Thermal Recovery of the Electrochemically Degraded LiCoO₂/Li₇La₃Zr₂O₁₂:Al,Ta Interface in an All-Solid-State Lithium Battery

All-solid-state lithium batteries are promising candidates for next-generation energy storage systems. Their performance critically depends on the capacity and cycling stability of the cathodic layer. Cells with a garnet Li₇La₃Zr₂O₁₂ (LLZO) electrolyte can show high areal storage capacity. However, they commonly suffer from performance degradation during cycling. For fully inorganic cells based on LiCoO₂ (LCO) as cathode active material and LLZO, the electrochemically induced interface amorphization has been identified as an origin of the performance degradation. This study shows that the amorphized interface can be recrystallized by thermal recovery (annealing) with nearly full restoration of the cell performance. The structural and chemical changes at the LCO/LLZO heterointerface associated with degradation and recovery were analyzed in detail and justified by thermodynamic modeling. Based on this comprehensive understanding, this work demonstrates a facile way to recover more than 80% of the initial storage capacity through a thermal recovery (annealing) step. The thermal recovery can be potentially used for cost-efficient recycling of ceramic all-solid-state batteries.