Synergistic Optimization of LiMn _0.6 Fe _0.4 PO ₄ Cathode Material Structure and Electron/Ion Transport via Trace V‐Ti Co‐Doping to Achieve Electrochemical Performance Enhancement

Abstract Although LiMn _0.6 Fe _0.4 PO ₄ (LMFP) cathode material has garnered significant attention due to its high theoretical capacity and cost‐effectiveness, its commercial application is hindered by issues such as poor ion diffusivity, slow electron transfer rate, and inadequate cycle life. To address these challenges, this work employs a trace V‐Ti co‐doping strategy to modify LMFP and delves into the underlying mechanisms of this modification. Utilizing a co‐precipitation method to prepare Mn _0.6 Fe _0.4 O precursors, followed by solid‐state sintering, V‐Ti co‐doped LMFP samples are synthesized successfully. Test results demonstrate that V and Ti are doped into the Mn/Fe and Li sites of LMFP respectively, optimizing the crystal structure and enhancing Li⁺ diffusion. The V‐Ti co‐doped LMFP exhibits an initial capacity of 154.1 mAh g ⁻¹ at a 1C rate, with a capacity retention rate of 93.81% after 500 cycles significantly enhancing the electrochemical performance of LMFP. Furthermore, dynamic analysis reveals that after V‐Ti co‐doping, the polarization of LMFP is weakened and the electrochemical impedance (67.8 Ω) of LMFP is reduced, enhancing its structural stability and endowing the cathode material with improved conductivity and structural integrity, thereby extending its cycle life. These findings provide a strong theoretical underpinning for developing high‐performance LMFP‐based cathode materials for next‐gen energy storage.