Confining Pyrrhotite Fe₇ S₈ in Carbon Nanotubes Covalently Bonded onto 3D Few-Layer Graphene Boosts Potassium-Ion...

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.