CNT‐Assembled Octahedron Carbon‐Encapsulated Cu ₃P/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 ₃P/Cu encapsulated by carbon‐nanotube‐assembled hierarchical octahedral carbonaceous matrix (Cu ₃P/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 ₃P/Cu@CNHO is credited to the large specific surface area, conductive carbon matrix and metallic copper dopants, synergistic effects of the intrinsic Cu ₃P/Cu heterostructure, and well‐defined micro/nanostructure, facilitating a boosted electrochemical conductivity and accelerated diffusion kinetics.

Abstract

A facile in situ metal–organic framework‐derived engineering method is proposed for carbon‐nanotube‐assembled octahedron carbon‐encapsulated Cu ₃P/Cu heterostructure toward superior lithium storage (cycling stability, rate performance, and heat‐resistant capability). The quantitative kinetics analysis, ex situ characterizations, and density functional theory calculations further manifest the reversible conversion mechanism and the boosted kinetics of this micro/nanostructured Cu ₃P/Cu@CNHO anode with distinguished cyclability and rate performance.