Anisotropic Compositional Expansion and Chemical Potential of Lithiated SiO₂ Electrodes: Multiscale Mechanical...

The use of high-capacity electrode materials (i.e., Si) in Li-ion batteries is hindered by their mechanical degradation. Thus, oxides (i.e., SiO₂) are commonly used to obtain high expected capacities and long-term cycle performances. Despite extensive studies of the electrochemical-mechanical behaviors of high-capacity energy storage materials, the mechanical behaviors of amorphous SiO₂ during electrochemical reaction remain largely unknown. Here, we systematically investigate the stress evolution, electronic structure, and mechanical deformation of lithiated SiO₂ through first-principles computation and the finite element method. The structural and thermodynamic role of O in the amorphous Li-O-Si system is reported and compared with that in Si. Strong Si-O bonds in SiO₂ show high mechanical strength and brittle behavior, but as Li is inserted, the Li-rich SiO₂ phases become mechanically softened. The relaxation kinetics of SiO₂, inducing deviatoric inelastic strains under mechanical constraints, is also compared with that of Si. The finite element model including the kinetic model for anisotropic expansion demonstrates that the long-term cycling stability of core-shell Si-SiO₂ nanoparticles mainly arises from the reaction kinetics and high mechanical strength of SiO₂. These results provide fundamental insights into the chemomechanical behavior of SiO₂ for practical use.