Tetrahedral Bonding Structure (Ni₃‐Se) Induced by Lattice‐Distortion of Ni to Achieve High Catalytic Activity in Na–Se Battery

Abstract Fabrication of transition‐metal catalytic materials is regarded as a promising strategy for developing high‐performance sodium–selenium (Na–Se) batteries. However, more systematic explorations are further demanded to find out how their bonding interactions and electronic structures can affect the Na storage process. This study finds that lattice‐distorted nickel (Ni) structure can form different bonding structures with Na₂Se₄, providing high activity to catalyze the electrochemical reactions in Na–Se batteries. Using this Ni structure to prepare electrode (Se@NiSe₂/Ni/CTs) can realize rapid charge transfer and high cycle stability of the battery. The electrode exhibits high storage performance of Na⁺; i.e., 345 mAh g⁻¹ at 1 C after 400 cycles, and 286.4 mAh g⁻¹ at 10 C in rate performance test. Further results reveal the existence of a regulated electronic structure with upshifts of the d‐band center in the distorted Ni structure. This regulation changes the interaction between Ni and Na₂Se₄ to form a Ni₃–Se tetrahedral bonding structure. This bonding structure can provide higher adsorption energy of Ni to Na₂Se₄ to facilitate the redox reaction of Na₂Se₄ during the electrochemical process. This study can inspire the design of bonding structure with high performance in conversion‐reaction‐based batteries.