Confining Pyrrhotite Fe 7 S 8 in Carbon Nanotubes Covalently Bonded onto 3D Few‐Layer Graphene Boosts Potassium‐Ion Storage and Full‐Cell Applications

The pyrrhotite Fe7 S8 with mixed Fe-valence possesses high theoretical capacity, high conductivity, low discharge/charge voltage plateaus, and superior redox reversibility but suffers from structural degradation upon (de)potassiation process due to severe volume variations. Herein, to conquer this issue, a novel hierarchical architecture of confining nano-Fe7 S8 in carbon nanotubes covalently bonded onto 3D few-layer graphene (Fe7 S8 @CNT@3DFG) is designed for potassium storage. Notably, CNTs could successfully grow on the surface of 3DFG via a tip-growth model under the catalytic effect of Fe3 C. Such structure enables the hierarchical confinement of 0D nano-Fe7 S8 to 1D CNTs and further 1D CNTs to 3DFG, effectively buffering the volume variations, prohibiting the agglomeration of Fe7 S8 nanograins, and boosting the ionic/electronic transportation through the stable and conductive CNTs-grafted 3DFG framework. The as-prepared Fe7 S8 @CNT@3DFG electrode delivers an exceptional rate capability (502 mAh g-1 at 50 mA g-1 with 277 mAh g-1 at 1000 mA g-1 ) and an excellent long-term cyclic stability up to 1300 cycles. Besides, the in-situ XRD and ex-situ XPS/HRTEM results first elucidate the highly reversible potassium-storage mechanism of Fe7 S8 . Furthermore, the designed potassium full-cell employing Fe7 S8 @CNT@3DFG anode and potassium Prussian blue (KPB) cathode delivers a promising energy density of ≈120 Wh kg-1 , demonstrating great application prospects.