Discharge Rate-Driven Li₂O₂ Growth Exhibits Unconventional Morphology Trends in Solid-State Li-O₂ Batteries

Solid-state lithium oxygen batteries (LOBs) are known for their enhanced safety, higher electrochemical stability, and improved energy density compared to liquid-state LOBs. However, the investigation of solid-state LOBs is limited with little understanding of their discharge and charge processes. In this work, a polymer-based solid-state LOB is used to investigate the effect of discharge rate on lithium peroxide (Li₂O₂) formation, the oxygen evolution reaction (OER), and cycle performance. Notably, we observe a counterintuitive trend: Li₂O₂ particle size increases with increasing discharge current density, in contrast to liquid systems. This behavior arises from inherent space charge layers that restrict Li⁺ transport under high current, and spatially heterogeneous active sites at the solid electrolyte-cathode interface, directly evidenced by small angle X-ray scattering (SAXS), which govern nucleation accessibility and promote site-selective Li₂O₂ growth. Furthermore, higher current densities improve ORR and OER efficiency but accelerate anode degradation, while lower currents promote side reactions. These opposing effects result in a trade-off that defines an optimal discharge rate (0.1 mA cm⁻²) for maximizing cycle life. This study provides a new mechanistic perspective on discharge-driven processes in solid-state LOBs and offers practical guidelines for performance optimization in future high-energy battery systems.