Ni2P@Carbon Core–Shell Nanoparticle‐Arched 3D Interconnected Graphene Aerogel Architectures as Anodes for High‐Performance Sodium‐Ion Batteries

To alleviate large volume change and improve poor electrochemical reaction kinetics of metal phosphide anode for sodium‐ion batteries, for the first time, an unique Ni₂P@carbon/graphene aerogel (GA) 3D interconnected porous architecture is synthesized through a solvothermal reaction and in situ phosphorization process, where core–shell Ni₂P@C nanoparticles are homogenously embedded in GA nanosheets. The synergistic effect between components endows Ni₂P@C/GA electrode with high structural stability and electrochemical activity, leading to excellent electrochemical performance, retaining a specific capacity of 124.5 mA h g^?1 at a current density of 1 A g^?1 over 2000 cycles. The robust 3D GA matrix with abundant open pores and large surface area can provide unblocked channels for electrolyte storage and Na⁺ transfer and make fully close contact between the electrode and electrolyte. The carbon layers and 3D GA together build a 3D conductive matrix, which not only tolerates the volume expansion as well as prevents the aggregation and pulverization of Ni₂P nanoparticles during Na⁺ insertion/extraction processes, but also provides a 3D conductive highway for rapid charge transfer processes. The present strategy for phosphides via in situ phosphization route and coupling phosphides with 3D GA can be extended to other novel electrodes for high‐performance energy storage devices.