JP2007510255A - 固体酸化物燃料電池の製造 - Google Patents
固体酸化物燃料電池の製造 Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 45
- 239000007787 solid Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 70
- 239000002001 electrolyte material Substances 0.000 claims abstract description 53
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000151 deposition Methods 0.000 claims abstract description 10
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- 239000002270 dispersing agent Substances 0.000 claims description 18
- 239000004014 plasticizer Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
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- ZXIMJENGZNNPHH-UHFFFAOYSA-N cobalt(2+) gadolinium(3+) oxygen(2-) Chemical compound [O-2].[Gd+3].[Co+2] ZXIMJENGZNNPHH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 2
- 229940075613 gadolinium oxide Drugs 0.000 claims description 2
- HZLLPQBYQASDPK-UHFFFAOYSA-N gadolinium(3+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Gd+3].[Ni+2] HZLLPQBYQASDPK-UHFFFAOYSA-N 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
- 239000011262 electrochemically active material Substances 0.000 claims 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 2
- 229910052726 zirconium Inorganic materials 0.000 claims 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 2
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- RIAXXCZORHQTQD-UHFFFAOYSA-N lanthanum magnesium Chemical compound [Mg].[La] RIAXXCZORHQTQD-UHFFFAOYSA-N 0.000 claims 1
- -1 lanthanum manganite-yttrium Chemical compound 0.000 claims 1
- IKBUJAGPKSFLPB-UHFFFAOYSA-N nickel yttrium Chemical compound [Ni].[Y] IKBUJAGPKSFLPB-UHFFFAOYSA-N 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
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- BQENXCOZCUHKRE-UHFFFAOYSA-N [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O Chemical compound [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O BQENXCOZCUHKRE-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- NFYLSJDPENHSBT-UHFFFAOYSA-N chromium(3+);lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[La+3] NFYLSJDPENHSBT-UHFFFAOYSA-N 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
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- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
Classifications
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- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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Abstract
【選択図】図2
Description
この出願は、発明の名称 燃料電池の製造のための単一段階による共焼成方法として、2003年9月10日に、アメリカ合衆国仮出願第60/501,742号に基づく優先権を主張する。
燃料電池は酸素と水素が結合して水になる電気化学的反応により電気を発生するシステムまたは装置である。電池内の電解質は、電荷粒子をカソードからアノードへ輸送する。触媒はしばしば使用されて、電気化学的反応を促進してその効率を向上する。燃料電池機器は代替エネルギー源として見こみあるものである。これらの機器は従来の電源よりも効率よくまた公害源となることが少ない。燃料電池から製造される電力は、たとえば、航空機、コンピューター機器、自動車および携帯電話機器などへ電力を供給する。
本発明は、電力キロワット当たり500ドルよりも安価なコストで固体酸化物燃料電池を製造する方法を提供する。本方法は、電極層を形成し、電極面に電解質材料を沈積することからなる。形成される構造は、電極−電解質の二層構造である。第2の電極は、この二層構造の上に沈積されて、多層燃料電気構造体となり、それは二つの電極間に電解質が位置する。この多層構造体は、その後、単一の加熱サイクルで加熱・焼成されて、バインダーを除去されて、焼結されて燃料電池となる。この加熱サイクルは、一つまたはそれ以上のチャンバーを有する炉の中で行なわれる。一つまたは複数のチャンバーは好ましくは、電池を加熱して電解質と電極構造体のバインダー材料を除去するために、可変のまたは多重の周波数のマイクロウエーブ源を含む。チャンバーはまた、好ましくは焼結のための対流または放射加熱源を含む。
本発明の他の特徴と利点は、以下の図面を参考にして、次ぎの本発明の詳細な説明から明らかであり、添付の図面は以下のとおりである:
図1は、多孔質構造体の間に位置する高密度電解質からなる固体酸化物燃料電池の部分説明図である。
図2は、数個の電池が各電池を仕切る相互連通板で配列した固体酸化物燃料電池(SOFC)の積み重ねの斜視図である。
図3は、本発明の方法で形成される多孔質電極層のフローチャートである。
図4は、本発明の方法により図3の電極面上に高密度電解質層が形成されるフローチャートであり、電極−電解質二層構造体である。
図5は、図4のフローチャーに示される本発明の方法で形成される電極−電解質二層構造体の画像である。
図6は、図4のフローチャートに示される本発明の方法により形成される電極−電解質・二層構造体の走査電子顕微鏡写真の図である。
図7は、図4の電解質面上に多孔質電極層が沈積するフローチャートであり、形成された多層構造体は、本発明に従う単一の加熱サイクルで加熱されて焼成される。
そして、
図8は、図3、4および7の方法に従い製造されるSOFCの部分斜視図であり、多層燃料電池は固体のイットリア安定化(yttria-stabilized)ジルコニア(YSZ)電解質からなり、それは、ストロンチウムをドープしたランタン マンガナイト−YSZカソードとニッケル−YSZ酸化物アノードの間に位置する。
本発明は単一の温度サイクルで固体酸化物燃料電池(SOFC)を製造する方法を提供する。このサイクルはバッチ式または連続式でも使用できる。SOFCは、本発明に従い、電力1キロワット当たり500ドルよりも安価なコストで適切に製造され得る。製造されるSOFCは約700〜1100℃の温度範囲で動作する。同様に、本発明の方法は数個の電池が各電池を仕切る相互連通販で配列するSOFCのスタック(積み重ね)を製造し得る。開示する方法で製造される燃料電池機器は、たとえば、航空機機器、コンピュータ機器、自動車機器および携帯電話機器に電力を供給するのに使用され得る。
22 ガイド板
24 アノード
26 カソード
28 分離板
Claims (28)
- 固体酸化物燃料電池の製造方法であって、前記方法は以下からなる:
第1の電極層を形成し、前記第1の電極層は面を有し;
第1の電極層の前記面上に電解質層を形成し;
電解質層の面上に第2の電極層を形成し、ここで当該層は多層の電気化学的構造体からなり;
マイクロウエーブのエネルギーを前記多層構造体に付与して各層から実質的にバインダーを除去し;そして
前記多層構造体を焼成して各層を焼結させる。 - さらに以下を含む請求項1の方法:
スラリーを沈積させて各層を形成し、前記スラリーはバインダー、分散剤、溶剤、可塑剤および複合材固体からなり;そして
スラリーを乾燥させて実質的に分散剤、溶剤および可塑材を除去する。 - マイクロウエーブ源は可変または多重周波数のマイクロウエーブ源から供給される請求項1の方法。
- 焼成が対流加熱、放射加熱またはこの組合せにより行なわれる請求項1の方法。
- 焼成が約1000℃よりも高温で行なわれる請求項1の方法。
- マイクロウエーブのエネルギーが約800℃よりも低い温度で供給される請求項1の方法。
- 第1の電極層がアノードとして作用する請求項1の方法。
- 第1の電極層が多孔質である請求項1の方法。
- 第1の電極層が約0.5〜2.0mmの範囲の厚みを有する請求項1の方法。
- 第2の電極層がカソードとして作用する請求項1の方法。
- 第2の電極層が多孔質である請求項10の方法。
- 第2の電極層が約50〜150μmの範囲の厚みを有する請求項11の方法。
- 電解質層が高密度固体である請求項1の方法。
- 電解質層が約5〜1000μmの範囲の厚みを有する請求項13の方法。
- 第1の電極層はセラミック複合体からなり、セラミック複合体は、ニッケル−イットリウム安定化ジルコニウム酸化物、ニッケル−ガドリニウム酸化物ドープのセリウム酸化物、ニッケル−サマリウム酸化物ドープのセリウム酸化物、コバルト−イットリウム安定化ジルコニウム酸化物、コバルト−ガドリニウム酸化物ドープのセリウム酸化物およびこれらの組合せからなる請求項7の方法。
- 第2の電極層がストロンチウムドープのランタン 亜マンガン酸−イットリウム安定化ジルコニウム セラミック複合材からなる請求項10の方法。
- 電解質層が伝導体からなり、該伝導体は、イットリウム安定化ジルコニウム、セリア・ガドリウム酸化物、ストロンチウム、マグネシウム・ランタン没食子酸塩、希土類金属ドープのセリウム酸化物およびこれらの組合せからなる請求項13の方法。
- 固体酸化物燃料電池の製造方法であって、該方法は以下からなる:
電気化学的に活性の材料の第1の層を備え、該第1の層は表面を有し;
第1の層の面上に電解質材料を沈積し;
電解質材料の面上に電気化学的に活性な材料を沈積し、ここで前記電解質材料は層間に配置されて多層の電気化学的構造体が構成され;そして
多層構造体を焼成して実質的に電解質材料と層を焼結させる。 - 電解質材料と層が、バインダー、分散剤、溶剤、可塑剤および複合体固体からなる請求項1の方法。
- さらに、多層構造体を加熱して電解質材料と層からバインダーを実質的に除去し、ここで多層構造体は焼成の前に加熱される請求項19の方法。
- さらに、第1の層を乾燥して実質的に分散剤、溶剤および可塑剤を除去し、ここで第1の層は電解質材料の沈積の前に乾燥され、そして乾燥した第1の層は所定の厚みを有する請求項1の方法。
- さらに、電解質材料を乾燥して実質的に分散剤、溶剤および可塑剤を除去し、ここで電解質材料は第2の層の沈積の前に乾燥され、そして乾燥した電解質材料は所定の厚みを有する請求項1の方法。
- さらに、第2の層を乾燥して実質的に分散剤、溶剤および可塑剤を除去し、ここで第2の層は多層構造体の焼成の前に乾燥され、そして乾燥した第2の層は所定の厚みを有する請求項1の方法。
- さらに以下からなる:
乾燥した第1の層の厚みを測定して要求厚みと比較し;
測定した厚みが要求値よりも薄い場合は、乾燥した第1の層の上に電気化学的活性な材料の追加の層を供給し、ここで前記追加の層は、バインダー、分散剤、溶剤、可塑剤および複合体固体からなるものであり;
追加の層を乾燥して分散剤、溶剤および可塑剤を実質的に除去し、該層は所定の厚みを有し;
前記所定の厚みを測定して要求値と比較し;そして
測定の値と要求値とがほぼ等しくなるまで追加と乾燥の工程を繰り返す、請求項21の方法。 - さらに以下からなる:
乾燥した電解質材料の厚みを測定して要求厚みと比較し;
測定した厚みが要求値よりも薄い場合は、乾燥した電解質材料の上に電気化学的活性な材料の追加の層を供給し、ここで前記追加の層は、バインダー、分散剤、溶剤、可塑剤および複合体固体からなるものであり;
追加の層を乾燥して分散剤、溶剤および可塑剤を実質的に除去し、該層は所定の厚みを有し;
前記所定の厚みを測定して要求値と比較し;そして
測定の値と要求値とがほぼ等しくなるまで追加と乾燥の工程を繰り返す、請求項22の方法。 - さらに以下からなる:
乾燥した第2の層の厚みを測定して要求厚みと比較し;
測定した厚みが要求値よりも薄い場合は、乾燥した第2の層の上に電気化学的活性な材料の追加の層を供給し、ここで前記追加の層は、バインダー、分散剤、溶剤、可塑剤および複合体固体からなるものであり;
追加の層を乾燥して分散剤、溶剤および可塑剤を実質的に除去し、該層は所定の厚みを有し;
前記所定の厚みを測定して要求値と比較し;そして
測定の値と要求値とがほぼ等しくなるまで追加と乾燥の工程を繰り返す、請求項23の方法。 - 固体酸化物燃料電池スタックの製造方法であって、該方法は以下からなる:
請求項1〜18のいずれかの方法を行ない;
多層電気化学的構造体の表面上に相互導通配線を配置し;そして
請求項1〜18のいずれかの方法を繰り返し、ここで相互導通配線は実質的に多層構造体を分離する。 - 化学エネルギーを電気と発熱に変換するように作用する固体酸化物燃料電池であって、該燃料電池は以下からなる:
多孔質アノード、該アノードは約0.5〜2.0mmの範囲の厚みを有し;
アノードの表面上に配置される固体電解質材料、該電解質材料は約5〜1000μmの範囲の厚みを有し;そして
電解質材料の表面上に配置される多孔質カソード、該カソードは約50〜150μmの範囲の厚みを有し、ここでアノード、電解質およびカソードは請求項1〜18のいずれかの方法により調製されるものである。
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- 2004-09-10 RU RU2006110158/09A patent/RU2362239C2/ru not_active IP Right Cessation
- 2004-09-10 CA CA2538224A patent/CA2538224C/en active Active
- 2004-09-10 WO PCT/US2004/029571 patent/WO2005027239A2/en active Application Filing
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- 2004-09-10 CN CN2004800328167A patent/CN101061596B/zh not_active Expired - Fee Related
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- 2004-09-10 KR KR1020067005088A patent/KR101136191B1/ko not_active IP Right Cessation
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Cited By (4)
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JP2012028088A (ja) * | 2010-07-21 | 2012-02-09 | Sumitomo Electric Ind Ltd | 膜電極複合体、燃料電池、ガス除害装置、および膜電極複合体の製造方法 |
JPWO2021025051A1 (ja) * | 2019-08-06 | 2021-02-11 | ||
WO2021025051A1 (ja) * | 2019-08-06 | 2021-02-11 | 株式会社村田製作所 | 固体酸化物形燃料電池用電解質シート、固体酸化物形燃料電池用電解質シートの製造方法及び固体酸化物形燃料電池用単セル |
JP7168090B2 (ja) | 2019-08-06 | 2022-11-09 | 株式会社村田製作所 | 固体酸化物形燃料電池用電解質シート、固体酸化物形燃料電池用電解質シートの製造方法及び固体酸化物形燃料電池用単セル |
Also Published As
Publication number | Publication date |
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CN101061596B (zh) | 2010-08-18 |
KR101136191B1 (ko) | 2012-04-17 |
CA2538224A1 (en) | 2005-03-24 |
AU2004272186B2 (en) | 2009-10-29 |
WO2005027239A2 (en) | 2005-03-24 |
CR8281A (es) | 2007-08-28 |
US7485385B2 (en) | 2009-02-03 |
EP1671385A4 (en) | 2009-03-25 |
JP5015598B2 (ja) | 2012-08-29 |
BRPI0414240A (pt) | 2006-10-31 |
KR20070019944A (ko) | 2007-02-16 |
US20050089739A1 (en) | 2005-04-28 |
AU2004272186B8 (en) | 2010-02-18 |
EP1671385A2 (en) | 2006-06-21 |
RU2362239C2 (ru) | 2009-07-20 |
WO2005027239A3 (en) | 2007-03-29 |
RU2006110158A (ru) | 2007-10-20 |
CA2538224C (en) | 2012-01-24 |
EP1671385B1 (en) | 2013-01-02 |
CN101061596A (zh) | 2007-10-24 |
AU2004272186A1 (en) | 2005-03-24 |
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