MOF-derived nitrogen-doped core–shell hierarchical porous carbon confining selenium for advanced lithium–selenium batteries

Abstract

The lithium–selenium (Li–Se) battery has attracted growing interest recently due to its high energy density and theoretical capacity. However, the shuttle effect and volume change during cycling severely hinder its further application. In this work, we report a metal–organic framework (MOF)-derived nitrogen-doped core–shell hierarchical porous carbon (N-CSHPC) with interconnected meso/micropores to effectively confine Se for high-performance Li–Se batteries. The micropores were located at the ZIF-8-derived core and the ZIF-67-derived shell, while mesopores appeared at the core–shell interface after the pyrolysis of the core–shell ZIF-8@ZIF-67 precursor. Such a special hierarchical porous structure effectively confined selenium and polyselenides to prevent their dissolution from the pores and also alleviated the volume change. In particular, in situ nitrogen doping, which afforded N-CSHPC, not only improved the electrical conductivity of Se but also provided strong chemical adsorption on Li₂Se, as confirmed by density functional theory calculations. On the basis of dual-physical confinement and strong chemisorption, Se/N-CSHPC-II (molar ratio of Co source to Zn source of 1.0 in the core–shell ZIF-8@ZIF-67 precursor) exhibited reversible capacities of up to 555 mA h g⁻¹ after 150 cycles at 0.2 C and 462 mA h g⁻¹ after 200 cycles at 0.5 C and even a discharge capacity of 432 mA h g⁻¹ after 200 cycles at 1 C. Our demonstration here suggests that the carefully designed Se/C composite can improve the reversible capacity and cycling stability of Se cathodes for Li–Se batteries.