Solid electrolyte cracking due to lithium filament growth and concept of mechanical reinforcement - An operando study

Lithium metal solid state batteries (LMSSB) attract great interest in academia and industry due to their projected high energy density and safety. However, hard short circuits due to the penetration of lithium filaments through the solid electrolyte impede their development for practical application. Here, multi-characterization methods ranging from operando and in situ scanning electron microscopy to ex situ focused ion beam scanning electron microscopy are employed for comprehensive understanding of the cell failure. The rapid failure is attributed to coupled crack propagation and subsequent lithium filament growth during the plating process which is demonstrated in a Li6PS5Cl (lithium argyrodite) based LMSSB. Cracking initiates at current constriction spots and voids, where inhomogeneous lithium plating/stripping causes high local stress fields that trigger continuous crack propagation. Lithium filament growth finally leads to a hard short circuit. Considering the low fracture toughness of ceramic electrolytes, strengthening with Al2O3 fibers is shown to be effective in significantly improving the critical current density and cycling stability. Our results clearly show that cracks can have a detrimental effect on LMSSB and we suggest focusing on strategies to improve the fracture toughness of thiophosphate electrolytes in order to suppress lithium filament growth.