Redox-active organic molecules are promising charge-storage materials for redox-flow batteries (RFBs), but material crossover between the posolyte and negolyte and chemical degradation are limiting factors in the performance of all-organic RFBs. We demonstrate that the bipolar electrochemistry of 1,2,4-benzotriazin-4-yl (Blatter) radicals allows the construction of batteries with symmetrical electrolyte composition. Cyclic voltammetry shows that these radicals also retain reversible bipolar electrochemistry in the presence of water. The redox potentials of derivatives with a C(3)-CF 3 substituent are the least affected by water, and moreover, these compounds show >90% capacity retention after charge/discharge cycling in a static H-cell for 7 days (ca. 100 cycles). Testing these materials in a flow regime at a 0.1 M concentration of the active material confirmed the high cycling stability under conditions relevant for RFB operation and demonstrated that polarity inversion in a symmetrical flow battery may be used to rebalance the cell. Chemical synthesis provides insight in the nature of the charged species by spectroscopy and (for the oxidized state) X-ray crystallography. The stability of these compounds in all three states of charge highlights their potential for application in symmetrical organic redox-flow batteries.

Redox-active organic molecules are promising charge-storage materials for redox-flow batteries (RFBs), but material crossover between posolyte/negolyte and chemical degradation are limiting factors in the performance of all-organic RFBs. We demonstrate that the bipolar electrochemistry of 1,2,4-benzotriazin-4-yl (Blatter) radicals allows construction of batteries with symmetric electrolyte composition. Cyclic voltammetry shows that these radicals retain reversible bipolar electrochemistry also in the presence of water. The redox potentials of derivatives with a C(3)-CF3 substituent are least affected by water and, moreover, these compounds show >90% capacity retention after charge/discharge cycling in a static H-cell for seven days (ca. 100 cycles). Testing these materials in a flow regime at 0.1 M concentration of active material confirmed the high cycling stability under conditions relevant for RFB operation, and demonstrated that polarity inversion in a symmetric flow battery may be used to rebalance the cell. Chemical synthesis provides insight in the nature of the charged species by spectroscopy and (for the oxidized state) X-ray crystallography. The stability of these compounds in all three states of charge highlights the potential for application in symmetric organic redox-flow batteries.