Gradient Distribution of Zincophilic Sites for Stable Aqueous Zinc-Based Flow Batteries with High Capacity.

Current collectors, as reaction sites, play a crucial role in influencing various electrochemical performances in emerging cost-effective zinc-based flow batteries (Zn-based FBs). 3D carbon felts (CF) are commonly used but lack effectiveness in improving Zn metal plating/stripping. Here, a current collector with gravity-induced gradient copper nanoparticles (CF-G-Cu NPs) is developed, integrating gradient conductivity and zincophilicity to regulate Zn deposition and suppress side reactions. The CF-G-Cu NPs electrode modulates Zn nucleation and growth via the zincophilic Cu/CuZn₅ alloy has been confirmed by density functional theory (DFT) calculations. Finite element simulation demonstrates the gradient internal structure effectively optimizes the local electric/current field distribution to regulate the Zn²⁺ flux, improving bottom-up plating behavior for Zn metal and mitigating top-surface dendrite growth. As a result, Zn-based asymmetrical FBs with CF-G-Cu NPs electrodes achieve an areal capacity of 30 mAh cm^-2 over 640 h with Coulombic efficiency of 99.5% at 40 mA cm^-2. The integrated Zn-Iodide FBs exhibit a competitive long-term lifespan of 2910 h (5800 cycles) with low energy efficiency decay of 0.062% per cycle and high cumulative capacity of 112800 mAh cm^-2 at a high current density of 100 mA cm^-2. This gradient distribution strategy offers a simple mode for developing Zn-based FB systems.