Show simple item record

dc.contributor.authorHua, Xiaoen
dc.contributor.authorRobert, Rosaen
dc.contributor.authorDu, Lin-Shuen
dc.contributor.authorWiaderek, Kamila Men
dc.contributor.authorLeskes, Michalen
dc.contributor.authorChapman, Karena Wen
dc.contributor.authorChupas, Peter Jen
dc.contributor.authorGrey, Clareen
dc.date.accessioned2015-04-22T12:57:19Z
dc.date.available2015-04-22T12:57:19Z
dc.date.issued2014-06-11en
dc.identifier.citationJournal of Physical Chemistry C 2014, 118 (28), pp 15169–15184. DOI: 10.1021/jp503902zen
dc.identifier.issn1932-7447
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/247425
dc.description.abstractConversion materials for lithium ion batteries have recently attracted considerable attention due to their exceptional specific capacities. Some metal fluorides, such as CuF2, are promising candidates for cathode materials owing to their high operating potential, which stems from the high electronegativity of fluorine. However, the high ionicity of the metal–fluorine bond leads to a large band gap that renders these materials poor electronic conductors. Nanosizing the active material and embedding it within a conductive matrix such as carbon can greatly improve its electrochemical performance. In contrast to other fluorides, such as FeF2 and NiF2, good capacity retention has not, however, been achieved for CuF2. The reaction mechanisms that occur in the first and subsequent cycles and the reasons for the poor charge performance of CuF2 are studied in this paper via a variety of characterization methods. In situ pair distribution function analysis clearly shows CuF2 conversion in the first discharge. However, few structural changes are seen in the following charge and subsequent cycles. Cyclic voltammetry results, in combination with in situ X-ray absorption near edge structure and ex situ nuclear magnetic resonance spectroscopy, indicate that Cu dissolution is associated with the consumption of the LiF phase, which occurs during the first charge via the formation of a Cu1+ intermediate. The dissolution process consequently prevents Cu and LiF from transforming back to CuF2. Such side reactions result in negligible capacity in subsequent cycles and make this material challenging to use in a rechargeable battery.
dc.description.sponsorshipWe acknowledge the funding from the U.S. DOE BES via funding to the EFRC NECCES, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001294 (support for Rosa Robert and Lin-Shu Du) and EPSRC via the “nanoionics” programme grant (support for Xiao Hua). Use of the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory (BNL), was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.
dc.languageEnglishen
dc.language.isoenen
dc.publisherAmerican Chemical Society
dc.titleComprehensive Study of the CuF2 Conversion Reaction Mechanism in a Lithium Ion Batteryen
dc.typeArticle
dc.description.versionThis is the final published version of the article. It first appeared at http://pubs.acs.org/doi/abs/10.1021/jp503902z and is posted here under the terms of ACS's Editors' Choice scheme (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html).en
prism.endingPage15184
prism.publicationDate2014en
prism.publicationNameJournal of Physical Chemistry Cen
prism.startingPage15169
prism.volume118en
dc.rioxxterms.funderEPSRC
rioxxterms.versionofrecord10.1021/jp503902zen
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2014-06-11en
dc.contributor.orcidGrey, Clare [0000-0001-5572-192X]
dc.identifier.eissn1932-7455
rioxxterms.typeJournal Article/Reviewen


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record