Heterogeneity in Point Defect Distribution and Mobility in Solid Ion Conductors

Alkali metal anodes paired with solid ion conductors offer promising avenues for enhancing battery energy density and safety. To facilitate rapid ion transport crucial for fast charging and discharging of batteries, it is essential to understand the behavior of point defects in these conductors. In this study, we investigate the heterogeneity of defect distribution in two prototypical solid ion conductors, Li₃OCl and Li₂PO₂N (LiPON), by quantifying the defect formation energy (DFE) as a function of distance from the surface and interface through first-principles simulations. To simulate defects at the electrode-electrolyte interface, we perform calculations of Li⁺ vacancy in Li₃OCl near its interface with lithium metal. Our results reveal a significant difference between the bulk and surface/interface DFE which could lead to defect aggregation/depletion near the surface/interface. Interestingly, while Li₃OCl has a lower surface DFE than the bulk in most cases, LiPON follows the opposite trend with a higher surface DFE compared to the bulk. Due to this difference between bulk and surface DFE, the defect density can be up to 14 orders of magnitude higher at surfaces compared to the bulk. Further, we reveal that the DFE transition from surface/interface to bulk is precisely characterized by an exponentially decaying function. By incorporating this exponential trend, we develop a revised model for the average behavior of defects in solid ion conductors that offers a more accurate description of the influence of grain sizes. Surface effects dominate for grain sizes ≲1 μm, highlighting the importance of surface defect engineering and the DFE function for accurately capturing ion transport in devices. We further explore the kinetics of defect redistribution by calculating the migration barriers for defect movement between bulk and surfaces. We find a highly asymmetric energy landscape for the lithium vacancies, exhibiting lower migration barriers for movement toward the surface compared to the bulk, while interstitial defects exhibit comparable kinetics between surface and bulk regions. These insights highlight the importance of considering both thermodynamic and kinetic factors in designing solid ion conductors for improved ion transport at surfaces and interfaces.