Radiation Damage Mechanisms in Oxide-Based Solid Electrolytes

Ion implantation is a promising approach to mitigate dendrite formation in metal anode solid-state batteries by modifying the chemical and mechanical properties of oxide-based electrolyte surfaces such as Li7La3Zr2O12 (LLZO). Yet, the detailed atomistic mechanisms and potentially adverse side effects of ion implantation remain poorly understood. In this study, we used molecular dynamics simulations to elucidate the evolution of radiation-induced damage in LLZO. The results reveal that radiation damage is primarily driven by recoils from heavy ions in the lattice, producing antisite defect clusters whose density decreases as recoil energy increases, a counterintuitive finding that highlights complex cascade fragmentation. Radiation-induced disruption to the crystal sublattice connectivity, especially in the La-O network critical for Li-ion transport, leads to degradation in ionic pathways at low energies, while higher energy cascades can form new conduction pathways via enhanced Zr-O network connectivity. These findings provide a mechanistic foundation for optimizing ion implantation strategies that balance disruption of the lattice for surface modification for dendrite resistance with preservation of essential ionic conductivity.