dc.creator | Somerville, James W. | es |
dc.creator | Sobkowiak, Adam | es |
dc.creator | Tapia-Ruiz, Nuria | es |
dc.creator | Billaud, Juliette | es |
dc.creator | Lozano Suárez, Juan Gabriel | es |
dc.creator | House, Robert A. | es |
dc.creator | Gallington, Leighanne C. | es |
dc.creator | Ericsson, Tore | es |
dc.creator | Häggström, Lennart | es |
dc.creator | Roberts, Matthew R. | es |
dc.creator | Maitra, Urmimala | es |
dc.creator | Bruce, Peter G. | es |
dc.date.accessioned | 2019-09-18T07:41:43Z | |
dc.date.available | 2019-09-18T07:41:43Z | |
dc.date.issued | 2019-05-17 | |
dc.identifier.citation | Somerville, J.W., Sobkowiak, A., Tapia-Ruiz, N., Billaud, J., Lozano Suárez, J.G., House, R.A.,...,Bruce, P.G. (2019). Nature of the Z-phase in layered Na-ion battery cathodes. Energy and Environmental Science, 12 (7), 2223-2232. | |
dc.identifier.issn | 1754-5692 | es |
dc.identifier.issn | 1754-5706 | es |
dc.identifier.uri | https://hdl.handle.net/11441/89185 | |
dc.description.abstract | Layered sodium transition metal oxides with the P2 structure, e.g. Na2/3[Ni1/3Mn2/3]O2, are regarded as candidates for Na-ion battery cathodes. On charging, extraction of Na destabilizes the P2 phase (ABBA oxide ion stacking) in which Na+ is in trigonal prismatic coordination, resulting in layer gliding and formation of an O2 phase (ABAC stacking) with octahedral coordination. However, many related compounds do not exhibit such a simple P2 to O2 transition but rather form a so called "Z"-phase. Substituting Ni by Fe in Na2/3[Ni1/3Mn2/3]O2 is attractive as it reduces cost. The Fe containing compounds, such as Na2/3[Ni1/6Mn1/2Fe1/3]O2, form a "Z"-phase when charged above 4.1 V vs. Na+/Na. By combining ex situ and operando X-ray diffraction with scanning transmission electron microscopy and simulated diffraction patterns, we demonstrate that the "Z"-phase is most accurately described as a continuously changing intergrowth structure which evolves from P2 to O2 through the OP4 structure as an intermediate. On charging, Na+ removal results in O-type stacking faults within the P2 structure which increase in proportion. At 50% O-type stacking faults, the ordered OP4 phase forms and on further charging more O-type stacking faults are formed progressing towards a pure O2 structure. This gives the superficial appearance of a solid solution. Furthermore, in contrast to some previous studies, we did not detect Fe migration at any state-of-charge using 57Fe-Mössbauer spectroscopy. It was, however, found that the Fe-substitution serves to disrupt cation ordering in the material. | es |
dc.description.sponsorship | U.S. Department of Energy FIRG007 FIRG008 EP/R010145/1 | es |
dc.description.sponsorship | Argonne National Laboratory EP/M009521/1 EP/L019469/1 | es |
dc.format | application/pdf | es |
dc.language.iso | eng | es |
dc.publisher | Royal Society of Chemistry | es |
dc.relation.ispartof | Energy and Environmental Science, 12 (7), 2223-2232. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Nature of the "Z"-phase in layered Na-ion battery cathodes | es |
dc.type | info:eu-repo/semantics/article | es |
dcterms.identifier | https://ror.org/03yxnpp24 | |
dc.type.version | info:eu-repo/semantics/publishedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Ingeniería y Ciencia de los Materiales y del Transporte | es |
dc.relation.projectID | FIRG007 | es |
dc.relation.projectID | FIRG008 | es |
dc.relation.projectID | EP/R010145/1 | es |
dc.relation.projectID | EP/M009521/1 | es |
dc.relation.projectID | EP/L019469/1 | es |
dc.relation.publisherversion | http://doi.org/10.1039/c8ee02991a | es |
dc.identifier.doi | 10.1039/c8ee02991a | es |
idus.format.extent | 10 p. | es |
dc.journaltitle | Energy and Environmental Science | es |
dc.publication.volumen | 12 | es |
dc.publication.issue | 7 | es |
dc.publication.initialPage | 2223 | es |
dc.publication.endPage | 2232 | es |