Accelerated Li Penetration and Crack Propagation Due to Mechanical Degradation of Sulfide‐Based Solid Electrolyte

Cl (LPSCl) solid electrolyte (SE), crack nucleation and propagation in the SE, and the associated mechanical forces driving these dendrites and cracks. Two different growth modes for lithium dendrites are identified by ex situ scanning electron microscopy (SEM) observation: longitudinal cracking inside pores in the SE and lateral penetration along boundaries of the SE particles. These in situ TEM tests reveal that concentrated Li plating in a nano-sized defect on the LPSCl surface will lead to the nucleation and propagation of cracks into the LPSCl under a stress much smaller than the expected mechanical strength of the LPSCl material. This unexpected mechanical degradation is caused by a reduction in the mechanical strength of LPSCl during electrochemical charge/discharge cycling, resulting from a disorder in the crystal structure of LPSCl as revealed by DFT simulations. Due to this mechanical degradation of LPSCl, the threshold force necessary to initiate crack growth is much lower than the previously expected force to drive dendrite growth.