Dynamic Solubility Limits in Nanosized Olivine LiFePO4

Marnix Wagemaker, Deepak P. Singh, Wouter J.H. Borghols, Ugo Lafont, Lucas Haverkate, Vanessa K. Peterson, Fokko M. Mulder

    Research output: Contribution to journalArticleAcademicpeer-review

    110 Citations (Scopus)

    Abstract

    Because of its stability, nanosized olivine LiFePO4 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 LiFePO4. 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.
    Original languageEnglish
    Pages (from-to)10222-10228
    Number of pages7
    JournalJournal of the American Chemical Society
    Volume133
    Issue number26
    DOIs
    Publication statusPublished - 6 Jul 2011

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    Olivine
    Thermodynamics
    Solubility
    Nanostructures
    Phase Transition
    Neutrons
    Chemical analysis
    Lithium
    Particle Size
    X-Ray Diffraction
    Plug-in hybrid vehicles
    Ions
    Technology
    Equipment and Supplies
    Temperature
    Phase boundaries
    Nanostructured materials
    Energy storage
    Phase transitions
    Particle size

    Cite this

    Wagemaker, 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 LiFePO4. Journal of the American Chemical Society, 133(26), 10222-10228. https://doi.org/10.1021/ja2026213
    Wagemaker, Marnix ; Singh, Deepak P. ; Borghols, Wouter J.H. ; Lafont, Ugo ; Haverkate, Lucas ; Peterson, Vanessa K. ; Mulder, Fokko M. / Dynamic Solubility Limits in Nanosized Olivine LiFePO4. In: Journal of the American Chemical Society. 2011 ; Vol. 133, No. 26. pp. 10222-10228.
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    abstract = "Because of its stability, nanosized olivine LiFePO4 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 LiFePO4. 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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    Wagemaker, M, Singh, DP, Borghols, WJH, Lafont, U, Haverkate, L, Peterson, VK & Mulder, FM 2011, 'Dynamic Solubility Limits in Nanosized Olivine LiFePO4' Journal of the American Chemical Society, vol. 133, no. 26, pp. 10222-10228. https://doi.org/10.1021/ja2026213

    Dynamic Solubility Limits in Nanosized Olivine LiFePO4. / Wagemaker, Marnix; Singh, Deepak P.; Borghols, Wouter J.H.; Lafont, Ugo; Haverkate, Lucas; Peterson, Vanessa K.; Mulder, Fokko M.

    In: Journal of the American Chemical Society, Vol. 133, No. 26, 06.07.2011, p. 10222-10228.

    Research output: Contribution to journalArticleAcademicpeer-review

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    AU - Wagemaker, Marnix

    AU - Singh, Deepak P.

    AU - Borghols, Wouter J.H.

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    AU - Haverkate, Lucas

    AU - Peterson, Vanessa K.

    AU - Mulder, Fokko M.

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    AB - Because of its stability, nanosized olivine LiFePO4 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 LiFePO4. 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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    Wagemaker M, Singh DP, Borghols WJH, Lafont U, Haverkate L, Peterson VK et al. Dynamic Solubility Limits in Nanosized Olivine LiFePO4. Journal of the American Chemical Society. 2011 Jul 6;133(26):10222-10228. https://doi.org/10.1021/ja2026213