Search for Active and Inactive Ion Insertion Sites in Organic Crystalline Materials

Abstract

The position of mobile active and inactive ions, specifically ion insertion sites, within organic crystals, significantly affects the properties of organic materials used for energy storage and ionic transport. Identifying the positions of these atom (and ion) sites in an organic crystal is difficult, especially when the element has a low X-ray scattering power, such as lithium (Li) and hydrogen, which are difficult to detect with powder X-ray diffraction (XRD) methods. First-principles calculations, exemplified by density functional theory (DFT), are very effective for confirming the relative stability of ion positions in materials. However, the lack of effective strategies to identify ion sites in these organic crystalline frameworks renders this task extremely challenging. This work presents two algorithms: (i) Efficient Location of Ion Insertion Sites from Extrema in electrostatic local potential and charge density (ELIISE), and (ii) ElectRostatic InsertioN (ERIN), which leverage charge density and electrostatic potential fields accessed from first-principles calculations, combined with the Simultaneous Ion Insertion and Evaluation (SIIE) workflow -- that inserts all ions simultaneously -- to determine ion positions in organic crystals. We demonstrate that these methods accurately reproduce known ion positions in 16 organic materials and also identify previously overlooked low-energy sites in tetralithium 2,6-naphthalenedicarboxylate (Li$_4$NDC), an organic electrode material, highlighting the importance of inserting all ions simultaneously as done in the SIIE workflow.