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dc.contributor.authorStrobridge, Fiona Cen
dc.contributor.authorClément, Raphaële Jen
dc.contributor.authorLeskes, Michalen
dc.contributor.authorMiddlemiss, Derek Sen
dc.contributor.authorBorkiewicz, Olaf Jen
dc.contributor.authorWiaderek, Kamila Men
dc.contributor.authorChapman, Karena Wen
dc.contributor.authorChupas, Peter Jen
dc.contributor.authorGrey, Clareen
dc.date.accessioned2014-10-17T14:41:33Z
dc.date.available2014-10-17T14:41:33Z
dc.date.issued2014-10-09en
dc.identifier.citationChemistry of Materials 2014, 26 (21), pp 6193–6205, DOI: 10.1021/cm502680wen
dc.identifier.issn0897-4756
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/246208
dc.description.abstractIn situ synchrotron diffraction measurements and subsequent Rietveld refinements are used to show that the high energy density cathode material LiCoPO_4 (space group Pnma) undergoes two distinct two-phase reactions upon charge and discharge, both occurring via an intermediate Li_2/3(Co^2+)_2/3(Co^3+)_1/3PO_4 phase. Two resonances are observed for Li_2/3CoPO_4 with intensity ratios of 2:1 and 1:1 in the ^31P and ^7Li NMR spectra, respectively. An ordering of Co^2+/Co^3+ oxidation states is proposed within a (a×3b×c) supercell, and Li^+/vacancy ordering is investigated using experimental NMR data in combination with first principles solid-state DFT calculations. In the lowest energy configuration, both the Co^3+ ions and Li vacancies are found to order along the b-axis. Two other low energy Li^+/vacancy ordering schemes are found only 5 meV per formula unit higher in energy. All three configurations lie below the LiCoPO_4-CoPO_4 convex hull and they may be readily interconverted by Li^+ hops along the b-direction.
dc.languageen_USen
dc.language.isoen_USen
dc.publisherACS
dc.rightsAttribution 2.0 UK: England & Wales
dc.rights.urihttp://creativecommons.org/licenses/by/2.0/uk/
dc.titleIdentifying the structure of the intermediate, Li_2/3CoPO_4, formed during electrochemical cycling of LiCoPO_4en
dc.typeArticle
dc.description.versionThis is the final version. It was first published by ACS Publications at http://pubs.acs.org/doi/abs/10.1021/cm502680wen
prism.endingPage6205
prism.publicationDate2014en
prism.publicationNameChemistry of Materialsen
prism.startingPage6193
prism.volume26en
dc.rioxxterms.funderEPSRC
dc.rioxxterms.funderERC
rioxxterms.versionofrecord10.1021/cm502680wen
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2014-10-09en
dc.contributor.orcidGrey, Clare [0000-0001-5572-192X]
dc.identifier.eissn1520-5002
rioxxterms.typeJournal Article/Reviewen


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Attribution 2.0 UK: England & Wales
Except where otherwise noted, this item's licence is described as Attribution 2.0 UK: England & Wales