High-entropy doping strengthens Ni-S covalent bonds for industrially stable oxygen evolution

doi:10.1016/j.jmst.2025.10.054

Abstract

Abstract: Nickel sulfide exhibits exceptional oxygen evolution reaction (OER) activity in alkaline water electrolysis owing to its near-metal conductivity and favorable reaction kinetics. However, its industrial implementation remains limited due to structural degradation induced by the instability of Ni-S covalent bonds. Herein, we propose a high-entropy doping strategy incorporating six transition metals (Fe, Co, Mn, Zn, Cr, and Mo) to stabilize high-entropy Ni₃S₂ (HE-Ni₃S₂). HE-Ni₃S₂ shows lattice contraction and tight Ni 3d-S 3p orbital overlap, substantially strengthening Ni-S covalent bonds and mitigating Ni and S dissolution. Abundant sulfur vacancies and interactions between Ni and dopants also synergistically optimize the electronic configuration and adsorption energy of Ni active sites, thus reducing the energy barrier for the OER. HE-Ni₃S₂ achieves an ultralow overpotential of 265 mV at 100 mA cm^-2 in 1 M KOH and demonstrates unprecedented stability, operating continuously for 2400 h (100 days) at 500 mA cm^-2 without considerable degradation. Under approximate industrial conditions (30 wt.% KOH, 60 °C), an electrolyzer using an HE-Ni₃S₂ anode also maintains stable performance for >1200 h (50 days) at 500 mA cm^-2. This study establishes a high-entropy doping method for designing robust catalysts towards various applications.

Key words: High-entropy doping, Electronic optimization, Oxygen evolution reaction, Catalytic stability, Metal sulfides

Xueqiang Zhang, Xuewen Xia, Ya Gao, Xing Yu, Zhongya Pang, Guangshi Li, Qian Xu, Hsien-Yi Hsu, Yufeng Zhao, Shen Hu, Li Ji, Xionggang Lu, Xingli Zou. High-entropy doping strengthens Ni-S covalent bonds for industrially stable oxygen evolution[J]. J. Mater. Sci. Technol., 2026, 263: 67-75.

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