Electrochemical‐Doping of Tungsten on Nickel‐Boron‐Phosphide Microspheres for Accelerated Industrial‐Scale Water Electrolysis at High Current Density

Abstract Development of alternative electrocatalysts with high efficiency and stable operation at high current density (HCD) put a challenge for industrial‐level green‐hydrogen production. Herein, tungsten doping is systematically demonstrated on nickel‐boron‐phosphide (W/NiBP) microsphere electrode (ME) by an electrodeposition approach for industrial‐level green‐hydrogen generation. The W/NiBP ME exhibits low hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials of 80 and 330 mV at 100 mA cm −2 in 1 m KOH, respectively, outperforming the benchmark electrocatalysts of Pt/C and RuO 2. The bi‐functional W/NiBP demonstrates a remarkably low voltage of 1.85 V at 500 mA cm −2 in 1 m KOH for overall water splitting (OWS), exceeding most of the state‐of‐the‐art electrocatalysts. Moreover, the W/NiBP exhibits an ultra‐low cell voltage of 2.50 V under harsh industrial conditions at 2,000 mA cm −2 in 6 m KOH at 60 °C and steady operation at 1,000 mA cm −2 for over 200 h, which is superior to most of the reported electrocatalysts at HCD. A small amount of W incorporation can significantly accelerate the catalytic activity of NiBP microspheres by the increased electrochemical surface area, optimized adsorption‐desorption kinetics of intermediates, high intrinsic activity, and corrosion resistance.