／Ｋ］がおよそ１.１ 以下（およそ６５０Ｋ以
下）程度の温度ではスカンジア配合比率（スカンジア固
溶量）の違いによる導電率特性に有意差は認められない
が、温度変数が１.１ 以上（およそ６５０Ｋ以上）の温
度ではスカンジアの配合比率が高くなるにつれて、つま
りスカンジアの固溶量が増すにつれて導電率特性の低下
が目立つ傾向にある。このことよりこのＳＯＦＣの使用
温度環境によってスカンジアの配合比率を考慮すること
が必要であることがわかる。
【００２１】図４は、ＳｃＳＺ 電解質板の室温〜１２
７３Ｋの温度範囲における熱膨張（温度歪）を調べた結
果を示している。スカンジアの配合比率としては、８モ
ル％のものと１１モル％のものとで比較した。その結
果、温度が高くなるにつれて１１モル％スカンジア固溶
量のＳｃＳＺ電解質板の方が、８モル％スカンジア固溶
量のＳｃＳＺ電解質板よりも熱膨張が少ない、つまり温
度歪が小さいことがわかる。他方、１１モル％スカンジ
ア固溶量のＳｃＳＺ電解質板は７００〜８００Ｋ付近で
熱膨張が急激に変化する。この様な急激な熱膨張はＳＯ
ＦＣとして利用した時に熱応力を生じるので好ましくな
い。このことからスカンジアの配合比率を低くした方が
良いということが言える。
【００２２】図５は、１０００℃（１２７３Ｋ）におけ
る導電率とＳｃＳＺ電解質板中のスカンジア（Ｓｃ２Ｏ
３）配合比率（スカンジア固溶量）との関係を示したも
のである。これによると、スカンジア固溶量が８〜１５
モル％の範囲で少ない方が導電率が高く、スカンジア固
溶量が多くなるにつれて導電率が低下することがわか
る。スカンジア固溶量が８〜１１モル％の範囲が最も好
ましいと言える。表１には、ＳｃＳＺ電解質板と、従来
から知られているＹＳＺ電解質板との間の既に前述した
導電率特性のほか、機械的特性（曲げ強度、破壊靭性強
度、ビッカース硬さ、熱膨張係数、結晶構造）の比較を
数値的に示している。
【００２３】
【表１】【００２４】ＹＳＺ電解質板については３モル％と８モ
ル％のイットリウム固溶量のものを示し、ＳｃＳＺ電解
質板については８モル％と１１モル％のスカンジア固溶
量のものを示している。この表よりわかるように、導電
率については既に図２ないし図５でも説明したようにＳ
ｃＳＺ電解質板の方がＹＳＺ電解質板よりも優れている
が、曲げ強度やビッカース硬さでは若干ＹＳＺ電解質板
の方がＳｃＳＺ電解質板よりも高い値を示している。し
かし使用上は耐久性という点ではほとんど有意差がない
ものと思われる。
【００２５】
【発明の効果】以上各種実験例に示したように、本発明
に係る自立膜平板型固体電解質型燃料電池（自立膜平板
型ＳＯＦＣ）によれば、発電電力密度の向上により発電
システムのコンパクト化を図ることができ、また電池抵
抗が小さいため、応答特性・発電効率に優れ、さらに、
発生電力に余裕を持って運転できることから、電池の長
寿命化を図ることができるといった多くの効果を奏し、
産業上の有益性は極めて高いものである。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-supporting flat plate type solid electrolyte fuel cell, and more particularly, to a solid electrolyte in a self-supporting flat plate type solid electrolyte fuel cell. is there. [0002] As a fuel cell, a phosphoric acid type, a molten carbonate type, a solid electrolyte type and the like are well known depending on the type of electrolyte. Among them, a solid oxide fuel cell (hereinafter referred to as “SOFC”) uses a solid material having ionic conductivity as an electrolyte instead of a liquid material such as a phosphoric acid aqueous solution or a molten carbonate. The SOFC has a higher power generation efficiency than other fuel cells such as a phosphoric acid type and a molten carbonate type, and has a high exhaust heat temperature, so that a power generation system that can be used efficiently can be constructed. In recent years, it has received particular attention. By the way, the SOFCs are generally broadly classified into a flat type shown in FIG. 6 and a cylindrical type (not shown). Also, in the flat plate type shown in FIG. 6, the external manifold type shown in FIG. 7A and the internal manifold type shown in FIG. Can be The SOF shown in FIGS. 6 and 7 (a) and (b)
Briefly describing the structure of C, the solid electrolyte plate 30 is sandwiched between the fuel electrode 10 in contact with the fuel gas and the oxygen electrode 20 in contact with the air, and separators 40a and 40b are provided outside the fuel electrode 10 and outside the oxygen electrode 20, respectively. A single cell having a structure provided with 40b is provided in a stacked manner over many layers.
In the SOFC thus configured, a fuel gas (hydrogen, carbon monoxide) contacts the fuel electrode, and an oxidizing gas (air or oxygen) contacts the oxygen electrode. Then, oxygen ions (O 2− ) generated at the oxygen electrode move in the solid electrolyte and reach the fuel electrode, where the oxygen ions react with hydrogen (H 2 ) to emit electrons. As a result, electricity is produced and a flow of electricity is generated. [0005] In this SOFC, the electrical characteristics of the solid electrolyte used, particularly the conductivity, greatly affect the performance of the battery. Conventionally, stabilized zirconia has been used as this type of solid electrolyte. This stabilized zirconia is
Since zirconia (ZrO 2 ) changes its volume at a high temperature (around 1150 ° C.) from a monoclinic to a tetragonal crystal structure, calcium (Ca) or Yttrium (Y)
Such oxides are used as a solid solution to stabilize the crystal structure. At present, yttria-stabilized zirconia (Y 2
O 3 Stabilized ZrO 2 , hereinafter referred to as “YSZ”. )
Is most often used. [0006] However, this Y
In an SOFC using an SZ solid electrolyte, the YSZ solid electrolyte itself has a high internal resistance, and thus has low conductivity.
Therefore, there is a problem that a high power density cannot be obtained. [0007] For example, in a so-called self-supporting flat plate type SOFC in which a fuel electrode or an oxygen electrode is formed on a solid electrolyte plate by a slurry coating method, the thickness of the solid electrolyte plate is 0.2 to 0 due to its structure. 0.3 mm, and 1000 ° C when using a YSZ solid electrolyte.
Has a problem that the electrical conductivity at about 0.05 to 0.15 S / cm is low and the power density is only about 0.5 W / cm 2 . For this reason, the conventional SOFC has the following disadvantages. In other words, the size of the power generation cell increases the installation area of the system. The internal resistance of the battery is high, and the power generation efficiency is low. Shorter cell life when operating at higher current densities, etc. The present invention has been made in order to solve such a problem, and an object thereof is to find a solid electrolyte material having a low internal resistance, that is, a high conductivity, as a material. An object of the present invention is to provide a self-supporting membrane plate type solid electrolyte fuel cell having high conductivity characteristics and excellent power generation power density. [0010] In order to achieve the above object, the present inventors have conducted experimental studies on various material properties, and as a result, have found that a conventional yttria-zirconia (Y 2
Scandia than solid electrolytes of the type O 3 —ZrO 2 ).
It has been found that a zirconia-based (Sc 2 O 3 -ZrO 2 -based) solid electrolyte is more excellent as a solid electrolyte in a self-supporting membrane plate type solid electrolyte fuel cell. That is, according to the first aspect of the present invention, there is provided a self-standing membrane flat type solid electrolyte fuel cell according to the present invention, wherein a self-standing membrane flat type solid electrolyte fuel cell is provided between a fuel electrode in contact with fuel gas and an oxygen electrode in contact with air. Having a solid structure in which zirconia has a solid solution of scandia in the range of 8 to 11 mol% and a conductivity at 1000 ° C. of 0.30 to 0.38 S / together consist of scandia-stabilized zirconia is in the range of cm, the thickness is 1
The gist is that it is within the range of 00 to 300 μm . Self-standing membrane flat-plate solid electrolyte fuel cell according to the present invention (hereinafter referred to as “self-supporting membrane flat-plate SOFC”)
Is a solid electrolyte in the form of a free-standing membrane in a cell structure, in which zirconia has a solid solution of scandia in the range of 8 to 11 mol% and a conductivity at 1000 ° C. of 0.30 to 0.30%.
It is made of scandia-stabilized zirconia in the range of 0.38 S / cm and has a thickness of 100 to 300 μm.
m, a solid electrolyte (hereinafter, referred to as “ScSZ solid electrolyte”) is used, which is compared with a self-standing membrane flat-plate SOFC using a YSZ solid electrolyte which has been widely used in the past. , The internal resistance of the solid electrolyte itself
Low had, i.e., the conductivity is not high. For this reason, it is possible to provide a self-supporting membrane-type SOFC having high conductivity and excellent power generation density without intentionally reducing the thickness of the solid electrolyte. Preferably, the fuel electrode and the oxygen electrode are provided on one surface and the other surface of the solid electrolyte of the self-supporting flat plate type by a slurry coating method, respectively. The fuel electrode material in that case may be nickel-yttria-stabilized zirconia (Ni-YSZ-based) or another material, and is not particularly limited. As the oxygen electrode material, lanthanum strontium manganate (La (Sr) MnO 3 )
Is an example. The present invention will be described below in detail. First, the manufacturing process of the solid electrolyte plate used for the free-standing membrane flat-plate SOFC according to one embodiment of the present invention will be described in order with reference to the manufacturing process diagram shown in FIG. According to this, zirconia (ZrO), which is a main material of a solid electrolyte plate, is first used.
2 ) The powder particles and the stabilizing material scandia (Sc)
2 O 3 ) and powder particles are mixed at an appropriate mixing ratio. The average particle size of the mixed powder is about 3 μm. In addition, as a method of adjusting the mixed powder of zirconia scandia,
If a liquid phase manufacturing process such as a sol-gel method or a coprecipitation method is applied, a uniform mixed powder with few impurities can be obtained. The mixing ratio of ZrO 2 and Sc 2 O 3, various conditions as described below (the blending ratio of Sc 2 O 3 is 8 mol% to 15 mol%) is selected. Next, this mixed powder is made to have a thickness of 100 to 300 μm.
m plate (about 20 cm square plate). In this embodiment, a hydrostatic press (CIP) is used as the molding means.
And press-molding with a pressing force of 1 t / cm 2 . However, the present invention is not limited to this forming means, and a thin plate may be manufactured by a doctor blade method or a calender roll method generally used conventionally.
Thereafter, the formed plate is fired at a temperature of 1500 to 1700 ° C. This allows Scandia (Sc
2 O 3 ) is 8 to 15 mol% in zirconia (ZrO 2 ).
Scandia stabilized zirconia (S)
A solid electrolyte plate made of c 2 O 3 ( Stabilized ZrO 2 ) (hereinafter referred to as “ScSZ electrolyte plate”) is obtained. Next, in forming a fuel electrode or an oxygen electrode on the ScSZ electrolyte plate, a ceramic powder of these electrode materials is formed into a mud-like shape by a so-called slurry coating method to form a surface opposite to one surface of the ScSZ electrolyte plate. And then fired at a predetermined temperature. In the case of the fuel electrode, for example, nickel (Ni) 40% by weight
Nickel-zirconia cermet of zirconia (ZrO 2 ) 60% by weight has a thickness of about 50 μm.
Coated on one side of the electrolyte plate, 1400-1500
Firing at a temperature of ° C. As a result, a thin-film fuel electrode is formed on one surface of the ScSZ electrolyte plate. In the case of an oxygen electrode, for example, lanthanum strontium manganate (La (Sr) MnO
3 ) is coated on the surface of the ScSZ electrolyte plate on the side opposite to the fuel electrode at a thickness of about 50 μm,
Bake at the temperature before and after. Thus, a thin-film oxygen electrode is similarly formed on the surface on the opposite side of the ScSZ electrolyte plate. The mixing ratio of the material of the oxygen electrode is preferably about 5 to 15 mol% of strontium with respect to 95 to 85 mol% of lanthanum manganate. Next, the self-supporting flat plate type SOFC and ScSZ manufactured as described above are used.
Various experiments were performed on the electrolyte plate, and these will be described. First, a comparison was made between the power generation characteristics of a conventional free-standing membrane-type SOFC using a YSZ electrolyte plate and a self-standing membrane-type SOFC using a ScSZ electrolyte plate according to the present invention. This will be described with reference to FIG. Here, the tested solid electrolytes were 8 mol% Y 2 O 3 -92 mol% ZrO 2 and ScS in the case of a YSZ electrolyte plate, respectively.
11 mol% Sc 2 O 3 -89 mol% Z for Z electrolyte plate
rO 2 . Both have the same plate thickness. In the figure, the horizontal axis represents the current [mA],
The vertical axis represents the voltage [mV] and the power density [W / cm 2 ], and the voltage characteristics and the power characteristics were compared. As a result, when the voltage characteristic is observed, the voltage value gradually decreases as the current value increases, as described in ScS.
The same applies to the case where a Z electrolyte plate is used and the case where a YSZ electrolyte plate is used.
It can be seen that the rate of voltage drop is smaller than that using the electrolyte plate, and a high voltage [mV] with respect to an equivalent current [mA] is shown in a range where the current value is high from around 700 mA. It can also be seen that the higher the current, the greater the voltage difference. On the other hand, when the power characteristics are examined, when the ScSZ electrolyte plate is used, the peak value of the power density is shown at 600 to 800 mA. 3 when using a plate
Although the peak value of the power density is shown at 00 to 500 mA, the peak value is about 1.1 W / cm 2 when the ScSZ electrolyte plate is used, whereas the peak value is about 1.1 W / cm 2 when the YSZ electrolyte plate is used. Is as low as about 0.8 W / cm 2 ,
It can be seen that the use of the ScSZ electrolyte plate shows a higher power density peak value than the use of the YSZ electrolyte plate.
In addition, the rate of decrease in power density after exceeding the peak value of the power density is smaller when the ScSZ electrolyte plate is used than when the YSZ electrolyte plate is used, and the power density is always higher for the same current [mA]. [W / cm 2 ]. In addition, it can be seen that the higher the current value, the greater the difference in power density. From the experimental results shown in FIG. 2, ScSZ
It is considered that the use of the electrolyte plate resulted in a higher electrical conductivity due to a lower internal resistance as a material, resulting in a higher power density. FIG. 3 shows that the mixing ratio of scandia (Sc 2 O 3 ) in the ScSZ electrolyte plate is changed, that is, the solid solution amount of Sc 2 O 3 is changed, so that the conductivity characteristic of the ScSZ electrolyte plate depends on the temperature. The result of having examined sex is shown. The horizontal axis shows the temperature variable 1000 / T [1 / K] (K: absolute temperature), and the vertical axis shows the conductivity variable log σ [S / cm]. Scandia (Sc 2) in the ScSZ electrolyte plate
The mixing ratio of O 3 ) was variously changed from 8 to 15 mol%, and as a result, it can be seen that the 8 mol% ScSZ electrolyte plate has the best conductivity characteristics. And the temperature variable 1000
At a temperature where / T [1 / K] is about 1.1 or less (about 650 K or less), there is no significant difference in the conductivity characteristics due to the difference in the scandia compounding ratio (the amount of scandia solid solution). At temperatures of 0.1 or more (approximately 650 K or more), as the blending ratio of scandia increases, that is, as the solid solution amount of scandia increases, the conductivity characteristics tend to decrease significantly. This shows that it is necessary to consider the blending ratio of scandia depending on the operating temperature environment of this SOFC. FIG. 4 shows the temperature of the ScSZ electrolyte plate from room temperature to 12 ° C.
The result of having investigated the thermal expansion (temperature distortion) in the temperature range of 73K is shown. As the blending ratio of scandia, a comparison was made between 8 mol% and 11 mol%. As a result, it can be seen that as the temperature increases, the thermal expansion of the ScSZ electrolyte plate of 11 mol% scandia solid solution is smaller than that of the ScSZ electrolyte plate of 8 mol% scandia solid solution, that is, the temperature distortion is smaller. On the other hand, the thermal expansion of the ScSZ electrolyte plate having a solid solution amount of 11 mol% scandia changes rapidly around 700 to 800K. Such rapid thermal expansion is caused by SO
It is not preferable because thermal stress occurs when used as FC. From this, it can be said that it is better to lower the blending ratio of scandia. FIG. 5 shows the conductivity at 1000 ° C. (1273 K) and the scandia (Sc 2 O) in the ScSZ electrolyte plate.
3 ) It shows the relationship with the mixing ratio (the amount of scandia solid solution). According to this, the scandia solid solution amount is 8 to 15
It can be seen that the smaller the molar percentage, the higher the conductivity, and the higher the amount of scandia solid solution, the lower the conductivity. It can be said that the scandia solid solution amount is most preferably in the range of 8 to 11 mol%. Table 1 shows the mechanical properties (bending strength, fracture toughness, Vickers hardness, thermal expansion coefficient) in addition to the above-mentioned conductivity properties between the ScSZ electrolyte plate and the conventionally known YSZ electrolyte plate. , Crystal structure) are shown numerically. [Table 1] The YSZ electrolyte plate shows the yttrium solid solution amount of 3 mol% and 8 mol%, and the ScSZ electrolyte plate shows the scandia solid solution amount of 8 mol% and 11 mol%. As can be seen from this table, the conductivity is S as already described in FIGS.
Although the cSZ electrolyte plate is superior to the YSZ electrolyte plate, the YSZ electrolyte plate shows slightly higher values in bending strength and Vickers hardness than the ScSZ electrolyte plate. However, it seems that there is almost no significant difference in terms of durability in use. As described above in the various experimental examples, according to the self-supporting flat-plate solid electrolyte fuel cell (self-supporting flat-plate SOFC) according to the present invention, the power generation system is improved by improving the power generation power density. It is possible to reduce the size of the battery, and because the battery resistance is small, it has excellent response characteristics and power generation efficiency.
Because it can operated with ease generating power, it exerts a number of effects such can prolong the life of the battery,
The industrial benefits are very high.
【図面の簡単な説明】
【図１】本発明に係る自立膜平板型ＳＯＦＣにおける固
体電解質板及び電極の製造工程図である。
【図２】本発明に係るＳｃＳＺ電解質板を用いた自立膜
平板型ＳＯＦＣと、従来一般に知られているＹＳＺ電解
質板を用いた自立膜平板型ＳＯＦＣとの発電比較特性デ
ータを示した図である。
【図３】本発明に係る自立膜平板型ＳＯＦＣにおけるＳ
ｃＳＺ電解質板の導電率特性に対する温度依存性のデー
タを示した図である。
【図４】本発明に係る自立膜平板型ＳＯＦＣにおけるＳ
ｃＳＺ電解質板の熱膨張（温度歪）データを示した図で
ある。
【図５】図３に示したＳｃＳＺ電解質板の１０００℃
（１２７３Ｋ）における導電率をスカンジア固溶量との
関係データとして示した図である。
【図６】従来一般に知られる平板型のＳＯＦＣの単セル
構造の一例を示した図である。
【図７】（ａ）は図６に示した平板型のＳＯＦＣにおけ
る外部マニホールドタイプのもの、（ｂ）は同じく内部
マニホールドタイプのものの概略構成を示した図であ
る。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a manufacturing process diagram of a solid electrolyte plate and an electrode in a self-standing membrane flat-plate SOFC according to the present invention. FIG. 2 is a diagram showing power generation comparison characteristic data between a self-standing membrane flat-plate SOFC using a ScSZ electrolyte plate according to the present invention and a self-standing membrane flat-plate SOFC using a conventionally generally known YSZ electrolyte plate. . FIG. 3 is a graph showing the relationship between S and S in the self-supporting flat-plate SOFC according to the present invention.
FIG. 5 is a diagram showing data of temperature dependence on the conductivity characteristics of a cSZ electrolyte plate. FIG. 4 is a graph showing the relationship between S in a free-standing film type SOFC according to the present invention.
FIG. 4 is a diagram showing thermal expansion (temperature distortion) data of a cSZ electrolyte plate. FIG. 5 shows a 1000 ° C. of the ScSZ electrolyte plate shown in FIG.
It is the figure which showed the electric conductivity in (1273K) as a relation data with the scandia solid solution amount. FIG. 6 is a diagram showing an example of a single-cell structure of a conventional flat-plate SOFC. 7A is a diagram showing a schematic configuration of an external manifold type in the flat plate type SOFC shown in FIG. 6, and FIG. 7B is a diagram showing a schematic configuration of an internal manifold type in the same type.
フロントページの続き (56)参考文献 特開 平４−215259（ＪＰ，Ａ) 特開 平５−33179（ＪＰ，Ａ) 特開 平１−227362（ＪＰ，Ａ) Ｄ．Ｗ．ＳＴＲＩＣＫＬＥＲ ａｎｄ Ｗ．Ｇ．ＣＡＲＬＳＯＮ，“Ｅｌｅｃ ｔｒｉｃａｌ Ｃｏｎｄｕｃｔｉｖｉｔ ｙ ｉｎ ｔｈｅ ＺｒＯ２−Ｒｉｃｈ Ｒｅｇｉｏｎ ｏｆ Ｓｅｖｅｒａｌ Ｍ２Ｏ３−ＺｒＯ２ Ｓｙｓｔｅｍ ｓ”，Ｊｏｕｒｎａｌ ｏｆ Ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｅｒａｍｉｃ Ｓ ｏｃｉｅｔｙ，Ｖｏｌ．48，Ｎｏ．６, ｐ．286〜289 Ｂ．Ｃ．Ｎｇｕｙｅｎ，Ｔ．Ａ．Ｌｉ ｎ，ａｎｄ Ｄ．Ｍ．Ｍａｓｏｎ，“Ｅ ｌｅｃｔｒｏｃａｔａｌｙｔｉｃ Ｒｅ ａｃｔｉｖｉｔｙ ｏｆ Ｈｙｄｒｏｃ ａｒｂｏｎｓ ｏｎ ａ Ｚｉｒｃｏｎ ｏｉａ Ｅｌｅｃｔｒｏｌｙｔｅ Ｓｕ ｒｆａｃｅ”，Ｊ．Ｅｌｅｃｔｒｏｃｈ ｅｍ．Ｓｏｃ．，Ｖｏｌ．133，Ｎｏ. ９（1986），ｐ．1807〜1815 Ｏ．ＹＡＭＡＭＯＴＯ，Ｙ．ＴＡＫＥ ＤＡ，Ｒ．ＫＡＮＮＯ，Ｋ．ＫＯＨＮ Ｏ，Ｔ．ＫＡＭＩＨＡＲＡＩ，“Ｅｌｅ ｃｔｒｉｃａｌ ｃｏｎｄｕｃｔｉｖｉ ｔｙ ｏｆ ｐｏｌｙｃｒｙｓｔａｌｌ ｉｎｅ ｔｅｔｒａｇｏｎａｌ ｚｉｒ ｃｏｎｉａ ＺｒＯ２−Ｍ２Ｏ３（Ｍ= Ｓｃ，Ｙ，Ｙｂ）”，ＪＯＵＲＮＡＬ ＯＦ ＭＡＴＥＲＩＡＬＳ ＳＣＩＥＮ ＣＥ ＬＥＴＴＥＲＳ，Ｖｏｌ．８ （1989），ｐ．198〜200 (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 8/12 H01M 8/02 Continuation of front page (56) References JP-A-4-215259 (JP, A) JP-A-5-33179 (JP, A) JP-A-1-227362 (JP, A) W. STRICKLER and W. G. FIG. CARLSON, "Electrical Conductivity in the ZrO2-Rich Region of Several M2O3-ZrO2 Systems", Journal of The American Ceramics. 48, no. 6, p. 286-289 B. C. Nguyen, T .; A. Lin, and D.L. M. Mason, "Electrocatalytic Reactivity of Hydrocarbons on a Zirconia Oia Electrolyte Surface", J. Org. Electrochem em. Soc. , Vol. 133, No. 9 (1986), p. 1807-1815 YAMAMOTO, Y. TAKE DA, R. KANNO, K .; KOHNO, T .; KAMIHARAI, "Electrical Conductive of Polycrystalline Intratetragonal Zirconia ZrO2-M2O3 (M = Sc, Y, Yb). 8 (1989), p. 198-200 (58) Field surveyed (Int. Cl. 7 , DB name) H01M 8/12 H01M 8/02
Claims (1)
酸素極との間に、自立膜平板型の固体電解質を有するセ
ル構造を備え、前記固体電解質は、ジルコニア中に８〜
１１モル％の範囲内でスカンジアが固溶され、かつ、１
０００℃における導電率が０．３０〜０．３８Ｓ／ｃｍ
の範囲内にあるスカンジア安定化ジルコニアからなると
ともに、その板厚は１００〜３００μｍの範囲内とされ
ていることを特徴とする自立膜平板型固体電解質型燃料
電池。(57) [Claim 1] A cell structure having a self-supporting flat plate-type solid electrolyte is provided between a fuel electrode in contact with a fuel gas and an oxygen electrode in contact with air, and the solid electrolyte comprises: 8 ~ in zirconia
Within a range of 11 mol%, scandia is dissolved and 1
Conductivity at 000 ° C. is 0.30 to 0.38 S / cm
When composed of scandia-stabilized zirconia is within the range of
In both cases, the plate thickness is in the range of 100-300 μm
Freestanding membrane plate type solid oxide fuel cell characterized by being.
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| JP17120693A JP3501409B2 (en) | 1993-06-17 | 1993-06-17 | Self-supporting flat-plate solid electrolyte fuel cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17120693A JP3501409B2 (en) | 1993-06-17 | 1993-06-17 | Self-supporting flat-plate solid electrolyte fuel cell |
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| JPH076774A JPH076774A (en) | 1995-01-10 |
| JP3501409B2 true JP3501409B2 (en) | 2004-03-02 |
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| JP17120693A Expired - Lifetime JP3501409B2 (en) | 1993-06-17 | 1993-06-17 | Self-supporting flat-plate solid electrolyte fuel cell |
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Families Citing this family (5)
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|---|---|---|---|---|
| JPH08250134A (en) * | 1995-03-14 | 1996-09-27 | Toho Gas Co Ltd | Solid oxide fuel cell and method for producing battery cell thereof |
| AU722980B2 (en) * | 1997-03-20 | 2000-08-17 | Siemens Aktiengesellschaft | High-temperature fuel cell |
| US5993989A (en) * | 1997-04-07 | 1999-11-30 | Siemens Westinghouse Power Corporation | Interfacial material for solid oxide fuel cell |
| US7569292B2 (en) | 2005-03-04 | 2009-08-04 | Toto Ltd. | Solid oxide fuel cell |
| US7462412B2 (en) | 2005-03-04 | 2008-12-09 | Toto Ltd. | Solid oxide fuel cell |
-
1993
- 1993-06-17 JP JP17120693A patent/JP3501409B2/en not_active Expired - Lifetime
Non-Patent Citations (3)
| Title |
|---|
| Ｂ．Ｃ．Ｎｇｕｙｅｎ，Ｔ．Ａ．Ｌｉｎ，ａｎｄ Ｄ．Ｍ．Ｍａｓｏｎ，"Ｅｌｅｃｔｒｏｃａｔａｌｙｔｉｃ Ｒｅａｃｔｉｖｉｔｙ ｏｆ Ｈｙｄｒｏｃａｒｂｏｎｓ ｏｎ ａ Ｚｉｒｃｏｎｏｉａ Ｅｌｅｃｔｒｏｌｙｔｅ Ｓｕｒｆａｃｅ"，Ｊ．Ｅｌｅｃｔｒｏｃｈｅｍ．Ｓｏｃ．，Ｖｏｌ．１３３，Ｎｏ．９（１９８６），ｐ．１８０７〜１８１５ |
| Ｄ．Ｗ．ＳＴＲＩＣＫＬＥＲ ａｎｄ Ｗ．Ｇ．ＣＡＲＬＳＯＮ，"Ｅｌｅｃｔｒｉｃａｌ Ｃｏｎｄｕｃｔｉｖｉｔｙ ｉｎ ｔｈｅ ＺｒＯ２−Ｒｉｃｈ Ｒｅｇｉｏｎ ｏｆ Ｓｅｖｅｒａｌ Ｍ２Ｏ３−ＺｒＯ２ Ｓｙｓｔｅｍｓ"，Ｊｏｕｒｎａｌ ｏｆ Ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｅｒａｍｉｃ Ｓｏｃｉｅｔｙ，Ｖｏｌ．４８，Ｎｏ．６，ｐ．２８６〜２８９ |
| Ｏ．ＹＡＭＡＭＯＴＯ，Ｙ．ＴＡＫＥＤＡ，Ｒ．ＫＡＮＮＯ，Ｋ．ＫＯＨＮＯ，Ｔ．ＫＡＭＩＨＡＲＡＩ，"Ｅｌｅｃｔｒｉｃａｌ ｃｏｎｄｕｃｔｉｖｉｔｙ ｏｆ ｐｏｌｙｃｒｙｓｔａｌｌｉｎｅ ｔｅｔｒａｇｏｎａｌ ｚｉｒｃｏｎｉａ ＺｒＯ２−Ｍ２Ｏ３（Ｍ＝Ｓｃ，Ｙ，Ｙｂ）"，ＪＯＵＲＮＡＬ ＯＦ ＭＡＴＥＲＩＡＬＳ ＳＣＩＥＮＣＥ ＬＥＴＴＥＲＳ，Ｖｏｌ．８（１９８９），ｐ．１９８〜２００ |
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| JPH076774A (en) | 1995-01-10 |
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