Stress-Dependent Chemo-Mechanical Performance of Amorphous Si Anodes for Li-Ion Batteries upon Lithiation

Alloying-type anodes are significantly governed by their chemo-mechanical performance during the electrochemical cycling. The reaction-induced huge volumetric change of these anodes may cause material degradation and failure under mechanical constraints. Here, we investigate the stress-dependent lithiation behavior of amorphous Si (a-Si) anodes using molecular dynamics simulations. It is indicated that a-Si anodes can sustain higher hydrostatic stress than biaxial/uniaxial ones without the occurrence of mechanical failure. Thermodynamic and electrochemical calculations demonstrate that although the lithiation procedure also affects the thermodynamic stability of a-Si anodes, it is mainly dominated by the external mean stresses. Compressive stress is confirmed to destabilize a-Si anodes and further trigger their capacity fading. Compared with our atomistic simulations, previous continuum models underestimate the open-cell potentials of a-Si anodes, due to their ignored large volumetric deformation at higher stresses and Li concentrations. This computational study provides the intensive atomic-level understanding of the stress-dependent lithiation behavior of a-Si anodes.

Automated summary

The study reveals that amorphous Si anodes can withstand higher hydrostatic stress, while prone to mechanical failure under biaxial or uniaxial stress. The thermodynamic stability of a-Si anodes is mainly influenced by external mean stresses, with compressive stress destabilizing the anodes and causing capacity fading. Previous continuum models underestimate the open-cell potentials of a-Si anodes due to neglected volumetric deformation at higher stresses and Li concentrations.