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 Li ₇La ₃Zr ₂O ₁₂ 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.