Show simple item record

dc.contributor.authorHua, Xiao
dc.contributor.authorEggeman, Alexander S
dc.contributor.authorCastillo-Martínez, Elizabeth
dc.contributor.authorRobert, Rosa
dc.contributor.authorGeddes, Harry S
dc.contributor.authorLu, Ziheng
dc.contributor.authorPickard, Chris J
dc.contributor.authorMeng, Wei
dc.contributor.authorWiaderek, Kamila M
dc.contributor.authorPereira, Nathalie
dc.contributor.authorAmatucci, Glenn G
dc.contributor.authorMidgley, Paul A
dc.contributor.authorChapman, Karena W
dc.contributor.authorSteiner, Ullrich
dc.contributor.authorGoodwin, Andrew L
dc.contributor.authorGrey, Clare P
dc.date.accessioned2020-12-01T00:31:30Z
dc.date.available2020-12-01T00:31:30Z
dc.date.issued2021-06
dc.identifier.issn1476-1122
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/313574
dc.description.abstractMetal fluorides, promising lithium-ion battery cathode materials, have been classified as conversion materials due to the reconstructive phase transitions widely presumed to occur upon lithiation. We challenge this view by studying FeF3 using X-ray total scattering and electron diffraction techniques that measure structure over multiple length scales coupled with density functional theory calculations, and by revisiting prior experimental studies of FeF2 and CuF2. Metal fluoride lithiation is instead dominated by diffusion-controlled displacement mechanisms, and a clear topological relationship between the metal fluoride F- sublattices and that of LiF is established. Initial lithiation of FeF3 forms FeF2 on the particle's surface, along with a cation-ordered and stacking-disordered phase, A-LixFeyF3, which is structurally related to α-/β-LiMn2+Fe3+F6 and which topotactically transforms to B- and then C-LixFeyF3, before forming LiF and Fe. Lithiation of FeF2 and CuF2 results in a buffer phase between FeF2/CuF2 and LiF. The resulting principles will aid future developments of a wider range of isomorphic metal fluorides.
dc.description.sponsorshipX.H. is supported by funding from EPSRC Doctoral Prize, Adolphe Merkle and the Swiss National Science Foundation (Program NRP70 No. 153990) and European Commission via MSCA (Grant 798169). A.S.E. acknowledges financial support from the Royal Society. E.C.M. acknowledges funding from European Commission via MSCA (Grant 747449) and RTI2018-094550-A-100 from MICINN. Z. L. acknowledges funding from the Faraday Institution via the FutureCat consortium. C.J.P. is supported by the Royal Society through a Royal Society Wolfson Research Merit award, and EPSRC grant EP/P022596/1. A.L.G. acknowledges funding from the ERC (Grant 788144). This research was supported as part of the North Eastern Center for Chemical Energy Storage, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award Number DE-SC0001294. Work done at Argonne and use of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE under Contract No. DE-AC02-06CH11357. Work done at Diamond Light Source was under Proposal EE17315-1. The authors are grateful to Prof. G. Ceder and other NECCES members for many stimulating discussions concerning fluoride-based conversion reactions and on the origins of structural hysteresis. The authors also acknowledge the help from S. Dutton, T. Dean, A. Docker, M. Leskes and D. Keeble.
dc.format.mediumPrint-Electronic
dc.languageeng
dc.publisherSpringer Science and Business Media LLC
dc.rightsAll rights reserved
dc.titleRevisiting metal fluorides as lithium-ion battery cathodes.
dc.typeArticle
prism.endingPage850
prism.issueIdentifier6
prism.publicationDate2021
prism.publicationNameNat Mater
prism.startingPage841
prism.volume20
dc.identifier.doi10.17863/CAM.60682
dcterms.dateAccepted2020-11-26
rioxxterms.versionofrecord10.1038/s41563-020-00893-1
rioxxterms.versionAM
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserved
rioxxterms.licenseref.startdate2021-06
dc.contributor.orcidHua, Xiao [0000-0002-8673-5678]
dc.contributor.orcidEggeman, Alexander S [0000-0002-3447-4322]
dc.contributor.orcidPickard, Chris J [0000-0002-9684-5432]
dc.contributor.orcidChapman, Karena W [0000-0002-8725-5633]
dc.contributor.orcidSteiner, Ullrich [0000-0001-5936-339X]
dc.contributor.orcidGoodwin, Andrew L [0000-0001-9231-3749]
dc.contributor.orcidGrey, Clare P [0000-0001-5572-192X]
dc.identifier.eissn1476-4660
rioxxterms.typeJournal Article/Review
pubs.funder-project-idRoyal Society (WM150023)
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/P022596/1)
pubs.funder-project-idEuropean Commission Horizon 2020 (H2020) Marie Sk?odowska-Curie actions (747449)
cam.issuedOnline2021-01-21
cam.orpheus.successMon Feb 01 07:31:35 GMT 2021 - Embargo updated
cam.orpheus.counter6
rioxxterms.freetoread.startdate2021-07-21


Files in this item

Thumbnail
Thumbnail

This item appears in the following Collection(s)

Show simple item record