JP2018504344A - 構造 - Google Patents
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- JP2018504344A JP2018504344A JP2017528514A JP2017528514A JP2018504344A JP 2018504344 A JP2018504344 A JP 2018504344A JP 2017528514 A JP2017528514 A JP 2017528514A JP 2017528514 A JP2017528514 A JP 2017528514A JP 2018504344 A JP2018504344 A JP 2018504344A
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- perovskite
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- fuel cell
- tungsten
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- 238000010276 construction Methods 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 32
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000446 fuel Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000007858 starting material Substances 0.000 claims abstract description 18
- 229910052788 barium Inorganic materials 0.000 claims abstract description 16
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 9
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 9
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052746 lanthanum Chemical group 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 description 34
- 239000013078 crystal Substances 0.000 description 17
- 239000002019 doping agent Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000003068 static effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- -1 oxygen ion Chemical class 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910002722 Ba0.5Sr0.5Co0.5Fe0.125Mo0.375O3−δ Inorganic materials 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000003991 Rietveld refinement Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ABEXEQSGABRUHS-UHFFFAOYSA-N 16-methylheptadecyl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC(C)C ABEXEQSGABRUHS-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 238000004813 Moessbauer spectroscopy Methods 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001383 neutron diffraction data Methods 0.000 description 1
- 238000001956 neutron scattering Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002216 synchrotron radiation X-ray diffraction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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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
- 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
- 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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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
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- H01M4/90—Selection of catalytic material
-
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
-
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
- C01G51/68—Cobaltates containing alkaline earth metals, e.g. SrCoO3 containing rare earth, e.g. La0.3Sr0.7CoO3
-
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/70—Cobaltates containing rare earth, e.g. LaCoO3
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/521—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of iron for aqueous cells
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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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- 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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Abstract
Description
本発明は、燃料電気中で用いられる構造に関する。具体的には、固体酸化物型燃料電池(SOFC)中で電極として用いられるペロブスカイト構造及びその製造方法に関する。
SOFCは、(通常水素系の)燃料ガスの電気化学酸化による電気エネルギーの生成のための電気化学デバイスである。デバイスは、一般的にはセラミック系であり、その電解質として酸素イオン伝導性の金属酸化物由来セラミックを用いる。ほとんどのセラミック酸素イオン伝導体(例えば、ドープジルコニア酸化物又はドープセリウム酸化物)は、(セリウム酸化物系電解質に関して)500℃又は(ジルコニウム酸化物系セラミックに関して)650℃を超える温度にて技術的に関連したイオン伝導を示すのみであるため、SOFCは高温で動作する。
本発明の第一の側面において、第一の元素X、ストロンチウム、鉄、コバルト、酸素、及びタングステンを含むペロブスカイト構造であって、第一の元素Xがバリウム及び/又はランタニドであり、構造がシングルペロブスカイト(SP)の領域及びダブルペロブスカイト(DP)の領域を含む、構造が提供される。
(Ba1-xSrx)(Co1-yFey)aWbOc
(式中、x及びyの両方は独立して0.1〜0.9の範囲であり、a+bは1に等しい。)
を有する。この構造は、本発明の典型的なペロブスカイト材料に関する平均的な化学式であることが意図される。典型的なペロブスカイト構造の異なる領域は、組成及び構造が変化するであろう。この式中の元素のモル比、及び対応する記載の値(a、b又はa+bの値を含む)は、厳密な値又は整数として解釈されるべきではない。結晶構造中の欠陥、格子間イオン、不純物及び他のバリエーションは、全てのイオン格子中に本質的に生じ、更に、本開示に記載のペロブスカイト構造は、少なくともシングル及びダブルペロブスカイトの両方の領域を有する。
製造方法
高純度のBaCo3、SrCo3、Co3O4、Fe2O3及びWO3が、Ba0.5Sr0.5(CoxFey)1-zWzO3-δサンプルを調製するのに用いられた。粉末はボールミルされ(350rpm終夜、Fritsch Pulverisette 7 Planetary Mill)、再びボールミルする前に、初めに700℃に6時間、次いで900℃に8時間加熱された。得られた粉末は、次いでペレット(1.3cm直径)として圧縮され、12時間1200℃にて焼結された。相純度は、x線粉末回折(Co Kα1放射=1.78901ÅによるPanalytical X‐pert Pro Bragg‐Brentano geometry laboratory x‐ray diffractometer)を用いて決定された。Ba0.5Sr0.5(Co0.7Fe0.3)0.6875W0.3125O3-δの詳細な構造の情報に関して、シンクトロンx線回折データがダイアモンド光源(UK)にてビームラインI11で記録され、中性子飛行時間回折データが、ISIS施設(Rutherford Appleton研究所、UK)における回折計HRRDに記録された。構造パラメータは、ソフトウェアTopasを用いてリートベルト法により精密化された。
相図(図1)中の全ての組成に関する研究x線回折パターンは、他の不純物を含まないシングル(SP)及びダブル(DP)相の共存を示し、そのTEM研究は、SPとDP間のエンドタキシャル相互成長を確認した(図2及び3)。初めに、Ba0.5Sr0.5(Co0.8Fe0.2)1-zWzO3-dシリーズが調製され、特性評価された。z=0.3125サンプルは、シリーズ中で最も低いASR(600℃において約0.1Ωcm2)を示したが、5日間以上750℃にて静的空気中でアニールされた場合(図4)、BSCFのものよりはるかに重要ではなく、遅いものの、六方晶相の形成を被った。モリブデンドープの従来の研究より良好な熱的安定性を示すことが期待されたため(Demont,A.ら、「Single Sublattice Endotaxial Phase Separation Driven by Charge Frustration in a Complex Oxide」、J.Am.Chem.Soc、2013、135、第10114〜10123頁参照)、より高いz値を有するサンプルが次いで試行された。一見してz=0.375サンプルは、熱的安定性試験後に六方晶相の兆候を示さなかった。しかし、それがより長くアニールされ、図5において示されたようにパターンの強度が対数軸で表示された際、六方晶相の結晶化の明確な証拠があった。Ba0.5Sr0.5(Co0.8Fe0.2)1-zWzO3-dシリーズから離れた相図の体系的な研究が続けられ、カソード性能及び安定性の観点で最適化された組成はBa0.5Sr0.5(Co0.7Fe0.3)1-zWzO3-δと特定された。
Claims (28)
- 第一の元素X、ストロンチウム、鉄、コバルト、酸素、及びタングステンを含むペロブスカイト構造であって、
前記第一の元素Xがバリウム及び/又はランタニドであり、
前記構造が、シングルペロブスカイトの領域及びダブルペロブスカイトの領域を含む、前記構造。 - 前記第一の元素Xが、バリウム又はランタンである、請求項1に記載の構造。
- 前記第一の元素Xがバリウムである、請求項2に記載の構造。
- タングステンのモルパーセントが、5〜10%の範囲である、請求項1〜3のいずれか1項に記載の構造。
- 前記構造が、化学式:
(Ba1-xSrx)(Co1-yFey)aWbOc
(式中、x及びyの両方は独立して0.1〜0.9の範囲であり、a+bは1に等しく、cは2〜3の範囲である。)
を有する、請求項1〜4のいずれか1項に記載の構造。 - cが3である、請求項5に記載の構造。
- xが0.4〜0.6の範囲である、請求項6に記載の構造。
- yが0.1〜0.4の範囲である、請求項6又は7に記載の構造。
- シングルペロブスカイトとダブルペロブスカイトとの比が、1:1〜1:9の範囲である、請求項1〜8のいずれか1項に記載の構造。
- 請求項1〜9のいずれか1項に記載の構造を含む、燃料電池用の電極。
- 前記電極がカソードである、請求項10に記載の電極。
- 請求項1〜9のいずれか1項に記載の構造を含む燃料電池。
- 前記燃料電池が固体酸化物型燃料電池である、請求項12に記載の燃料電池。
- 請求項12又は13に記載の1つ又はそれより多くの燃料電池を含む、燃料電池スタック。
- 請求項1〜9のいずれか1項に記載のペロブスカイト構造の形成方法であって、
第一の元素X、ストロンチウム、鉄、コバルト、酸素、及びタングステンを含む出発材料を混合して混合物を形成することと、
前記混合物を第一の所定の期間、第一の温度に加熱してシングルペロブスカイトを形成することと、
前記混合物を第二の所定の期間、第二の温度に加熱してダブルペロブスカイトを形成することとを含み、
前記第一の元素Xがバリウム及び/又はランタニドである、前記方法。 - 前記第一の元素Xがバリウムである、請求項15に記載の方法。
- 前記加熱工程の前に粉砕工程を更に含む、請求項15又は16に記載の方法。
- 前記粉砕工程がボールミルである、請求項17に記載の方法。
- 粉砕された出発物質が加熱工程の前に圧縮される、請求項17又は18に記載の方法。
- 前記第一の温度が650℃〜750℃の範囲である、請求項15〜19のいずれか1項に記載の方法。
- 前記第二の温度が850℃〜1000℃の範囲である、請求項15〜20のいずれか1項に記載の方法。
- 前記第一の所定の期間が4〜8時間の範囲である、請求項15〜21のいずれか1項に記載の方法。
- 前記第二の所定の期間が6〜10時間の範囲である、請求項15〜22のいずれか1項に記載の方法。
- 前記第二の加熱工程の後に、第三の所定の期間、空気中で第三の温度にて焼結する工程を更に含む、請求項15〜23のいずれか1項に記載の方法。
- 前記第三の温度が950℃〜1100℃の範囲である、請求項24に記載の方法。
- 前記第三の所定の期間が8〜12時間の範囲である、請求項24又は25に記載の方法。
- 前記方法が少なくとも1回繰り返される、請求項15〜26のいずれか1項に記載の方法。
- 添付の明細書及び図面に関連して本開示に記載された構造、電極、燃料電池、燃料電池スタック又は方法。
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