LAUSR

The integration of highly‐safe Mg anode and fast Li+ kinetics endows hybrid Mg2+/Li+ batteries (MLIBs) a promising future, but the practical application is circumvented by the lack of appropriate cathodes that enable the realization of an enough participation of Mg2+ in the reactions, resulting in a high dependence on Li+. Herein, the authors develop a series of size‐controllable nickel sulfide nanoparticles embedded in carbon nanofibers (NiS@C) with synergistic effect of particle diameter and carbon content as the cathode material for MLIBs. The optimized particle size is designed to maximize the utilization of the active material and remit internal stress, and appropriate carbon encapsulation efficiently inhibiting the pulverization of particles and accelerates the ability of conducting ions and electrons. In consequence, the representative NiS@C delivers superior electrochemical performance with a highest discharge capacity of 435 mAh g−1 at 50 mA g−1. Such conversion cathode also exhibits excellent rate performance and remarkable cycle life. Significantly, the conversion mechanism of NiS in MLIBs is unambiguously demonstrated for the first time, affirming the corporate involvement of both Mg2+ and Li+ at the cathodic side. This work underlines a guide for developing conversion‐type materials with high rate capability and cyclic performance for energy storage applications.