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dc.contributor.authorStrobridge, Fiona Cen
dc.contributor.authorLiu, Haoen
dc.contributor.authorLeskes, Michalen
dc.contributor.authorBorkiewicz, Olaf Jen
dc.contributor.authorWiaderek, Kamila Men
dc.contributor.authorChupas, Peter Jen
dc.contributor.authorChapman, Karena Wen
dc.contributor.authorGrey, Clareen
dc.date.accessioned2016-05-26T09:40:06Z
dc.date.available2016-05-26T09:40:06Z
dc.date.issued2016-04-25en
dc.identifier.issn0897-4756
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/256097
dc.description.abstractThe delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention owing to the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFexCo1-xPO4 (x = 0, 0.05, 0.125, 0.25, 0.5, 0.75, 0.875, 0.95 and 1) are electrochemically cycled is reported here, using in situ X-ray diffraction (XRD) data, and supporting ex situ 31P NMR spectra. On the first charge, two intermediate phases are observed and identified: Li1-x(Fe3+)x(Co2+)1-xPO4 for 0 < x < 1 (i.e. after oxidation of Fe2+ => Fe3+) and Li2/3FexCo1-xPO4 for 0 ≤ x ≤ 0.5 (i.e. the Co-majority materials). For the Fe-rich materials, we study how nonequilibrium, single-phase mechanisms that occur discretely in single particles, as observed for LiFePO4 at high rates, are affected by Co substitution. In the Co-majority materials, a two-phase mechanism with a coherent interface is observed, as was seen in LiCoPO4, and we discuss how it is manifested in the XRD patterns. We then compare the nonequilibrium, single-phase mechanism with the bulk single-phase and the coherent interface two-phase mechanisms. Despite the apparent differences between these mechanisms, we discuss how they are related and interconverted as a function of Fe/Co substitution and the potential implications for the electrochemistry of this system.
dc.languageEnglishen
dc.language.isoenen
dc.publisherAmerican Chemical Society
dc.rightsAttribution 4.0 International
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.titleUnraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFexCo1-xPO4en
dc.typeArticle
dc.description.versionThis is the final version of the article. It first appeared from The American Chemical Society via https://doi.org/10.1021/acs.chemmater.6b00319en
prism.endingPage3690
prism.publicationDate2016en
prism.publicationNameChemistry of Materialsen
prism.startingPage3676
prism.volume28en
dc.identifier.doi10.17863/CAM.34
dcterms.dateAccepted2016-04-25en
rioxxterms.funderEngineering and Physical Sciences Research Councilen
rioxxterms.funderSeventh Framework Programmeen
rioxxterms.identifier.projectDoctoral Training Partnership Awarden
rioxxterms.identifier.projectFP7-265368en
rioxxterms.versionofrecord10.1021/acs.chemmater.6b00319en
rioxxterms.versionVoRen
rioxxterms.licenseref.urihttp://creativecommons.org/licenses/by/4.0/en
rioxxterms.licenseref.startdate2016-04-25en
dc.contributor.orcidGrey, Clare [0000-0001-5572-192X]
dc.identifier.eissn1520-5002
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEC FP7 CP (NMP3-SL-2010-265368)
cam.orpheus.successThu Jan 30 10:20:21 GMT 2020 - The item has an open VoR version.*
rioxxterms.funder.projectd671930e-8b85-4db8-b48a-6573e5d9f5aben
rioxxterms.funder.project93b56f2e-4771-4230-bf0b-c50f262e73d0en
rioxxterms.freetoread.startdate2100-01-01


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