Analysis of the Ordering Effects in Anthraquinone Thin Films and Its Potential Application for Sodium Ion Batteries

[Image: see text] The ordering effects in anthraquinone (AQ) stacking forced by thin-film application and its influence on dimer solubility and current collector adhesion are investigated. The structural characteristics of AQ and its chemical environment are found to have a substantial influence on its electrochemical performance. Computational investigation for different charged states of AQ on a carbon substrate obtained via basin hopping global minimization provides important insights into the physicochemical thin-film properties. The results reveal the ideal stacking configurations of the individual AQ-carrier systems and show ordering effects in a periodic supercell environment. The latter reveals the transition from intermolecular hydrogen bonding toward the formation of salt bridges between the reduced AQ units and a stabilizing effect upon the dimerlike rearrangement, while the strong surface–molecular interactions in the thin-film geometries are found to be crucial for the formed dimers to remain electronically active. Both characteristics, the improved current collector adhesion and the stabilization due to dimerization, are mutual benefits of thin-film electrodes over powder-based systems. This hypothesis has been further investigated for its potential application in sodium ion batteries. Our results show that AQ thin-film electrodes exhibit significantly better specific capacities (233 vs 87 mAh g(–1) in the first cycle), Coulombic efficiencies, and long-term cycling performance (80 vs 4 mAh g(–1) after 100 cycles) over the AQ powder electrodes. By augmenting the experimental findings via computational investigations, we are able to suggest design strategies that may foster the performance of industrially desirable powder-based electrode materials.