Continuous Conducting Architecture Developed by Supporting Prussian Blue Analogue on Metal-Organic Framework Derived Carbon-Doped Manganese-Oxide Nanorods for High-Performance Sodium-Ion Batteries

Abstract

Prussian blue analogues (PBA) are regarded as promising cathode materials for sodium-ion batteries (SIBs) owing to their open framework with large interstitial sites to accommodate Na+ ions. However, PBA suffer from low electronic conductivity and mechanical instability, which may be improved by their structural modification leading to enhanced kinetics. In this regard, we report an in-situ integration of ultra-small PBA cubes into threedimensional metal organic framework (MOF) derived carbon-doped manganese oxide nanorods (C-Mn2O3), which form a continuous conductive architecture with intimate PBA/C-Mn2O3 contact. The C-Mn2O3 nanorods provide nucleation sites for the growth of PBA cubes and further act as the electronic pathway to improve electrode reaction kinetics. This hierarchical configuration effectively buffers the lattice expansion, which improve the structural stability of NiCoPBA. Consequently, the composite exhibits promising performance in aqueous Na+ batteries. Specifically, it delivers a high capacity of 97 mAh/g within a narrow potential window of and retained 82% capacity for 1000 cycles in aqueous electrolyte. It shows even higher capacity of 136 mAh/g and similar capacity retention (76% after 1000 cycles) in non-aqueous electrolytes. The promising performance of developed materials demonstrates the significant impact decreasing the size of PBA cubes has on the capacity by reducing the diffusion pathways and thus facilitating intercalation/deintercalation within the cubes. This study offers new insights of exploiting redox-active substrates to modify and stabilize PBA materials for energy storage applications.