CNT‐Assembled Octahedron Carbon‐Encapsulated Cu3P/Cu Heterostructure by In Situ MOF‐Derived Engineering for Superior Lithium Storage: Investigations by Experimental Implementation and First‐Principles Calculation

Abstract Conspicuously, metal–organic frameworks (MOFs) serve as homogenously and periodically atom‐dispersed self‐sacrificial template for in situ engineering of hierarchical porous carbon‐encapsulated micro/nanoheterostructure materials, integrating the merits of micro/nanostructure to high‐volumetric energy storage. Copper phosphide represents a promising candidate due to its compact material density compared to commercial graphite. Herein, micro/nanostructured Cu 3 P/Cu encapsulated by carbon‐nanotube‐assembled hierarchical octahedral carbonaceous matrix (Cu 3 P/Cu@CNHO) is constructed by an in situ MOF‐derived engineering for novel anode material in LIBs, which achieves an extraordinary cycling stability (a well‐maintained gravimetric/volumetric capacity of 463.2 mAh g −1 /1878.4 mAh cm −3 at 1 A g −1 up to 1600 cycles) and distinguished rate capability (an ameliorated capacity of 317.7 mAh g −1 even at 10 A g −1 ), together with unprecedented heat‐resistant capability (an elevated temperature of 50 °C for 1000 cycles maintaining 434.7 mAh g −1 at 0.5 A g −1 ). The superior electrochemical performance of Cu 3 P/Cu@CNHO is credited to the large specific surface area, conductive carbon matrix and metallic copper dopants, synergistic effects of the intrinsic Cu 3 P/Cu heterostructure, and well‐defined micro/nanostructure, facilitating a boosted electrochemical conductivity and accelerated diffusion kinetics.