Accelerating Li‐Ion Diffusion in LiFePO₄ by Polyanion Lattice Engineering

Abstract Despite the widespread commercialization of LiFePO₄ as cathodes in lithium‐ion batteries, the rigid 1D Li‐ion diffusion channel along the [010] direction strongly limits its fast charge and discharge performance. Herein, lattice engineering is developed by the planar triangle BO₃³⁻ substitution on tetrahedron PO₄³⁻ to induce flexibility in the Li‐ion diffusion channels, which are broadened simultaneously. The planar structure of BO₃³⁻ may further provide additional paths between the channels. With these synergetic contributions, LiFe(PO₄)_0.98(BO₃)_0.02 shows the best performance, which delivers the high‐rate capacity (66.8 mAh g⁻¹ at 50 C) and long cycle stability (ultra‐low capacity loss of 0.003% every cycle at 10 C) at 25 °C. Furthermore, excellent rate performance (34.0 mAh g⁻¹ at 40 C) and capacity retention (no capacity loss after 2500 cycles at 10 C) at −20 °C are realized.