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dc.contributor.authorOyama, Gosukeen
dc.contributor.authorPecher, Oliveren
dc.contributor.authorGriffith, Kenten
dc.contributor.authorNishimura, Shin-ichien
dc.contributor.authorPigliapochi, Robertaen
dc.contributor.authorGrey, Clareen
dc.contributor.authorYamada, Atsuoen
dc.date.accessioned2016-08-17T08:56:27Z
dc.date.available2016-08-17T08:56:27Z
dc.date.issued2016-07-05en
dc.identifier.issn0897-4756
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/257304
dc.description.abstractAlluaudite sodium iron sulfate Na$_{2+2x}$Fe$_{2−x}$(SO$_4$)$_3$ is one of the most promising candidates for a Na-ion battery cathode material with earth-abundant elements; it exhibits the highest potential among any Fe$^{3+}$/Fe$^{2+}$ redox reactions (3.8 V vs Na/Na$^+$ ), good cycle performance, and high rate capability. However, the reaction mechanism during electrochemical charging/discharging processes is still not understood. Here, we surveyed the intercalation mechanism via synchrotron X-ray diffraction (XRD), $^{23}$Na nuclear magnetic resonance (NMR), density functional theory (DFT) calculations, X-ray absorption near edge structure (XANES), and Mössbauer spectroscopy. Throughout charging/discharging processes, the structure undergoes a reversible, single-phase (solid solution) reaction based on a Fe$^{3+}$/Fe$^{2+}$ redox reaction with a small volume change of ca. 3.5% after an initial structural rearrangement upon the first charging process, where a small amount of Fe irreversibly migrates from the original site to a Na site. Sodium extraction occurs in a sequential manner at various Na sites in the structure at their specific voltage regions.
dc.description.sponsorshipThe present work was financially supported from the Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT) under the “Element Strategy Initiative for Catalysts & Batteries” (ESICB) project. The synchrotron XRD experiments were performed under KEK-PF User Program (No. 2013G670). Crystal structures and the Fourier difference maps were drawn by VESTA.65 G.O. acknowledges financial support from JSPS Research Fellowships under “Materials Education Program for the Future Leaders in Research, Industry, and Technology” (MERIT) project. This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 655444 (O.P.). R.P. gratefully acknowledges financial support through the Marie Curie Actions People Program of the EU’s Seventh Frame work Program (FP7/2007-2013), under the grant agreement n.317127, the ‘pNMR project’. K.J.G. gratefully acknowledges funding from The Winston Churchill Foundation of the United States and the Herchel Smith Scholarship. This work made use of the facilities of the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.
dc.languageEnglishen
dc.language.isoenen
dc.publisherAmerican Chemical Society
dc.rightsAttribution 4.0 International
dc.rightsAttribution 4.0 Internationalen
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.titleSodium Intercalation Mechanism of 3.8 V Class Alluaudite Sodium Iron Sulfateen
dc.typeArticle
dc.description.versionThis is the final version of the article. It first appeared from American Chemical Society via http://dx.doi.org/10.1021/acs.chemmater.6b01091en
prism.endingPage5328
prism.publicationDate2016en
prism.publicationNameChemistry of Materialsen
prism.startingPage5321
prism.volume28en
dc.identifier.doi10.17863/CAM.1235
dcterms.dateAccepted2016-07-05en
rioxxterms.versionofrecord10.1021/acs.chemmater.6b01091en
rioxxterms.versionVoRen
rioxxterms.licenseref.urihttp://creativecommons.org/licenses/by/4.0/en
rioxxterms.licenseref.startdate2016-07-05en
dc.contributor.orcidGriffith, Kent [0000-0002-8096-906X]
dc.contributor.orcidGrey, Clare [0000-0001-5572-192X]
dc.identifier.eissn1520-5002
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEuropean Commission (655444)
pubs.funder-project-idEC FP7 MC ITN (317127)


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Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International