Electrochemical shock and transverse cracking in solid electrolytes

Ceramic solid electrolytes are crucial for electrochemical devices, including emerging solid-state batteries. However, they are susceptible to degradation and failure under harsh conditions, leading to dendrite growth, cracking and short circuits. While longitudinal lithium dendrites have been identified as a primary degradation mechanism, recent experiments have revealed transverse reduction fronts and bowl-shaped cracks that differ significantly from the longitudinal picture. We propose an electrochemical shock model to explain these transverse degradation modes in solid electrolytes (SE) and mixed ionic-electronic conductors (MIEC), where SE is taken to be the very weakly electronic leaking limit of MIEC. The model describes a transverse layer with an abrupt oxygen potential jump over a short distance, caused by the electronic transport bottleneck on the Brouwer diagram. Using Li7La3Zr2O12 as an example, we demonstrate that even minor nonuniform lithium distribution associated with an electrochemical shock can induce stress concentrations, resulting in electrolyte cracking and bowl-shaped cracks. The electrochemical shock model highlights the significance of finite electronic conductivity in the degradation of SE and MIEC, providing insights for the design of durable solid electrolytes.