Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating LiXFePO4 electrode particles

Heo, Tae Wook; Chen, Long-Qing; Wood, Brandon C.

doi:10.1016/j.commatsci.2015.03.020

Title: Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating Li_XFePO₄ electrode particles

Journal Article · Wed Apr 08 00:00:00 EDT 2015 · Computational Materials Science

DOI:https://doi.org/10.1016/j.commatsci.2015.03.020· OSTI ID:1251071

Heo, Tae Wook ^[1]; Chen, Long-Qing ^[2]; Wood, Brandon C. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division
Pennsylvania State Univ., University Park, PA (United States). Dept. of Materials Science and Engineering

In this paper, we present a comprehensive phase-field model for simulating diffusion-mediated kinetic phase behaviors near the surface of a solid particle. The model incorporates elastic inhomogeneity and anisotropy, diffusion mobility anisotropy, interfacial energy anisotropy, and Cahn–Hilliard diffusion kinetics. The free energy density function is formulated based on the regular solution model taking into account the possible solute-surface interaction near the surface. The coherency strain energy is computed using the Fourier-spectral iterative-perturbation method due to the strong elastic inhomogeneity with a zero surface traction boundary condition. Employing a phase-separating Li_XFePO₄ electrode particle for Li-ion batteries as a model system, we perform parametric three-dimensional computer simulations. The model permits the observation of surface phase behaviors that are different from the bulk counterpart. For instance, it reproduces the theoretically well-established surface modes of spinodal decomposition of an unstable solid solution: the surface mode of coherent spinodal decomposition and the surface-directed spinodal decomposition mode. We systematically investigate the influences of major factors on the kinetic surface phase behaviors during the diffusional process. Finally, our simulation study provides insights for tailoring the internal phase microstructure of a particle by controlling the surface phase morphology.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Pennsylvania State Univ., University Park, PA (United States)

Sponsoring Organization:: USDOE; LLNL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)

Grant/Contract Number:: AC52-07NA27344; CMMI-1235092

OSTI ID:: 1251071

Alternate ID(s):: OSTI ID: 1250075

Report Number(s):: LLNL-JRNL-665469

Journal Information:: Computational Materials Science, Vol. 108, Issue B; ISSN 0927-0256

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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Title: Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating LiXFePO4 electrode particles

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Title: Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating Li_XFePO₄ electrode particles