Supercritical-fluid synthesis of FeF2 and CoF2 Li-ion conversion materials

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dc.contributor.authorArmstrong, Mark J.
dc.contributor.authorPanneerselvam, Arunkumar
dc.contributor.authorO'Regan, Colm
dc.contributor.authorMorris, Michael A.
dc.contributor.authorHolmes, Justin D.
dc.contributor.funderHigher Education Authorityen
dc.contributor.funderScience Foundation Irelanden
dc.date.accessioned2016-02-10T17:43:25Z
dc.date.available2016-02-10T17:43:25Z
dc.date.issued2013-07-23
dc.date.updated2013-08-20T17:06:57Z
dc.description.abstractThe synthesis of the Li-ion conversion candidates, FeF2 and CoF2, obtained from the single source organometallic precursors [Fe(tta)3] (tta = C8H4F3O2S), and [Co(hfac)2[middle dot]2H2O] (hfac = C5H1F6O2), respectively, via a novel supercritical fluid (SCF) method is presented. The nature of the synthesis led to highly-crystalline FeF2 and CoF2 powders requiring no additional thermal treatment. The as-obtained powders were investigated for use as potential positive Li-ion conversion electrodes by means of chronopotentiometric measurements. The FeF2 cells displayed high initial capacities following electrochemical conversion (up to [similar]1100 mA h g-1 at a potential of 1.0 V vs. Li/Li+), with appreciable cyclic behaviour over 25 discharge-charge cycles. The deposition of a [similar]5 nm layer of amorphous carbon onto the surface of the active material following SCF treatment, likely facilitated adequate electron transport through an otherwise poorly conducting FeF2 phase. Similarly, CoF2 cells displayed high initial capacities (up to [similar]650 mA h g-1 at a potential of 1.2 V vs. Li/Li+), although significant capacity fading ensued in the subsequent cycles. Ex situ XRD measurements confirmed a poor reversibility in the conversion sequence for CoF2, with a complete loss of CoF2 crystallinity and the sole presence of a crystalline LiF phase following charging.en
dc.description.sponsorshipScience Foundation Ireland (SFI Grants: 07/SRC/I1172, 08/CE/I1432 and 09/SIRG/I1621); Higher Education Authority (Program for Research in Third Level Institutions (2007-2011) INSPIRE)en
dc.description.statusPeer revieweden
dc.description.versionSubmitted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationARMSTRONG, M. J., PANNEERSELVAM, A., O'REGAN, C., MORRIS, M. A. & HOLMES, J. D. 2013. Supercritical-fluid synthesis of FeF2 and CoF2 Li-ion conversion materials. Journal of Materials Chemistry A, 1, 10667-10676. http://dx.doi.org/10.1039/C3TA12436Cen
dc.identifier.doi10.1039/c3ta12436c
dc.identifier.endpage10676en
dc.identifier.issn2050-7488
dc.identifier.issued36en
dc.identifier.journaltitleJournal of Materials Chemistry Aen
dc.identifier.startpage10667en
dc.identifier.urihttps://hdl.handle.net/10468/2278
dc.identifier.volume1en
dc.language.isoenen
dc.publisherThe Royal Society of Chemistryen
dc.relation.urihttp://pubs.rsc.org/en/content/articlepdf/2013/ta/c3ta12436c
dc.rights© Royal Society of Chemistry 2013.en
dc.subjectActive materialen
dc.subjectCapacity fadingen
dc.subjectCrystallinitiesen
dc.subjectCyclic behaviouren
dc.subjectDischarge-charge cycleen
dc.subjectElectrochemical conversionen
dc.subjectElectron transporten
dc.subjectOrganometallic precursorsen
dc.subjectAmorphous carbonen
dc.subjectCrystalline materialsen
dc.subjectEffluent treatmenten
dc.subjectIonsen
dc.subjectOrganometallicsen
dc.subjectPowdersen
dc.subjectSupercritical fluidsen
dc.subjectLithiumen
dc.titleSupercritical-fluid synthesis of FeF2 and CoF2 Li-ion conversion materialsen
dc.typeArticle (peer-reviewed)en
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