Active-Site-Specific Structural Engineering Enabled Ultrahigh Rate Performance of the NaLi3Fe3(PO4)2(P2O7) Cathode for Lithium-Ion Batteries

Iron-based mixed-polyanionic cathode Na₄Fe₃(PO₄)₂(P₂O₇) (NFPP) has advantages of environmental benignity, easy synthesis, high theoretical capacity, and remarkable stability. From NFPP, a novel Li-replaced material NaLi₃Fe₃(PO₄)₂(P₂O₇) (NLFPP) is synthesized through active Na-site structural engineering by an electrochemical ion exchange approach. The NLFPP cathode can show high reversible capacities of 103.2 and 90.3 mA h g^-1 at 0.5 and 5C, respectively. It also displays an impressive discharge capacity of 81.5 mA h g^-1 at an ultrahigh rate of 30C. Density functional theory (DFT) calculation demonstrates that the formation energy of NLFPP is the lowest among NLFPP, NFPP, and NaFe₃(PO₄)₂(P₂O₇), indicating that NLFPP is the easiest to form and the conversion from NFPP to NLFPP is thermodynamically favorable. The Li substitution for Na in the NFPP lattice causes an increase in the unit cell parameter c and decreases in a, b, and V, which are revealed by both DFT calculations and in situ X-ray powder diffraction (XRD) analysis. With hard carbon (HC) as the anode, the NLFPP//HC full cell shows a high reversible capacity of 91.1 mA h g^-1 at 2C and retains 82.4% after 200 cycles. The proposed active-site-specific structural tailoring via electrochemical ion exchange will give new insights into the design of high-performance cathodes for lithium-ion batteries.