Impact of Structural Flexibility of Amine Moieties as Bridges for Redox-Active Sites on Secondary Battery Performance

Although environmentally benign organic cathode materials for secondary batteries are in demand, their high solubility in electrolyte solvents hinders broad applicability. In this study, a bridging fragment to link redox-active sites is incorporated into organic complexes with the aim of preventing dissolution in electrolyte systems with no significant performance loss. Evaluation of these complexes using an advanced computational approach reveals that the type of redox-active site (i. e., dicyanide, quinone, or dithione) is a key parameter for determining the intrinsic redox activity of the complexes, with the redox activity decreasing in the order of dithione>quinone>dicyanide. In contrast, the structural integrity is strongly reliant on the bridging style (i. e., amine-based single linkage or diamine-based double linkage). In particular, owing to their rigid anchoring effect, diamine-based double linkages incorporated at dithione sites allow structural integrity to be maintained with no significant decrease in the high thermodynamic performance of dithione sites. These findings provide insights into design directions for insoluble organic cathode materials that can sustain high performance and structural durability during repeated cycling.