Variations of boundary reaction rate and particle size on the diffusion-induced stress in a phase separating electrode

In contrast to the case of single-phase delithiation wherein faster discharging leads to higher diffusion-induced stress (DIS), this paper reports nonmonotonous dependency of the boundary reaction rate on the DIS in nanosized spherical electrode accompanying phase separation. It is attributed to a transition from two-phase to single-phase delithiation driven by increase of the boundary reaction rate leading to narrowing and vanishing of the miscibility gap in a range of the particle size. The profiles of lithium concentration and the DIS are identified during the transition based on a continuum model. The resultant maximum DIS first decreases in the region of two-phase delithiation and later returns to increase in the region of single-phase delithiation with the increase of the boundary reaction rate. A map for the failure behavior in the spherical electrode particle is constructed based on the Tresca failure criterion. These results indicate that the failure caused by the DIS can be avoided by appropriate selection of the said parameters in such electrodes.