Visualising plating-induced cracking in lithium anode solid electrolyte cells

Research by the Peter Bruce Group and collaborators in Oxford's departments of Materials, Chemistry, Engineering, and at the Paul Scherrer Institut and Diamond Light Source, as reported in Nature Materials, explains that the Lithium dendrite (filament) propagation through ceramic electrolytes, leading to short-circuits at high rates of charge, is one of the greatest barriers to realising high energy density all-solid-state lithium anode batteries.

Utilising in-situ X-ray computed tomography coupled with spatially mapped X-ray diffraction, the propagation of cracks and the propagation of lithium dendrites through the solid electrolyte have been tracked in a Li/Li₆PS₅Cl/Li cell as a function of the charge passed.

On plating, cracking initiates with spallation, conical 'pothole'-like cracks that form in the ceramic electrolyte near the surface with the plated electrode.  The spallations form predominantly at the lithium electrode edges where local fields are high.  Transverse cracks then propagate from the spallations across the electrolyte from the plated to the stripped electrode.  Lithium ingress drives the propogation of the spallation and transverse cracks by widening the crack from the rear, ie the crack front propagates ahead of the Li.

As a result, cracks traverse the entire electrolyte before the Li arrives at the other electrode and therefore before a short-circuit occurs.