001     20185
005     20240529111726.0
024 7 _ |2 pmid
|a pmid:21598941
024 7 _ |2 DOI
|a 10.1021/ja2026213
024 7 _ |2 WOS
|a WOS:000292715600050
024 7 _ |2 MLZ
|a doi:10.1021/ja2026213
037 _ _ |a PreJuSER-20185
041 _ _ |a eng
082 _ _ |a 540
084 _ _ |2 WoS
|a Chemistry, Multidisciplinary
100 1 _ |0 P:(DE-HGF)0
|a Wagemaker, M.
|b 0
245 _ _ |a Dynamic Solubility Limits in Nanosized Olivine LiFePO(4)
260 _ _ |a Washington, DC
|b American Chemical Society
|c 2011
300 _ _ |a 10222 - 10228
336 7 _ |a Journal Article
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336 7 _ |a article
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440 _ 0 |0 21462
|a Journal of the American Chemical Society
|v 133
|x 0002-7863
|y 26
500 _ _ |a This work is a contribution from the Delft Energy Initiative (DEI). Financial support from Shell is acknowledged for the Sustainable Mobility grant funding D.P.S. The Netherlands Organization for Scientific Research (NWO) is acknowledged for both beam time at ISIS and the CW-VIDI grant of M.W. The authors thank Ron Smith for assistance with the neutron diffraction experiments at POLARIS (ISIS), Michela Brunelli and Mark Johnson at D20 (ILL), and Vladimir Pomjakushin at HRPT (PSI). We thank the Alistore network for providing access to the TEM measurements.
520 _ _ |a Because 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.
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|a Peterson, V.K.
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|t Journal of the American Chemical Society
|v 133
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856 7 _ |u http://dx.doi.org/10.1021/ja2026213
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