Protocol in Evaluating Capacity of Zn–Mn Aqueous Batteries: A Clue of pH

In the literature, Zn–Mn aqueous batteries (ZMABs) confront abnormal capacity behavior, such as capacity fluctuation and diverse “unprecedented performances.” Because of the electrolyte additive-induced complexes, various charge/discharge behaviors associated with different mechanisms are being reported. However, the current performance assessment remains unregulated, and only the electrode or the electrolyte is considered. The lack of a comprehensive and impartial performance evaluation protocol for ZMABs hinders forward research and commercialization. Here, a pH clue (proton-coupled reaction) to understand different mechanisms is proposed and the capacity contribution is normalized. Then, a series of performance metrics, including rated capacity (C_r) and electrolyte contribution ratio from Mn²⁺ (CfM), are systematically discussed based on diverse energy storage mechanisms. The relationship between Mn (II) ↔ Mn (III) ↔ Mn (IV) conversion chemistry and protons consumption/production is well-established. Finally, the concrete design concepts of a tunable H⁺/Zn²⁺/Mn²⁺ storage system for customized application scenarios, opening the door for the next-generation high-safety and reliable energy storage system, are proposed.