A Metal‐Organic Framework‐Derived Strategy for Constructing Synergistic N‐Doped Carbon‐Encapsulated NiCoP@N‐C‐Based Anodes toward High‐Efficient Lithium Storage

Abstract Transition metal phosphides (TMPs) have been regarded as the prospective anodes for lithium‐ion batteries (LIBs). However, their poor intrinsic conductivity and inevitable large volume variation result in sluggish redox kinetics and the collapse of electrode structure during cycling, which substantially hinders their practical use. Herein, an effective composite electrodes design strategy of “assembly and phosphorization” is proposed to construct synergistic N‐doped carbon‐encapsulated NiCoP@N‐C‐based composites, employing a metal‐organic frameworks (MOFs) as sacrificial hosts. Serving as the anodes for LIBs, one representative P‐NCP‐NC‐600 electrode exhibits high reversible capacity (858.5 mAh g −1 , 120 cycles at 0.1 A g −1 ) and superior long‐cycle stability (608.7 mAh g −1 , 500 cycles at 1 A g −1 ). The impressive performances are credited to the synergistic effect between its unique composite structure, electronic properties and ideal composition, which achieve plentiful lithium storage sites and reinforce the structural architecture. By accompanying experimental investigations with theoretical calculations, a deep understanding in the lithium storage mechanism is achieved. Furthermore, it is revealed that a more ideal synergistic effect between NiCoP components and N‐doped carbon frameworks is fundamentally responsible for the realization of superb lithium storage properties. This strategy proposes certain instructive significance toward designable high‐performance TMP‐based anodes for high‐energy density LIBs.