JP2016525268A - 固体酸化物燃料電池およびその製造方法 - Google Patents
固体酸化物燃料電池およびその製造方法 Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 100
- 239000007787 solid Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims description 89
- 239000011521 glass Substances 0.000 claims description 88
- 239000002243 precursor Substances 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 13
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 229910007472 ZnO—B2O3—SiO2 Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- -1 B 2 O 3 Inorganic materials 0.000 claims description 5
- 238000010345 tape casting Methods 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 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
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 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 2
- 238000001035 drying Methods 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000001878 scanning electron micrograph Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012528 membrane Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 229910052712 strontium Inorganic materials 0.000 description 6
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002001 electrolyte material Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910003099 (Y2O3)x(ZrO2)1−x Inorganic materials 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- 229910019525 La0.6Sr0.4Co0.8Fe0.2O3 Inorganic materials 0.000 description 1
- 229910002204 La0.8Sr0.2MnO3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 241000968352 Scandia <hydrozoan> Species 0.000 description 1
- 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 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
空気極前駆体、電解質前駆体としてLa2O3−B2O3−BaO−TiO2系ガラスフリットが全体電解質前駆体に対して5重量%含まれたYSZ、および燃料極前駆体を、それぞれテープキャスティング法を利用して膜を形成し、これらを順次に積層した。さらに、前記積層された膜を1,350℃の温度で焼成して、固体酸化物燃料電池を製造した。そして、製造された固体酸化物燃料電池の電解質膜の緻密度を検査するために、電解質の断面を電子顕微鏡(SEM)で確認した。
ガラスフリットの含有量を10重量%にしたことを除き、前記実施例1と同様の方法で固体酸化物燃料電池を製造し、電解質の断面を電子顕微鏡(SEM)で確認した。
ガラスフリットを含まないことを除き、前記実施例1と同様の方法で固体酸化物燃料電池を製造し、電解質の断面を電子顕微鏡(SEM)で確認した。
空気極前駆体、電解質前駆体としてLa2O3−B2O3−BaO−TiO2系ガラスフリットが全体電解質前駆体に対して5重量%含まれたYSZ、および燃料極前駆体を、それぞれテープキャスティング法を利用して膜を形成し、これらを順次に積層した。さらに、前記積層された膜を1250℃の温度で焼成して、固体酸化物燃料電池を製造した。そして、製造された固体酸化物燃料電池の電解質膜の緻密度を検査するために、電解質の断面を電子顕微鏡(SEM)で確認した。
ガラスフリットの含有量を10重量%にしたことを除き、前記実施例3と同様の方法で固体酸化物燃料電池を製造し、電解質の断面を電子顕微鏡(SEM)で確認した。
ガラスフリットを含まないことを除き、前記実施例3と同様の方法で固体酸化物燃料電池を製造し、電解質の断面を電子顕微鏡(SEM)で確認した。
空気極前駆体、電解質前駆体としてLa2O3−B2O3−BaO−TiO2系ガラスフリットが全体電解質前駆体に対して5重量%含まれたGDC、および燃料極前駆体を、それぞれテープキャスティング法を利用して膜を形成し、これらを順次に積層した。さらに、前記積層された膜を1350℃の温度で焼成して、固体酸化物燃料電池を製造した。そして、製造された固体酸化物燃料電池の電解質膜の緻密度を検査するために、電解質の断面を電子顕微鏡(SEM)で確認した。
ガラスフリットの含有量を10重量%にしたことを除き、前記実施例5と同様の方法で固体酸化物燃料電池を製造し、電解質の断面を電子顕微鏡(SEM)で確認した。
ガラスフリットを含まないことを除き、前記実施例5と同様の方法で固体酸化物燃料電池を製造し、電解質の断面を電子顕微鏡(SEM)で確認した。
Claims (16)
- 空気極と、燃料極と、前記空気極および前記燃料極の間に備えられた電解質とを含み、
前記空気極、前記燃料極、および前記電解質のうちの少なくとも1つは、ガラスフリットまたは前記ガラスフリット由来の物質を含む固体酸化物燃料電池。 - 前記ガラスフリットまたは前記ガラスフリット由来の物質は、焼結助剤である請求項1に記載の固体酸化物燃料電池。
- 前記ガラスフリットは、SiO2、B2O3、Al2O3、Bi2O3、PbO、CaO、BaO、LiO、MgO、Na2O、K2O、ZnO、MnO、ZrO2、V2O5、P2O5、Y2O3、SrO、GaO、Se2O3、TiO2、およびLa2O3からなる群より選択される1種以上を含むものである請求項1に記載の固体酸化物燃料電池。
- 前記ガラスフリットは、ZnO−SiO2系、ZnO−B2O3−SiO2系、ZnO−B2O3−SiO2−Al2O3系、Bi2O3−SiO2系、Bi2O3−B2O3−SiO2系、Bi2O3−B2O3−SiO2−Al2O3系、Bi2O3−ZnO−B2O3−SiO2系、Bi2O3−ZnO−B2O3−SiO2−Al2O3系、およびLa2O3−B2O3−BaO−TiO2系ガラスフリットからなる群より選択される1種以上を含むものである請求項1に記載の固体酸化物燃料電池。
- 前記ガラスフリットのガラス転移温度(Tg)は、450℃以上900℃以下である請求項1に記載の固体酸化物燃料電池。
- 前記電解質は、前記ガラスフリットまたは前記ガラスフリット由来の物質を含むものである請求項1に記載の固体酸化物燃料電池。
- 前記ガラスフリットまたは前記ガラスフリット由来の物質の含有量は、前記電解質の総重量に対して0.01重量%以上10重量%以下である請求項6に記載の固体酸化物燃料電池。
- 前記電解質は、前記ガラスフリットまたはガラスフリット由来の物質がない状態より、焼成温度が1%〜50%さらに低いものである請求項6に記載の固体酸化物燃料電池。
- 前記ガラスフリット由来の物質は、前記ガラスフリットが溶融後再凝固したものである請求項1に記載の固体酸化物燃料電池。
- 前記電解質の空隙率は、0%以上5%以下である請求項1に記載の固体酸化物燃料電池。
- 前記電解質は、酸化ジルコニウム系、酸化セリウム系、酸化ランタン系、酸化チタン系、酸化ビズマス系物質からなる群より選択される1種以上を含む複合金属酸化物を含むものである請求項1に記載の固体酸化物燃料電池。
- 前記固体酸化物燃料電池は、平板型、円筒型、または平管型である請求項1に記載の固体酸化物燃料電池。
- 空気極前駆体を用意するステップと、
電解質前駆体を用意するステップと、
燃料極前駆体を用意するステップと、
前記空気極前駆体と前記燃料極前駆体との間に前記電解質前駆体を備えるステップと、
前記空気極前駆体、前記電解質前駆体、および前記燃料極前駆体を同時に焼成する焼成ステップとを含み、
前記空気極前駆体、前記電解質前駆体、および前記燃料極前駆体のうちの少なくとも1つは、ガラスフリットを含む固体酸化物燃料電池の製造方法。 - 前記焼成ステップの温度は、800℃以上1,600℃以下である請求項13に記載の固体酸化物燃料電池の製造方法。
- 前記電解質前駆体は、ガラスフリットを含むものである請求項13に記載の固体酸化物燃料電池の製造方法。
- 前記空気極前駆体を用意するステップ、前記電解質前駆体を用意するステップ、および前記燃料極前駆体を用意するステップは、それぞれ独立に、テープキャスティング法またはスクリーンプリンティング法を利用して膜を形成した後、乾燥するステップを含むものである請求項13に記載の固体酸化物燃料電池の製造方法。
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