Three-Dimensional (3D) Ordered Macroporous Bimetallic (Mn,Fe) Selenide/Carbon Composite with Heterojunction Interface for High-Performance Sodium Ion Batteries.

Transition-metal selenides have captured significant research attention as anode materials for sodium ion batteries (SIBs) due to their high theoretical specific capacities and excellent electronic conductivity. However, volumetric expansion and inferior cycle life still hinder their practical application. Herein, a three-dimensional (3D) ordered macroporous bimetallic (Mn,Fe) selenide modified by a carbon layer (denoted as 3DOM-MnFeSe@C) composite containing a heterojunction interface is fabricated through selenizing a 3D ordered macroporous Mn-based Prussian Blue analogue single crystal. The 3DOM-MnFeSe@C exhibits hierarchically porous architecture with enhanced mass-transfer efficiency; MnSe and FeSe particles are encapsulated into macroporous carbon framework, which can significantly promote the electronic conductivity and maintain the structural integrity. The density functional theory calculation indicates that the heterojunction interface between MnSe and FeSe has been successfully engineered so that Na can be readily adsorbed and rapidly converted, thus promoting the reaction kinetics and extending the cyclic life. As expected, the 3DOM-MnFeSe@C composite delivers excellent rate performance (277.6 mA h g at 10 A g), and prolonged cycling life (191.6 mA h g even after 1000 cycles at 2 A g) as a sodium storage anode. The sodium storage mechanism of the composite was further investigated by in situ X-ray diffraction and ex situ high-resolution transmission electron microscopy characterization techniques.