Morphology-Property Interplay in Chemo-Mechanics of Ion-Intercalation Active Particles

Abstract

Morphology, material property, and mechanical constraint jointly govern the chemo-mechanical behavior of ion-intercalation particles, yet their coupled effects remain insufficiently understood. Here we establish a thermodynamically consistent single-particle framework and combine analytical solutions with multiphysics simulations to determine how these factors regulate lithiation and stress generation. We study hollow spherical, cylindrical, and ellipsoidal particles with isotropic or transversely isotropic material properties under fully constrained, inner-free, or unconstrained boundary conditions. We show that the transient lithiation pathway and the associated stress and strain fields are governed not by morphology, property, or constraint alone, but by their coupled interaction: isotropic particles are sensitive to the mechanical constraint, whereas transversely isotropic particles exhibit persistent heterogeneous lithiation dominated by anisotropic diffusivity. Flux decomposition analysis reveals that the mechanical contribution to Li flux is negligible in spheres but dominant in ellipsoids. Correlation analysis further shows that Li concentration and volumetric strain exhibit strong anti-correlation in unconstrained particles but weak correlation under full constraints. Bayesian optimization of hollow ellipsoids identifies Pareto-optimal morphologies that balance lithiation capacity against peak tensile stress. These results provide a unified framework for the morphology-property interplay in intercalation particles and offer morphology design principles for chemo-mechanical stability.