Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cells
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Outros Autores: | , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10773/31784 |
Resumo: | Manganese-substituted 5 mol.% yttria-stabilized zirconia (5YSZ) was explored as a prospective material for protective interlayers between electrolyte and oxygen electrodes in reversible solid oxide fuel/electrolysis cells. [(ZrO2)0.95(Y2O3)0.05]1-x[MnOy]x (x = 0.05, 0.10 and 0.15) ceramics with cubic fluorite structure were sintered in air at 1600 °C. The characterization included X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetry and dilatometry in controlled atmospheres, electrical conductivity measurements, and determination of oxygen-ion transference numbers by the electromotive force (EMF) technique. Mn-substituted 5YSZ solid solutions exhibit variable oxygen nonstoichiometry with manganese cations in a mixed 2+/3+ oxidation state under oxidizing conditions. Substitution by manganese gradually increases the extent of oxygen content variation on thermal/redox cycling, chemical contribution to thermal expansion and dimensional changes on reduction. It also deteriorates oxygen-ionic conductivity and improves p-type electronic conductivity under oxidizing conditions, leading to a gradual transformation from predominantly ionic to prevailing electronic transport with increasing x. Mn2+/3+→Mn2+ transformation under reducing atmospheres is accompanied by the suppression of electronic transport and an increase in ionic conductivity. All Mn-substituted 5YSZ ceramics are solid electrolytes under reducing conditions. Prolonged treatments in reducing atmospheres, however, promote microstructural changes at the surface of bulk ceramics and Mn exsolution. Mn-substituted 5YSZ with 0.05 ≤ x < 0.10 is considered the most suitable for the interlayer application, due to the best combination of relevant factors, including oxygen content variations, levels of ionic/electronic conductivity and thermochemical expansion. |
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Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cellsSolid oxide fuel cellSolid oxide electrolysis cellZirconiaManganese oxideIonic conductivityThermochemical expansionOxygen nonstoichiometryMixed conductorBuffer layerManganese-substituted 5 mol.% yttria-stabilized zirconia (5YSZ) was explored as a prospective material for protective interlayers between electrolyte and oxygen electrodes in reversible solid oxide fuel/electrolysis cells. [(ZrO2)0.95(Y2O3)0.05]1-x[MnOy]x (x = 0.05, 0.10 and 0.15) ceramics with cubic fluorite structure were sintered in air at 1600 °C. The characterization included X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetry and dilatometry in controlled atmospheres, electrical conductivity measurements, and determination of oxygen-ion transference numbers by the electromotive force (EMF) technique. Mn-substituted 5YSZ solid solutions exhibit variable oxygen nonstoichiometry with manganese cations in a mixed 2+/3+ oxidation state under oxidizing conditions. Substitution by manganese gradually increases the extent of oxygen content variation on thermal/redox cycling, chemical contribution to thermal expansion and dimensional changes on reduction. It also deteriorates oxygen-ionic conductivity and improves p-type electronic conductivity under oxidizing conditions, leading to a gradual transformation from predominantly ionic to prevailing electronic transport with increasing x. Mn2+/3+→Mn2+ transformation under reducing atmospheres is accompanied by the suppression of electronic transport and an increase in ionic conductivity. All Mn-substituted 5YSZ ceramics are solid electrolytes under reducing conditions. Prolonged treatments in reducing atmospheres, however, promote microstructural changes at the surface of bulk ceramics and Mn exsolution. Mn-substituted 5YSZ with 0.05 ≤ x < 0.10 is considered the most suitable for the interlayer application, due to the best combination of relevant factors, including oxygen content variations, levels of ionic/electronic conductivity and thermochemical expansion.MDPI2021-08-04T09:44:14Z2021-02-01T00:00:00Z2021-02-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10773/31784eng10.3390/ma14030641Natoli, AlejandroArias-Serrano, Blanca I.Rodríguez-Castellón, EnriqueŻurawska, AgnieszkaFrade, Jorge R.Yaremchenko, Aleksey A.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-02-22T12:01:16Zoai:ria.ua.pt:10773/31784Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T03:03:33.749267Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cells |
title |
Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cells |
spellingShingle |
Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cells Natoli, Alejandro Solid oxide fuel cell Solid oxide electrolysis cell Zirconia Manganese oxide Ionic conductivity Thermochemical expansion Oxygen nonstoichiometry Mixed conductor Buffer layer |
title_short |
Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cells |
title_full |
Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cells |
title_fullStr |
Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cells |
title_full_unstemmed |
Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cells |
title_sort |
Mixed ionic-electronic conductivity, redox behavior and thermochemical expansion of Mn-Substituted 5YSZ as an interlayer material for reversible solid oxide cells |
author |
Natoli, Alejandro |
author_facet |
Natoli, Alejandro Arias-Serrano, Blanca I. Rodríguez-Castellón, Enrique Żurawska, Agnieszka Frade, Jorge R. Yaremchenko, Aleksey A. |
author_role |
author |
author2 |
Arias-Serrano, Blanca I. Rodríguez-Castellón, Enrique Żurawska, Agnieszka Frade, Jorge R. Yaremchenko, Aleksey A. |
author2_role |
author author author author author |
dc.contributor.author.fl_str_mv |
Natoli, Alejandro Arias-Serrano, Blanca I. Rodríguez-Castellón, Enrique Żurawska, Agnieszka Frade, Jorge R. Yaremchenko, Aleksey A. |
dc.subject.por.fl_str_mv |
Solid oxide fuel cell Solid oxide electrolysis cell Zirconia Manganese oxide Ionic conductivity Thermochemical expansion Oxygen nonstoichiometry Mixed conductor Buffer layer |
topic |
Solid oxide fuel cell Solid oxide electrolysis cell Zirconia Manganese oxide Ionic conductivity Thermochemical expansion Oxygen nonstoichiometry Mixed conductor Buffer layer |
description |
Manganese-substituted 5 mol.% yttria-stabilized zirconia (5YSZ) was explored as a prospective material for protective interlayers between electrolyte and oxygen electrodes in reversible solid oxide fuel/electrolysis cells. [(ZrO2)0.95(Y2O3)0.05]1-x[MnOy]x (x = 0.05, 0.10 and 0.15) ceramics with cubic fluorite structure were sintered in air at 1600 °C. The characterization included X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetry and dilatometry in controlled atmospheres, electrical conductivity measurements, and determination of oxygen-ion transference numbers by the electromotive force (EMF) technique. Mn-substituted 5YSZ solid solutions exhibit variable oxygen nonstoichiometry with manganese cations in a mixed 2+/3+ oxidation state under oxidizing conditions. Substitution by manganese gradually increases the extent of oxygen content variation on thermal/redox cycling, chemical contribution to thermal expansion and dimensional changes on reduction. It also deteriorates oxygen-ionic conductivity and improves p-type electronic conductivity under oxidizing conditions, leading to a gradual transformation from predominantly ionic to prevailing electronic transport with increasing x. Mn2+/3+→Mn2+ transformation under reducing atmospheres is accompanied by the suppression of electronic transport and an increase in ionic conductivity. All Mn-substituted 5YSZ ceramics are solid electrolytes under reducing conditions. Prolonged treatments in reducing atmospheres, however, promote microstructural changes at the surface of bulk ceramics and Mn exsolution. Mn-substituted 5YSZ with 0.05 ≤ x < 0.10 is considered the most suitable for the interlayer application, due to the best combination of relevant factors, including oxygen content variations, levels of ionic/electronic conductivity and thermochemical expansion. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-08-04T09:44:14Z 2021-02-01T00:00:00Z 2021-02-01 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10773/31784 |
url |
http://hdl.handle.net/10773/31784 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.3390/ma14030641 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
MDPI |
publisher.none.fl_str_mv |
MDPI |
dc.source.none.fl_str_mv |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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