Ni(3)S(2)–Ni Hybrid Nanospheres with Intra‐Core Void Structure Encapsulated in N‐Doped Carbon Shells for Efficient and Stable K‐ion Storage

Iron group metals chalcogenides, especially NiS, are promising candidates for K‐ion battery anodes due to their high theoretical specific capacity and abundant reserves. However, the practical application of NiS‐based anodes is hindered by slow electrochemical kinetics and unstable structure. Herein, a novel structure of Ni(3)S(2)–Ni hybrid nanosphere with intra‐core voids encapsulated by N‐doped carbon shells (Ni(3)S(2)‐Ni@NC‐AE) is constructed, based on the first electrodeposited NiS nanosphere particles, dopamine coating outer layer, oxygen‐free annealing treatment to form Ni(3)S(2)‐Ni core and N‐doped carbon shell, and selective etching of the Ni phase to form intra‐core void. The electron/K(+) transport and K(+) storage reaction kinetics are enhanced due to shortened diffusion pathways, increased active sites, generation of built‐in electric field, high K(+) adsorption energies, and large electronic density of states at Fermi energy level, resulting from the multi‐structures synergistic effect of Ni(3)S(2)‐Ni@NC‐AE. Simultaneously, the volume expansion is alleviated due to the sufficient buffer space and strong chemical bonding provided by intra‐core void and yolk–shell structure. Consequently, the Ni(3)S(2)‐Ni@NC‐AE exhibits excellent specific capacity (438 mAh g(−1) at 0.1 A g(−1) up to 150 cycles), outstanding rate performances, and ultra‐stable long‐cycle performance (176.4 mAh g(−1) at 1 A g(−1) up to 5000 cycles) for K‐ion storage.