Aqueous redox flow batteries (ARFBs) are promising technology for safe and long-duration energy storage owing to their flexible architecture decoupling power and energy, which is the key to achieving massive utilization of intermittent renewable energies (solar and wind power)1. However, the high-power density at low temperatures is prohibited by the weak stability, sluggish kinetics, and limited solubility of active materials. These challenges not only preclude the commercialization of ARFBs in the high-power density market (e.g., electric automobile) but also make the renewable electric grid vulnerable to severe weather fluctuations.In this study, we describe a polyoxometalate-based active material with exceptionally fast redox kinetics and high electron solubility at low temperatures2. We optimize the charging process to achieve high electrochemical performance and will discuss factors that would influence solubility. We evaluate the kinetics of the polyoxometalate-based materials by rotating ring-disk electrodes measurement (RRDE) and adjust the electrolyte composition to increase the energy density and electrochemical stability of polyoxometalate-based electrolytes. We will discuss the full polyoxometalate-based ARFBs’ electrochemical performance, the influence of the supporting, and the possible degradation mechanism of the full cell (e.g., side reaction (hydrogen evolution, decomposition of the active materials) and crossover). Acknowledgment: The work is supported by a grant from the Research Grant Council (RGC) of the Hong Kong Special Administrative Region, China (project no. CUHK 14308622). Reference: (1) Yao, Y.; Lei, J.; Shi, Y.; Ai, F.; Lu, Y.-C. Assessment methods and performance metrics for redox flow batteries. Nature Energy 2021, 6 (6), 582.(2) Ai, F.; Wang, Z.; Lai, N.-C.; Zou, Q.; Liang, Z.; Lu, Y.-C. Heteropoly acid negolytes for high-power-density aqueous redox flow batteries at low temperatures. Nature Energy 2022, 7 (5), 417.