Interplay of phase boundary anisotropy and electro-autocatalytic surface reactions on the lithium intercalation dynamics in Li$_X$FePO$_4$ platelet-like nanoparticles

TL;DR

This study uses a phase-field model to explore how surface reactions and interfacial tension anisotropy influence phase separation in LiFePO4 nanoparticles, aligning with experimental observations.

Contribution

It introduces a 2D electro-chemo-mechanical phase-field model that captures subsurface phase morphologies and highlights the role of anisotropy and surface reactions in phase behavior.

Findings

Anisotropic interfacial tension controls subsurface phase morphology.

Surface reactions suppress phase separation during lithiation.

Model results agree with in operando imaging experiments.

Abstract

Experiments on single crystal Li$_X$FePO$_4$ (LFP) nanoparticles indicate rich nonequilibrium phase behavior, such as suppression of phase separation at high lithiation rates, striped patterns of coherent phase boundaries, nucleation by binarysolid surface wetting and intercalation waves. These observations have been successfully predicted (prior to the experiments) by 1D depth-averaged phase-field models, which neglect any subsurface phase separation. In this paper, using an electro-chemo-mechanical phase-field model, we investigate the coherent non-equilibrium subsurface phase morphologies that develop in the $ab$- plane of platelet-like single-crystal platelet-like Li$_X$FePO$_4$ nanoparticles. Finite element simulations are performed for 2D plane-stress conditions in the $ab$- plane, and validated by 3D simulations, showing similar results. We show that the anisotropy of the interfacial tension tensor, coupled with electroautocatalytic surface intercalation reactions, plays a crucial role in determining the subsurface phase morphology. With isotropic interfacial tension, subsurface phase separation is observed, independent of the reaction kinetics, but for strong anisotropy, phase separation is controlled by surface reactions, as assumed in 1D models. Moreover, the driven intercalation reaction suppresses phase separation during lithiation, while enhancing it during delithiation, by electro-autocatalysis, in quantitative agreement with {\it in operando} imaging experiments in single-crystalline nanoparticles, given measured reaction rate constants.