The aqueous polysulfides is an important Earth-abundant and multielectron redox couple to construct high capacity density and low-cost aqueous redox flow batteries (RFB) ; nevertheless, the sluggish conversion and kinetic behavior of S2-/Sx2- result in a low power density output and poor active material utilizations. Herein, we present nanoconfined self-assembled ordered hierarchical porous Co and N codoped carbon (OHP-Co/NC) as an electrocatalytic reactor to enhance the mass transfer and redox activity of aqueous polysulfides. Finite element method simulation proves that the OHP-Co/NC with interconnected macropores and mesopores exhibits an enhanced mass transfer and delivers a larger redox electrolyte utilization of 50.1% compared to 23.3% of conventional Co/NC. Notably, the OHP-Co/NC obtained at 850 °C delivers the smallest redox peak potential difference (ΔE = 99 mV). Comparison studies of in operando Raman for aqueous polysulfides in the redox electrolyte and in situ electrochemical Raman on the single OHP-Co/NC particle for the adsorbed polysulfides were carried out. And it confirms that the OHP-Co/NC-850 catalyst has a strong adsorption of S42- and can retard the strong disproportionation and hydrolysis behavior of polysulfides on the electrocatalyst interface. Therefore, the polysulfide/ferrocyanide RFB with an OHP-Co/NC-850 based membrane-electrode assembly (MEA) exhibited a high power density of 110 mW cm-2, as well as a steady capacity retention over 99.7% in 300 cycles.
Keywords: finite element method; hierarchical nano-electrocatalytic reactor; in situ/operando Raman spectroscopy; polysulfides; redox flow battery.