JP6526204B2 - 固体酸化物燃料電池の製造方法、固体酸化物燃料電池およびこれを含む電池モジュール - Google Patents
固体酸化物燃料電池の製造方法、固体酸化物燃料電池およびこれを含む電池モジュール Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims description 136
- 239000007787 solid Substances 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000009792 diffusion process Methods 0.000 claims description 49
- 239000003792 electrolyte Substances 0.000 claims description 36
- 239000008188 pellet Substances 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- -1 oxygen ion Chemical class 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 16
- 239000010954 inorganic particle Substances 0.000 claims description 15
- 229910000859 α-Fe Inorganic materials 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000011267 electrode slurry Substances 0.000 claims description 6
- PACGUUNWTMTWCF-UHFFFAOYSA-N [Sr].[La] Chemical compound [Sr].[La] PACGUUNWTMTWCF-UHFFFAOYSA-N 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- HHWBWNRYGPXTSW-UHFFFAOYSA-N [Co]=O.[Sr].[Gd] Chemical compound [Co]=O.[Sr].[Gd] HHWBWNRYGPXTSW-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- MGYPLPRYNYINRY-UHFFFAOYSA-N [Cu]=O.[Sr].[La] Chemical compound [Cu]=O.[Sr].[La] MGYPLPRYNYINRY-UHFFFAOYSA-N 0.000 claims description 3
- UCZPLOPQBJXLFF-UHFFFAOYSA-N [Ni].[Ca].[La] Chemical compound [Ni].[Ca].[La] UCZPLOPQBJXLFF-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 3
- 241000968352 Scandia <hydrozoan> Species 0.000 claims description 2
- JZMOMQOPNXIJMG-UHFFFAOYSA-N [Co].[Sr].[Ba] Chemical compound [Co].[Sr].[Ba] JZMOMQOPNXIJMG-UHFFFAOYSA-N 0.000 claims description 2
- QBYHSJRFOXINMH-UHFFFAOYSA-N [Co].[Sr].[La] Chemical compound [Co].[Sr].[La] QBYHSJRFOXINMH-UHFFFAOYSA-N 0.000 claims description 2
- FZJJTYLFARYPAT-UHFFFAOYSA-N [Ni].[Sr].[La] Chemical compound [Ni].[Sr].[La] FZJJTYLFARYPAT-UHFFFAOYSA-N 0.000 claims description 2
- YMVZSICZWDQCMV-UHFFFAOYSA-N [O-2].[Mn+2].[Sr+2].[La+3] Chemical compound [O-2].[Mn+2].[Sr+2].[La+3] YMVZSICZWDQCMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910002086 ceria-stabilized zirconia Inorganic materials 0.000 claims description 2
- 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 2
- OPWCPCQWULFDNJ-UHFFFAOYSA-N [Sr].[Co]=O Chemical compound [Sr].[Co]=O OPWCPCQWULFDNJ-UHFFFAOYSA-N 0.000 claims 2
- 229910003099 (Y2O3)x(ZrO2)1−x Inorganic materials 0.000 claims 1
- GQHZBSPNWMRGMM-UHFFFAOYSA-N [Co].[Sr] Chemical compound [Co].[Sr] GQHZBSPNWMRGMM-UHFFFAOYSA-N 0.000 claims 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims 1
- 229910001195 gallium oxide Inorganic materials 0.000 claims 1
- 229910021318 lanthanum strontium oxide Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- ZXMVMNJYECENGY-UHFFFAOYSA-N strontium lanthanum(3+) oxygen(2-) Chemical compound [O-2].[Sr+2].[La+3] ZXMVMNJYECENGY-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000008901 benefit Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FGKCIYWRWOMEDX-UHFFFAOYSA-N [Fe].[Co].[Ba] Chemical compound [Fe].[Co].[Ba] FGKCIYWRWOMEDX-UHFFFAOYSA-N 0.000 description 1
- OQKOQEWPYHIUMN-UHFFFAOYSA-N [Sr].[Co]=O.[Sm] Chemical compound [Sr].[Co]=O.[Sm] OQKOQEWPYHIUMN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- LFKMKZZIPDISEK-UHFFFAOYSA-L magnesium;4-carboxy-2,6-dihydroxyphenolate Chemical compound [Mg+2].OC1=CC(C([O-])=O)=CC(O)=C1O.OC1=CC(C([O-])=O)=CC(O)=C1O LFKMKZZIPDISEK-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002002 slurry Substances 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
- 230000003746 surface roughness Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
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- H01M4/88—Processes of manufacture
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- H01M4/8828—Coating with slurry or ink
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- H—ELECTRICITY
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- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
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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
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
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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
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
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- 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
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Description
NiとGDCが5:5の体積比(NiO:GDC61:39の重量比)で混合されている燃料極(固形分総重量を基準として10wt.%carbon black)グリーンシートを1400℃で3時間仮焼結(pre−sintering)を進行させた後、アルミナプレートを燃料極支持体の両面に接触させ、1500℃で3時間完全焼結(full−sintering)した。
実施例において、拡散プレートを燃料極グリーンシートに接触させず、燃料極グリーンシートのみ1400℃で3時間仮焼結(pre−sintering)を進行させた後、1500℃で3時間完全焼結(full−sintering)したことを除き、実施例と同様にして燃料極を製造した。
実施例および比較例の燃料極の表面を走査電子顕微鏡(SEM)で観察し、その結果をそれぞれ図3および図4に示した。
実施例および比較例の燃料極のそれぞれの温度による還元度(Degree of Reduction)を4−point probe methodを用いて測定した結果を図5に示した。
10mmX25mmX0.8mmの体積で製造された実施例および比較例を、それぞれ表面の任意の地点を選択して、1mmX1.2mmの面積に対する表面粗さをNanoMap社のOptical Profilerで測定した。
200:電解質層
300:空気極
Claims (6)
- 酸素イオン伝導性無機物粒子およびNiOを含む燃料極スラリーを用いて燃料極グリーンシートを製造するか、酸素イオン伝導性無機物粒子およびNiOを含む固形分を用いてペレットを製造するステップと、
前記燃料極グリーンシートまたはペレットの一面に拡散プレートを接触させるステップと、
前記拡散プレートが接触した燃料極グリーンシートまたはペレットを焼結して燃料極を製造するステップと、
前記焼結された燃料極から拡散プレートを分離するステップと、
前記焼結された燃料極中の拡散プレートの分離された面に電解質層および空気極を順次に形成するステップとを含み、
前記拡散プレートは、アルミナ、ジルコニア、セリア、およびイットリア安定化ジルコニアのうちの少なくとも1つを含むものであり、
前記焼結された燃料極中の拡散プレートの分離された表面の反対表面のNiOの量の100重量部を基準として、前記焼結された燃料極中の拡散プレートの分離された表面のNiOの量は、70重量部以下である、固体酸化物燃料電池の製造方法。 - 前記焼結された燃料極は、燃料極支持体である、請求項1に記載の固体酸化物燃料電池の製造方法。
- 前記焼結された燃料極支持体の厚さは、100μm以上5mm以下である、請求項1または2に記載の固体酸化物燃料電池の製造方法。
- 前記拡散プレートが接触した燃料極グリーンシートまたはペレットの焼結温度は、1100℃以上1600℃以下である、請求項1から3のいずれか一項に記載の固体酸化物燃料電池の製造方法。
- 前記拡散プレートが接触した燃料極グリーンシートまたはペレットの焼結時間は、1時間以上5時間以下である、請求項1から4のいずれか一項に記載の固体酸化物燃料電池の製造方法。
- 前記酸素イオン伝導性無機物粒子は、イットリア(yttria)安定化酸化ジルコニウム(zirconia)(YSZ:(Y2O3)x(ZrO2)1−x、x=0.05〜0.15)、スカンジア安定化酸化ジルコニウム(ScSZ:(Sc2O3)x(ZrO2)1−x、x=0.05〜0.15)、サマリウムドープセリア(ceria)(SDC:(Sm2O3)x(CeO2)1−x、x=0.02〜0.4)、ガドリニウムドープセリア(ceria)(GDC:(Gd2O3)x(CeO2)1−x、x=0.02〜0.4)、ランタンストロンチウムマンガン酸化物(Lanthanum strontium manganese oxide:LSM)、ランタンストロンチウムコバルトフェライト(Lanthanum strontium cobalt ferrite:LSCF)、ランタンストロンチウムニッケルフェライト(Lanthanum strontium nickel ferrite:LSNF)、ランタンカルシウムニッケルフェライト(Lanthanum calcium nickel ferrite:LCNF)、ランタンストロンチウム銅酸化物(Lanthanum strontium copper oxide:LSC)、ガドリニウムストロンチウムコバルト酸化物(Gadolinium strontium cobalt oxide:GSC)、ランタンストロンチウムフェライト(Lanthanum strontium ferrite:LSF)、サマリウムストロンチウムコバルト酸化物(Samarium strontium cobalt oxide:SSC)およびバリウムストロンチウムコバルトフェライト(Barium Strontium cobalt ferrite:BSCF)、並びにランタンストロンチウムガリウムマグネシウム酸化物(Lanthanum strontium gallium magnesium oxide:LSGM)のうちの少なくとも1つを含むものである、請求項1から5のいずれか一項に記載の固体酸化物燃料電池の製造方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020150120160A KR102054537B1 (ko) | 2015-08-26 | 2015-08-26 | 고체 산화물 연료전지의 제조방법, 고체 산화물 연료전지 및 이를 포함하는 전지 모듈 |
KR10-2015-0120160 | 2015-08-26 | ||
PCT/KR2016/009415 WO2017034334A1 (ko) | 2015-08-26 | 2016-08-25 | 고체 산화물 연료전지의 제조방법, 고체 산화물 연료전지 및 이를 포함하는 전지 모듈 |
Publications (2)
Publication Number | Publication Date |
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JP2018509730A JP2018509730A (ja) | 2018-04-05 |
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US6228521B1 (en) * | 1998-12-08 | 2001-05-08 | The University Of Utah Research Foundation | High power density solid oxide fuel cell having a graded anode |
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