Intercalation Kinetics in Multiphase-Layered Materials
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1701.08858.pdf
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2.11 MB
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Author(s)
Smith, Raymond Barrett
Khoo, Edwin Sze Lun
Bazant, Martin Z
Date Issued
June 2017
Journal
Journal of Physical Chemistry C
Publisher
American Chemical Society (ACS)
Citation
Smith, Raymond B. et al. “Intercalation Kinetics in Multiphase-Layered Materials.” The Journal of Physical Chemistry C 121, 23 (June 2017): 12505–12523 © 2017 American Chemical Society
Version
Original manuscript
Abstract
Many intercalation compounds possess layered structures or interpenetrating lattices that enable phase separation into three or more stable phases, or "stages," driven by competing intralayer and interlayer forces. While these structures are often well characterized in equilibrium, their effects on intercalation kinetics and transport far from equilibrium are typically neglected or approximated by empirical solid solution models. Here, we formulate a general phase-field model with thermodynamically consistent reaction kinetics and cooperative transport to capture the dynamics of intercalation in layered materials. As an important case for Li-ion batteries, we model single particles of lithium intercalated graphite as having a periodic two-layer structure with three stable phases, corresponding to zero, one, or two layers full of lithium. The electrochemical intercalation reaction is described by a generalized Butler-Volmer equation with thermodynamic factors to account for the flexible structure of the graphene planes. The model naturally captures the "voltage staircase" discharge curves as a result of staging dynamics with internal "checkerboard" domains, which cannot be described by solid-solution models based on Fickian diffusion. On the other hand, the two-layer model is computationally expensive and excludes low-density stable phases with longer-range periodicity, so we also present a reduced model for graphite, which captures the high-density stages while fitting the low-density voltage profile as an effective solid solution. The two models illustrate the general trade-off between the explicit modeling of periodic layers or lattices and the needs for computational efficiency and accurate fitting of experimental data.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Mathematics
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DOI of Published Version
https://doi.org/10.1021/ACS.JPCC.7B00185
