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dc.contributor.authorMichan, Alison Len
dc.contributor.authorDivitini, Giorgioen
dc.contributor.authorPell, Andrew Jen
dc.contributor.authorLeskes, Michalen
dc.contributor.authorDucati, Caterinaen
dc.contributor.authorGrey, Clareen
dc.date.accessioned2016-07-15T13:16:12Z
dc.date.available2016-07-15T13:16:12Z
dc.date.issued2016-05-27en
dc.identifier.issn0002-7863
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/256753
dc.description.abstractThe solid electrolyte interphase (SEI) of the high capacity anode material Si is monitored over multiple electrochemical cycles by $^{7}$Li, $^{19}$F, and $^{13}$C solid-state nuclear magnetic resonance spectroscopies, with the organics dominating the SEI. Homonuclear correlation experiments are used to identify the organic fragments −OCH$_{2}$CH$_{2}$O−, −OCH$_{2}$CH$_{2}$−, −OCH$_{2}$CH$_{3}$, and −CH$_{2}$CH$_{3}$ contained in both oligomeric species and lithium semicarbonates ROCO$_{2}$Li, RCO$_{2}$Li. The SEI growth is correlated with increasing electrode tortuosity by using focused ion beam and scanning electron microscopy. A two-stage model for lithiation capacity loss is developed: initially, the lithiation capacity steadily decreases, Li$^{+}$ is irreversibly consumed at a steady rate, and pronounced SEI growth is seen. Later, below 50% of the initial lithiation capacity, less Si is (de)lithiated resulting in less volume expansion and contraction; the rate of Li$^{+}$ being irreversibly consumed declines, and the Si SEI thickness stabilizes. The decreasing lithiation capacity is primarily attributed to kinetics, the increased electrode tortuousity severely limiting Li$^{+}$ ion diffusion through the bulk of the electrode. The resulting changes in the lithiation processes seen in the electrochemical capacity curves are ascribed to non-uniform lithiation, the reaction commencing near the separator/on the surface of the particles.
dc.description.sponsorshipThis work was partially supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract #7057154 and the European Commission (EC), through the project EuroLion. G.D. and C.D. acknowledge funding from the ERC under Grants 259619 PHOTO EM and 312483 ESTEEM2. A.L.M. is an awardee of a Schiff Foundation Studentship and a nanoDTC Associate. M.L. is an awardee of the Weizmann Institute of Science - National Postdoctoral Award for Advancing Women in Science and thanks the EU Marie Curie intra-European fellowship for funding.
dc.languageEnglishen
dc.language.isoenen
dc.publisherAmerican Chemical Society
dc.titleSolid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodesen
dc.typeArticle
dc.description.versionThis is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/jacs.6b02882en
prism.endingPage7931
prism.publicationDate2016en
prism.publicationNameJournal of the American Chemical Societyen
prism.startingPage7918
prism.volume138en
dc.identifier.doi10.17863/CAM.688
dcterms.dateAccepted2016-05-27en
rioxxterms.versionofrecord10.1021/jacs.6b02882en
rioxxterms.versionAMen
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2016-05-27en
dc.contributor.orcidDivitini, Giorgio [0000-0003-2775-610X]
dc.contributor.orcidDucati, Caterina [0000-0003-3366-6442]
dc.contributor.orcidGrey, Clare [0000-0001-5572-192X]
dc.identifier.eissn1520-5126
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEuropean Research Council (259619)
pubs.funder-project-idEC FP7 CP WITH CSA (312483)
rioxxterms.freetoread.startdate2017-05-27


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