JP2008153213A - セラミック電解質構造体及び製造方法並びに関連物品 - Google Patents
セラミック電解質構造体及び製造方法並びに関連物品 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000446 fuel Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 17
- 230000035699 permeability Effects 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 241000588731 Hafnia Species 0.000 claims description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 40
- 238000000576 coating method Methods 0.000 abstract description 25
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- 238000006243 chemical reaction Methods 0.000 description 7
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- 150000004706 metal oxides Chemical class 0.000 description 3
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 3
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- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
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- ZUWXYYNYQIKFSJ-UHFFFAOYSA-N zirconium(2+);dinitrate Chemical compound [Zr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZUWXYYNYQIKFSJ-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910019858 La0.8Sr0.2Co0.8Ni0.2O3 Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052963 cobaltite Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
【解決手段】少なくとも、第1の平均微小亀裂長さと第1の平均微小亀裂幅を有する複数の微小亀裂12を含む第1の領域と、第2の平均微小亀裂長さと第2の平均微小亀裂幅を有する第2の領域とを含んでなるミクロ組織を有する。かかるミクロ組織は、(a)第1の平均微小亀裂長さが第2の平均微小亀裂長さと異なるか、或いは(b)第1の平均微小亀裂幅が第2の平均微小亀裂幅と異なるという基準を満足するセラミック電解質10を含んでなる固体酸化物型燃料電池が提供される。
【選択図】図1
Description
図1は、ナノサイズ微小亀裂及び細孔を有する大気プラズマ溶射イットリア安定化ジルコニアセラミック電解質試料の断面走査電子顕微鏡写真である。
硝酸イットリウム及び酸化二硝酸ジルコニウムの前駆体水溶液を調製し、適当な比率で混合することで、硝酸塩分解後に8モル%Y2O3−ZrO2(8YSZ)の最終組成を有する0.6M溶液を得た。厚さ65ミクロンの8YSZ大気プラズマ溶射(APS)電解質を有する直径1インチの多孔質ステンレス鋼基板を基線として使用した。8YSZ硝酸塩溶液をAPSコーティング上に3.5mg/cm2で塗布し、その間に溶液は透過性コーティング中に目に見えて浸透した。基板を室温及び70℃でそれぞれ約5分間ずつ風乾した。次に、2℃/分の加熱及び冷却速度で基板に500℃で0.5時間の熱処理を施すことで、硝酸塩を分解して酸化物を生成させた。塗布から熱処理までの操作を全部で10回繰り返した。
硝酸イットリウム及び酸化二硝酸ジルコニウムの前駆体水溶液を調製し、適当な比率で混合することで、硝酸塩分解後に8モル%Y2O3−ZrO2(8YSZ)の最終組成を有する0.9M溶液を得た。電気化学的試験に使用されるものの典型例である、8YSZ大気プラズマ溶射(APS)電解質を有する4インチ平方のSOFC陽極包囲体を以後の硝酸塩溶液含浸のための基線として使用した。
12 ナノサイズ微小亀裂
14 細孔
Claims (12)
- ミクロ組織を有するセラミック電解質(10)であって、ミクロ組織は少なくとも、第1の平均微小亀裂長さと第1の平均微小亀裂幅を有する複数の微小亀裂(12)を含む第1の領域と、第2の平均微小亀裂長さと第2の平均微小亀裂幅を有する第2の領域とを含んでなり、
(a)第1の平均微小亀裂長さが第2の平均微小亀裂長さと異なるか、或いは
(b)第1の平均微小亀裂幅が第2の平均微小亀裂幅と異なる、セラミック電解質(10)。 - モノリシック構造体をなす、請求項1記載のセラミック電解質(10)。
- モノリシック構造体が約5〜約70μmの範囲内の厚さを有する、請求項2記載のセラミック電解質(10)。
- 第2の平均微小亀裂長さが第1の平均微小亀裂長さよりも約10%以上大きい、請求項1記載のセラミック電解質(10)。
- 第2の平均微小亀裂幅が第1の平均微小亀裂幅よりも約5%以上大きい、請求項1記載のセラミック電解質(10)。
- ミクロ組織がさらに、第1の領域において第1の多孔度を有し、第2の領域において第2の異なる多孔度を有する、請求項1記載のセラミック電解質(10)。
- 当該セラミック電解質(10)が、ジルコニア、セリア、ハフニア、酸化ビスマス、ランタンガレート及びトリアからなる群から選択される材料からなる、請求項1記載のセラミック電解質(10)。
- 請求項1記載のセラミック電解質(10)を含んでなる固体酸化物型燃料電池(20)。
- アノード(24)、カソード(22)、及びアノード(24)とカソード(22)との間に配設されたセラミック電解質(10)を含んでなる固体酸化物型燃料電池(20)であって、セラミック電解質(10)が、少なくとも、第1の平均微小亀裂長さと第1の平均微小亀裂幅を有する複数の微小亀裂(12)を含む第1の領域と、第2の平均微小亀裂長さと第2の平均微小亀裂幅を有する第2の領域とを含むミクロ組織を有し、
(a)第1の平均微小亀裂長さが第2の平均微小亀裂長さと異なるか、或いは
(b)第1の平均微小亀裂幅が第2の平均微小亀裂幅と異なる、固体酸化物型燃料電池(20)。 - 1以上の気密領域及び1以上のコンプライアント領域を有するセラミック電解質(10)の製造方法であって、
複数のナノサイズ微小亀裂を含むセラミック電解質(10)を設ける段階と、
セラミック電解質(10)の一方の表面から優先的にナノサイズ微小亀裂(12)を閉鎖することで、セラミック電解質(10)が1以上の気密領域及び1以上のコンプライアント領域を有するようにする段階と
を含んでなる方法。 - 気密領域が第1の平均微小亀裂長さと第1の平均微小亀裂幅を有する複数のナノサイズ微小亀裂(12)を含み、コンプライアント領域が第2の平均微小亀裂長さと第2の平均微小亀裂幅を有していて、
(a)第1の平均微小亀裂長さが第2の平均微小亀裂長さと異なるか、或いは
(b)第1の平均微小亀裂幅が第2の平均微小亀裂幅と異なる、請求項10記載の方法。 - 複数のナノサイズ微小亀裂(12)を含むセラミック電解質(10)が、空気中で測定して約8×10−10cm2Pa−1sec−1未満の気体透過度を有する、請求項10記載の方法。
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JP2014009157A (ja) * | 2012-06-29 | 2014-01-20 | Korea Institute Of Science And Technology | 酸化ビズマスを含むセリア系組成物、セリア系複合電解質粉末、及びこれらの焼結方法、並びにその焼結体 |
JP2018129215A (ja) * | 2017-02-09 | 2018-08-16 | 株式会社日本触媒 | ジルコニア電解質およびその製造方法 |
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US8182965B2 (en) * | 2008-09-30 | 2012-05-22 | Battelle Memorial Institute | Optimized cell configurations for stable LSCF-based solid oxide fuel cells |
DE112013003084T5 (de) * | 2012-06-19 | 2015-03-05 | Robert Bosch Gmbh | Metall/Luft-Batterie mit Gasseperations-Nanostruktur |
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