Mo-Doped Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 /C Composites for High-Rate and Long-Life Sodium-Ion Batteries.

Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 /C (NFPP) is a promising cathode material for sodium-ion batteries, but its electrochemical performance is heavily impeded by its low electronic conductivity. To address this, pure-phase Mo 6+ -doped Na 4 Fe 3-x Mo x (PO 4 ) 2 P 2 O 7 /C (Mox-NFPP, x = 0, 0.05, 0.10, 0.15) with the Pn21a space group is successfully synthesized through spray drying and annealing methods. Density functional theory (DFT) calculations reveal that Mo 6+ doping facilitates the transition of electrons from the valence to the conduction band, thus enhancing the intrinsic electron conductivity of Mox-NFPP. With an optimal Mo 6+ doping level of x = 0.10, Mo0.10-NFPP exhibits lower charge transfer resistance, higher sodium-ion diffusion coefficients, and superior rate performance. As a result, the Mo0.10-NFPP cathode offers an initial discharge capacity of up to 123.9 mAh g -1 at 0.1 C, nearly reaching its theoretical capacity. Even at a high rate of 10 C, it delivers a high discharge capacity of 86.09 mAh g -1 , maintaining 96.18% of its capacity after 500 cycles. This research presents a new and straightforward strategy to enhance the electrochemical performance of NFPP cathode materials for sodium-ion batteries.