Influence of Linker Group on Bipolar Redox‐Active Molecule Performance in Non‐Aqueous Redox Flow Batteries

Abstract Redox flow batteries (RFBs) are an attractive choice for stationary energy storage of renewables such as solar and wind. Non‐aqueous redox flow batteries (NARFBs) have garnered broad interest due to their high voltage operation compared to their aqueous counterparts. Further, the utilization of bipolar redox‐active molecules (BRMs) is a practical way to alleviate crossover faced by asymmetric RFBs. In this work, ferrocene (Fc) and phthalimide (PI) are covalently linked with various tethering groups which vary in structure and length. The compiled results suggest that the length and steric shielding ability of the linker group can greatly influence the stability and overall performance of Fc‐ n ‐PI BRM‐based NARFBs. Primary sources of capacity loss are found to be BRM degradation for straight chain spacers <6 carbons and membrane (Nafion) fouling. Fc‐hexyl‐PI provided the most stable battery cycling and coulombic efficiencies of >98 % over 100 cycles (~13 days). NARFB using Fc‐hexyl‐PI as an active material exhibited high working voltage (1.93 V) and maximum capacity (1.28 Ah L −1 ). Additionally, this work highlights rational strategies to improve cycling stability and optimize NARFB performance.