Dynamic solubility limits in nanosized olivine LiFePO(4)

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dc.contributor.authorWagemaker, Men_AU
dc.contributor.authorSingh, DPen_AU
dc.contributor.authorBorghols, WJHen_AU
dc.contributor.authorLafont, Uen_AU
dc.contributor.authorHaverkate, LAen_AU
dc.contributor.authorPeterson, VKen_AU
dc.contributor.authorMulder, FMen_AU
dc.date.accessioned2011-12-06T04:47:35Zen_AU
dc.date.available2011-12-06T04:47:35Zen_AU
dc.date.issued2011-07-06en_AU
dc.date.statistics2011-12-06en_AU
dc.description.abstractBecause of its stability, nanosized olivine LiFePO(4) opens the door toward high-power Li-ion battery technology for large-scale applications as required for plug-in hybrid vehicles. Here, we reveal that the thermodynamics of first-order phase transitions in nanoinsertion materials is distinctly different from bulk materials as demonstrated by the decreasing miscibility gap that appears to be strongly dependent on the overall composition in LiFePO(4). In contrast to our common thermodynamic knowledge, that dictates solubility limits to be independent of the overall composition, combined neutron and X-ray diffraction reveals strongly varying solubility limits below particle sizes of 35 nm. A rationale is found based on modeling of the diffuse interface. Size confinement of the lithium concentration gradient, which exists at the phase boundary, competes with the in bulk energetically favorable compositions. Consequently, temperature and size diagrams of nanomaterials require complete reconsideration, being strongly dependent on the overall composition. This is vital knowledge for the future nanoarchitecturing of superior energy storage devices as the performance will heavily depend on the disclosed nanoionic properties. © 2011, American Chemical Societyen_AU
dc.identifier.citationWagemaker, M., Singh, D.P., Borghols, W.J.H., Lafont, U., Haverkate, L., Peterson, V.K., Mulder, F.M. (2011). Dynamic solubility limits in nanosized olivine LiFePO(4). Journal of the American Chemical Society, 133(26), 10222-10228. doi:10.1021/ja2026213en_AU
dc.identifier.govdoc3831en_AU
dc.identifier.issn0002-7863en_AU
dc.identifier.issue26en_AU
dc.identifier.journaltitleJournal of the American Chemical Societyen_AU
dc.identifier.pagination10222-10228en_AU
dc.identifier.urihttp://dx.doi.org/10.1021/ja2026213en_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/3923en_AU
dc.identifier.volume133en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectOlivineen_AU
dc.subjectStrainsen_AU
dc.subjectLithiumen_AU
dc.subjectSolubilityen_AU
dc.subjectHybridizationen_AU
dc.subjectThermodynamicsen_AU
dc.titleDynamic solubility limits in nanosized olivine LiFePO(4)en_AU
dc.typeJournal Articleen_AU
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