Defect structure and redox energetics of NdBaCo2O6-δ
The oxygen content in the double perovskite NdBaCo2O6-δ was measured as a function of oxygen partial pressure (1–10−5 atm) at different temperatures (623–1323 K) using thermogravimetry analysis (TG) and coulometric titration technique. The defect structure model of the oxide studied was proposed and...
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| Veröffentlicht in: | Solid state ionics 2021-03, Vol.361, p.115549, Article 115549 |
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| creator | Tsvetkov, Dmitry S. Yagovitin, Roman E. Sereda, Vladimir V. Malyshkin, Dmitry A. Ivanov, Ivan L. Zuev, Andrey Yu Maignan, Antoine |
| description | The oxygen content in the double perovskite NdBaCo2O6-δ was measured as a function of oxygen partial pressure (1–10−5 atm) at different temperatures (623–1323 K) using thermogravimetry analysis (TG) and coulometric titration technique. The defect structure model of the oxide studied was proposed and successfully verified using the pO2 – T – δ data, yielding the enthalpies and entropies of the defect reactions involved. Standard enthalpy of formation from elements (ΔfH298∘) was measured for quenched NdBaCo2O6-δ samples with different oxygen content. Regarding the ΔfH298∘(6-δ) dependences, two important observations were made. First, the ΔfH298∘(6-δ) consists of two linear fragments with different slopes reflecting different modes of oxygen exchange, accompanied by either reduction of cobalt from Co+3 to Co+2 or from Co+4 to Co+3 in the ranges 5.0 ≤ 6-δ ≤5.5 and 5.5 |
| doi_str_mv | 10.1016/j.ssi.2021.115549 |
| format | Article |
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•Oxygen content in NdBaCo2O6-δ was determined as a function of T and pO2•Defect structure model of NdBaCo2O6-δ was proposed and successfully verified•Enthalpies of formation, ΔfH298∘, were measured for NdBaCo2O6-δ with different δ•Relationship between ΔfH298∘(δ) and high-temperature redox energetics was established•Oxygen vacancies were found to remain disordered in quenched NdBaCo2O6-δ samples</description><identifier>ISSN: 0167-2738</identifier><identifier>EISSN: 1872-7689</identifier><identifier>DOI: 10.1016/j.ssi.2021.115549</identifier><language>eng</language><publisher>Amsterdam: Elsevier B.V</publisher><subject>Cobalt ; Coulometers ; Defect structure ; Defects ; Double perovskites ; Enthalpy ; Formation enthalpy ; Oxygen ; Oxygen content ; Partial pressure ; Perovskite ; Perovskites ; Redox energetics ; Temperature ; Thermogravimetry ; Titration ; Vacancy ordering</subject><ispartof>Solid state ionics, 2021-03, Vol.361, p.115549, Article 115549</ispartof><rights>2021 Elsevier B.V.</rights><rights>Copyright Elsevier BV Mar 2021</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c325t-81c72a789efa1d45fb562f0abc2dd4cbf0bfbe57e6fc5aae1464640ec917c38b3</citedby><cites>FETCH-LOGICAL-c325t-81c72a789efa1d45fb562f0abc2dd4cbf0bfbe57e6fc5aae1464640ec917c38b3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://www.sciencedirect.com/science/article/pii/S0167273821000023$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,776,780,3537,27901,27902,65306</link.rule.ids></links><search><creatorcontrib>Tsvetkov, Dmitry S.</creatorcontrib><creatorcontrib>Yagovitin, Roman E.</creatorcontrib><creatorcontrib>Sereda, Vladimir V.</creatorcontrib><creatorcontrib>Malyshkin, Dmitry A.</creatorcontrib><creatorcontrib>Ivanov, Ivan L.</creatorcontrib><creatorcontrib>Zuev, Andrey Yu</creatorcontrib><creatorcontrib>Maignan, Antoine</creatorcontrib><title>Defect structure and redox energetics of NdBaCo2O6-δ</title><title>Solid state ionics</title><description>The oxygen content in the double perovskite NdBaCo2O6-δ was measured as a function of oxygen partial pressure (1–10−5 atm) at different temperatures (623–1323 K) using thermogravimetry analysis (TG) and coulometric titration technique. The defect structure model of the oxide studied was proposed and successfully verified using the pO2 – T – δ data, yielding the enthalpies and entropies of the defect reactions involved. Standard enthalpy of formation from elements (ΔfH298∘) was measured for quenched NdBaCo2O6-δ samples with different oxygen content. Regarding the ΔfH298∘(6-δ) dependences, two important observations were made. First, the ΔfH298∘(6-δ) consists of two linear fragments with different slopes reflecting different modes of oxygen exchange, accompanied by either reduction of cobalt from Co+3 to Co+2 or from Co+4 to Co+3 in the ranges 5.0 ≤ 6-δ ≤5.5 and 5.5 < 6-δ < 5.7, respectively. Second, when corrected for the quenching effect arising from the oxygen vacancy disordering, the experimental ΔfH298∘(6-δ) values and those calculated using the partial molar enthalpy of oxygen, which was evaluated using the defect structure model, agree well with each other. This can be regarded as an independent verification of both the model and the related defect reaction thermodynamics.
•Oxygen content in NdBaCo2O6-δ was determined as a function of T and pO2•Defect structure model of NdBaCo2O6-δ was proposed and successfully verified•Enthalpies of formation, ΔfH298∘, were measured for NdBaCo2O6-δ with different δ•Relationship between ΔfH298∘(δ) and high-temperature redox energetics was established•Oxygen vacancies were found to remain disordered in quenched NdBaCo2O6-δ samples</description><subject>Cobalt</subject><subject>Coulometers</subject><subject>Defect structure</subject><subject>Defects</subject><subject>Double perovskites</subject><subject>Enthalpy</subject><subject>Formation enthalpy</subject><subject>Oxygen</subject><subject>Oxygen content</subject><subject>Partial pressure</subject><subject>Perovskite</subject><subject>Perovskites</subject><subject>Redox energetics</subject><subject>Temperature</subject><subject>Thermogravimetry</subject><subject>Titration</subject><subject>Vacancy ordering</subject><issn>0167-2738</issn><issn>1872-7689</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNp9kLtOxDAQRS0EEsvCB9BFok6wnfgRUcHylFZsA7Xl2GPkCOLFThD8F9_BN-FVqNEU09xzZ3QQOiW4Ipjw875KyVcUU1IRwljT7qEFkYKWgst2Hy1yRpRU1PIQHaXUY4x5LfkCsWtwYMYijXEy4xSh0IMtItjwWcAA8QVGb1IRXPFor_Qq0A0vf76P0YHTrwlO_vYSPd_ePK3uy_Xm7mF1uS5NTdlYSmIE1UK24DSxDXMd49Rh3RlqbWM6hzvXARPAnWFaA2l4HgymJcLUsquX6Gzu3cbwPkEaVR-mOOSTijJcN5zRhuQUmVMmhpQiOLWN_k3HL0Ww2tlRvcp21M6Omu1k5mJmIL__4SGqZDwMBqyP2Yeywf9D_wL8mWzJ</recordid><startdate>202103</startdate><enddate>202103</enddate><creator>Tsvetkov, Dmitry S.</creator><creator>Yagovitin, Roman E.</creator><creator>Sereda, Vladimir V.</creator><creator>Malyshkin, Dmitry A.</creator><creator>Ivanov, Ivan L.</creator><creator>Zuev, Andrey Yu</creator><creator>Maignan, Antoine</creator><general>Elsevier B.V</general><general>Elsevier BV</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7U5</scope><scope>8FD</scope><scope>L7M</scope></search><sort><creationdate>202103</creationdate><title>Defect structure and redox energetics of NdBaCo2O6-δ</title><author>Tsvetkov, Dmitry S. ; Yagovitin, Roman E. ; Sereda, Vladimir V. ; Malyshkin, Dmitry A. ; Ivanov, Ivan L. ; Zuev, Andrey Yu ; Maignan, Antoine</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c325t-81c72a789efa1d45fb562f0abc2dd4cbf0bfbe57e6fc5aae1464640ec917c38b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Cobalt</topic><topic>Coulometers</topic><topic>Defect structure</topic><topic>Defects</topic><topic>Double perovskites</topic><topic>Enthalpy</topic><topic>Formation enthalpy</topic><topic>Oxygen</topic><topic>Oxygen content</topic><topic>Partial pressure</topic><topic>Perovskite</topic><topic>Perovskites</topic><topic>Redox energetics</topic><topic>Temperature</topic><topic>Thermogravimetry</topic><topic>Titration</topic><topic>Vacancy ordering</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tsvetkov, Dmitry S.</creatorcontrib><creatorcontrib>Yagovitin, Roman E.</creatorcontrib><creatorcontrib>Sereda, Vladimir V.</creatorcontrib><creatorcontrib>Malyshkin, Dmitry A.</creatorcontrib><creatorcontrib>Ivanov, Ivan L.</creatorcontrib><creatorcontrib>Zuev, Andrey Yu</creatorcontrib><creatorcontrib>Maignan, Antoine</creatorcontrib><collection>CrossRef</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Solid state ionics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tsvetkov, Dmitry S.</au><au>Yagovitin, Roman E.</au><au>Sereda, Vladimir V.</au><au>Malyshkin, Dmitry A.</au><au>Ivanov, Ivan L.</au><au>Zuev, Andrey Yu</au><au>Maignan, Antoine</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Defect structure and redox energetics of NdBaCo2O6-δ</atitle><jtitle>Solid state ionics</jtitle><date>2021-03</date><risdate>2021</risdate><volume>361</volume><spage>115549</spage><pages>115549-</pages><artnum>115549</artnum><issn>0167-2738</issn><eissn>1872-7689</eissn><abstract>The oxygen content in the double perovskite NdBaCo2O6-δ was measured as a function of oxygen partial pressure (1–10−5 atm) at different temperatures (623–1323 K) using thermogravimetry analysis (TG) and coulometric titration technique. The defect structure model of the oxide studied was proposed and successfully verified using the pO2 – T – δ data, yielding the enthalpies and entropies of the defect reactions involved. Standard enthalpy of formation from elements (ΔfH298∘) was measured for quenched NdBaCo2O6-δ samples with different oxygen content. Regarding the ΔfH298∘(6-δ) dependences, two important observations were made. First, the ΔfH298∘(6-δ) consists of two linear fragments with different slopes reflecting different modes of oxygen exchange, accompanied by either reduction of cobalt from Co+3 to Co+2 or from Co+4 to Co+3 in the ranges 5.0 ≤ 6-δ ≤5.5 and 5.5 < 6-δ < 5.7, respectively. Second, when corrected for the quenching effect arising from the oxygen vacancy disordering, the experimental ΔfH298∘(6-δ) values and those calculated using the partial molar enthalpy of oxygen, which was evaluated using the defect structure model, agree well with each other. This can be regarded as an independent verification of both the model and the related defect reaction thermodynamics.
•Oxygen content in NdBaCo2O6-δ was determined as a function of T and pO2•Defect structure model of NdBaCo2O6-δ was proposed and successfully verified•Enthalpies of formation, ΔfH298∘, were measured for NdBaCo2O6-δ with different δ•Relationship between ΔfH298∘(δ) and high-temperature redox energetics was established•Oxygen vacancies were found to remain disordered in quenched NdBaCo2O6-δ samples</abstract><cop>Amsterdam</cop><pub>Elsevier B.V</pub><doi>10.1016/j.ssi.2021.115549</doi></addata></record> |
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| subjects | Cobalt Coulometers Defect structure Defects Double perovskites Enthalpy Formation enthalpy Oxygen Oxygen content Partial pressure Perovskite Perovskites Redox energetics Temperature Thermogravimetry Titration Vacancy ordering |
| title | Defect structure and redox energetics of NdBaCo2O6-δ |
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