Synergistic Effect of Co–Ni Hybrid Phosphide Nanocages for Ultrahigh Capacity Fast Energy Storage

Rational design of metal compounds in terms of the structure/morphology and chemical composition is essential to achieve desirable electrochemical performances for fast energy storage because of the synergistic effect between different elements and the structure effect. Here, an approach is presented to facilely fabricate mixed‐metal compounds including hydroxides, phosphides, sulfides, oxides, and selenides with well‐defined hollow nanocage structure using metal–organic framework nanocrystals as sacrificial precursors. Among the as‐synthesized samples, the porous nanocage structure, synergistic effect of mixed metals, and unique phosphide composition endow nickel cobalt bimetallic phosphide (NiCo‐P) nanocages with outstanding performance as a battery‐type Faradaic electrode material for fast energy storage, with ultrahigh specific capacity of 894 C g(−1) at 1 A g(−1) and excellent rate capability, surpassing most of the reported metal compounds. Control experiments and theoretical calculations based on density functional theory reveal that the synergistic effect between Ni and Co in NiCo‐P can greatly increase the OH(−) adsorption energy, while the hollow porous structure facilitates the fast mass/electron transport. The presented work not only provides a promising electrode material for fast energy storage, but also opens a new route toward structural and compositional design of electrode materials for energy storage and conversion.