Rethinking battery degradation in presence of surface effects: mechanical versus electrochemical peformance mediated by charging condition

Abstract: Surface stresses, in nano-sized anode particles undergoing chemomechanical interactions, have a relaxing effect on the diffusion-induced stresses thus improving the mechanical endurance of the particles, whereas, the compressive effect of surface stresses degrades the electrochemical performance. However, this straightforward prediction of an improved mechanical performance is challenged in this work. Silicon nanowires undergoing huge volumetric changes during lithiation, may undergo significant axial length-increase, which serves as an important criterion in determining the mechanical performance of SiNWs. Interestingly, surface stresses tend to reduce the length-increase under potentiostatic charging condition, but under galvanostatic charging, the length-increase gets enhanced, thus degrading the mechanical performance of the SiNWs. To further make the study more inclusive, the nanowire is modelled with a constraining material at its core, and a competitive analysis is presented for the overall performance of the anode particles under the combined effects of surface stresses and constraining material. The mathematical model is based on large deformation theory, considering two-way coupling of diffusion-induced stresses and stress-enhanced diffusion. It is hoped that this study will provide a fresh perspective in designing next-generation lithium-ion battery particles.