One-step in situ doping of Sb achieves enhanced performance of [001]-oriented nano-LiFe0.6Mn0.4PO4/C cathode high-rate materials

Abstract

The LiFe0.6Mn0.4PO4/C composite has become a cost-effective and reliable material for lithium battery storage in commercial applications, due to its significant safety benefits. However, its industrial application is limited by its suboptimal high-rate capacity and unsatisfactory cycling performance. To address this issue, Li(Fe0.6Mn0.4)1-xSbxPO4 (x = 0, 0.01, 0.03, 0.04, 0.05) materials were synthesized using a one-step solvothermal method in this study, aiming to modulate the microstructure and achieve Sb doping, thereby enhancing the electrochemical performance. The electrochemical test results indicate that LFMP/C doped with Sb (designated as LFMP/C-Sb0.04) displays exceptional electrochemical performance, with remarkable capacities of 166.6 mAh·g−1 and 146.8 mAh·g−1 at 0.2C and 1C, respectively. Notably, it achieves a capacity of 126.1 mAh·g−1 at a high rate (5C) and maintains an impressive capacity retention rate of 93.6 % after 300 cycles, outperforming the original LMFP/C (109.5 mAh·g−1), which retains only 61.5 % of its initial capacity. Further characterization of the samples reveals that in situ Sb doping promotes the growth of the [001] crystal orientation, enhancing the lithium-ion diffusion rate and effectively reducing electrode polarization and charge transfer resistance, thereby contributing to its exceptional rate performance. Moreover, Sb doping increases the M − O binding energy, strengthens the metal-oxygen framework, mitigates the Jahn-Teller effect caused by Mn3+ dissolution, and enhances its cycling stability.