Lithiation-delithiation cycles of amorphous Si nanowires investigated by molecular dynamics simulations

TL;DR

This study uses molecular dynamics simulations to investigate the atomistic mechanisms of lithiation and delithiation in amorphous silicon nanowires, revealing two-phase lithiation, stress behaviors, and the effects of cycling and temperature on phase transformations.

Contribution

The paper introduces an optimized MEAM potential for simulating amorphous Si nanowires and provides detailed insights into their lithiation/delithiation mechanisms and stress responses.

Findings

Two-phase lithiation process observed in amorphous Si nanowires.

Compressive stresses in the amorphous alloy are easily released.

Full delithiation may heal Si nanowires, enhancing battery cycle life.

Abstract

The atomistic mechanisms during lithiation and delithiation of amorphous Si nanowires ($a$-SiNW) have been investigated over cycles by molecular dynamics simulations. First, the Modified Embedded Atom Method (MEAM) potential from Cui et al. [J. Power Sources. 2012, (207) 150] has been further optimized on static (Li$_x$Si alloy phases and point defect energies) and on dynamic properties (Li diffusion) to reproduce the lithiation of small crystalline Si nanowires calculated at the {\it ab initio} level. The lithiation of $a$-SiNW reveals a two-phase process of lithiation with a larger diffusion interface compared to crystalline Si lithiation. Compressive axial stresses are observed in the amorphous Si$_x$Li alloy outer shell. They are easily released thanks to the soft glassy behavior of the amorphous alloy. Conversely, in crystalline SiNW, the larger stress in the narrow crystalline lithiated interface is hardly released and requires a phase transformation to amorphous to operate, which delays the lithiation. The history of the charge-discharge cycles as well as the temperature appear as driving forces for phase transformation from amorphous Li$_x$Si alloy to the more stable crystalline phase counterpart. Our work suggest that a full delithiation could heal the SiNWs to improve the life cycles of Li-ion batteries with Si anode.